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Resources, Conservation and Recycling 54 (2010) 752–758

Contents lists available at ScienceDirect

Resources, Conservation and Recycling


journal homepage: www.elsevier.com/locate/resconrec

Novel approach for the treatment and recycle of wastewater from soya edible
oil refinery industry—An economic perspective
K. Rajkumar a,b,∗ , M. Muthukumar a , R. Sivakumar b
a
Department of Environmental Sciences, Bharathiar University, Coimbatore 641046, Tamilnadu, India
b
Sakthi Sugars Limited-Soya Division, Pollachi, 642103, Tamilnadu, India

a r t i c l e i n f o a b s t r a c t

Article history: The soya edible oil manufacturing industries with a capacity of 18,000 tones/annum, generate wastew-
Received 20 October 2008 aters and solid wastes. The streams of wastewater originate primarily after several processes viz. soap
Received in revised form splitting, floor washing, cooling tower and boiler. The wastewater from cooling tower, boiler sections and
12 November 2009
solid wastes can be recycled and reused after essential preliminary treatment. In this study, we observed
Accepted 16 December 2009
that wastewater from the site of study and other peripheral streams did not conform to the legislated
permissible limits prescribed for discharge, by the Central Pollution Control Board, Government of India.
Keywords:
Hence, we adopted certain novel measures to enhance the treatment efficacy of the effluent treatment
Cost estimated
Effluent treatment plant
plant (ETP). The overall percentage removal of COD, TDS, and O&G was 94–98, 92–97 and 97–99%, respec-
Edible oil refinery tively. Moreover the fixed capital cost of ETP was estimated 50 lakhs—Indian Rupees (Rs.) and annual
Reuse and recycle operation and maintenance cost was estimated Rs. 10.356 lakhs, the cost of treatment of 1 m3 wastewater
Soybean was Rs. 82.67 (U$ dollar = 1.79). Further recycle, recovery and reuse of water were adopted to achieve the
Solid wastes target of zero discharge for ecological and economical gains.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction ular structures which make them more stable and difficult to be
biodegraded.
Saving water to save the planet earth and to ensure a safe future India has approximately 90 units of edible oil refineries located
for mankind is the ultimate need of the hour. With the growth of in different states. The sources of edible oil are soybean, ground-
mankind, society, science, and technology our world is reaching nut, rapeseed, sunflower, safflower, cotton, sesame, coconut, palm,
to new high horizons but the cost which we are paying or will mustard, rice bran, watermelon, neem, etc. This crude oil is then
pay in near future is surely going to be too high. Environmental refined in order to remove free fatty acids and other non-TAG (tri-
disorder with an increased pollution problem is one of the con- acylglyceride) components which contribute to undesirable flavor,
sequences of this rapid growth. Besides other needs, the demand odor and appearance (Anderson, 1953). Crude oil is refined using
for water (“Water for People Water for Life” United Nations World several processes to remove undesirable components before mak-
Water Development Report UNESCO) has increased tremendously ing it available for human consumption (Dumont and Narine, 2007).
with agricultural, industrial and domestic sectors consuming 70, The refinery process generates by-products produced after crude
22 and 8% of the available fresh water, respectively and this has oil refining. Fig. 1 summarizes the conventional processing steps
resulted in the generation of large amounts of wastewater contain- encountered from crude to refined rapeseed oil. The refining of
ing a number of ‘pollutants’ (Helmer and Hespanhol, 1997; Lehr et crude edible oils generates large amounts of wastewater. The neu-
al., 1980; Nemerrow, 1978). One of the important classes of the pol- tralization step, in particular, produces sodium salts of free fatty
lutants is edible oil refinery process, and once they are discharged acids (“soapstocks”) whose splitting through the use of H2 SO4 gen-
into enter the water bodies it is no longer good and sometimes erates highly acidic and oily wastewater. Its characteristics depend
difficult to treat as the oil refinery wastewater have complex molec- largely on the type of oil processed and on the process implemented
(Azbar and Yonar, 2004). Several successive physical processes are
involved in depollution of such effluents before a final biological
step in a waste treatment station. Oil and grease in oily wastewa-
ter may take various forms namely: free, dispersed and emulsified.
∗ Corresponding author at: Department of Environmental Sciences, Bharathiar
Decantation and skimming are effective in removing free oil
University, Coimbatore 641046, Tamilnadu, India. Tel.: +91 98653 10077.
E-mail addresses: rajkumar env@yahoo.co.in (K. Rajkumar),
(Cheryan and Rajagopalon, 1998). For decades, aerobic treatment
mmuthukumar@yahoo.com (M. Muthukumar), sivakumar@sakthisoyas.com has been used to remove biodegradable organic pollutants present
(R. Sivakumar). in the wastewater generated during various industrial processes.

0921-3449/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2009.12.005
K. Rajkumar et al. / Resources, Conservation and Recycling 54 (2010) 752–758 753

and then discharged directly into soil or ground water. But, due
to the emergence of environmental consciousness, the Pollution
Control Boards have become stricter and impose very stringent
norms. The scarcity of water is also another incentive for recov-
ering pure water from effluents. For the treatment of an effluent
by conventional methods like aerobic or anaerobic digestion, the
ratio of BOD to COD should be >0.6 (Chian and Dewalle, 1977).
However, an effluent from the vegetable oil industry usually has
a BOD/COD ratio around 0.2, which could cause the destruction
of micro-organisms useful for the biodegradation. The combined
wastewater from these sections of the refined edible oil manufac-
turing industry is acidic and contaminated with oil and colloidal
particles. Generally, physico-chemical processes followed by bio-
logical processes are adopted for the treatment of such wastewater.
The physico-chemical processes include air flotation, skimming of
oil, flocculation and coagulation for colloidal pollutants followed
by biological processes for dissolved organics (Pathe et al., 2000;
Saha et al., 1998).
Flotation is a unit operation which is applied to separate solid or
liquid particles from a liquid phase, the dissolved air flotation (DAF)
for the removal of emulsified oils from oily wastewater. A dissolved
air flotation unit has been designed for this purpose and the ulti-
mate goal is to explore the technical viability of this technique. The
design and construction of the dissolved air flotation pilot plant
have been conducted to treat 1.0 m3 h−1 of oily wastewater. Sepa-
ration is achieved by introducing fine gas (with help of compressor
air) bubbles into the liquid phase. Being the bubble attached to the
(oil) particulate matter, and the buoyant force of the combined par-
Fig. 1. Simplified schematic diagram of soybean vegetable oil refining processes. ticle and gas bubbles are great enough to cause the particle to rise to
the surface. Particles that have a higher density than the liquid can
The refined edible oil manufacturing units generate solid waste be facilitated (e.g., oil suspension in water). Once the particles have
(spent earth) and wastewater which are of environmental con- been floated to the surface, they can be collected by a skimming
cern and need proper treatment prior to their disposal (Pandey et operation (Rajkumar, 2006).
al., 2003). In a vegetable oil industry, the effluent mainly comes The refinery uses chemical and physical methods for the
from the degumming, deacidification, neutralization, bleaching, refining of oils (soybean). The entire process involved is sum-
and deodorization steps, etc. (Kale et al., 1999). The blow-down marized in Fig. 1. On an average, the refinery and other process
of the boiler and wash water from de-oiling of the bleaching earth generate around 200 m3 of wastewater daily, which includes
also contribute to the effluent in small amounts. Previously, effluent acid wastewater (60–80 m3 /day) and technological wastewater
from a vegetable oil industry used to undergo primary treatment (90–120 m3 /day). In view of the present emphasis placed on envi-

Fig. 2. Simplified schematic diagram of the treatment system for the vegetable oil refinery wastewater.
754 K. Rajkumar et al. / Resources, Conservation and Recycling 54 (2010) 752–758

ronmental pollution control, new legislations and regulations, and Table 1


Specific raw material requirements in the edible oil refinery.
changes in economic factors, the company installed a physico-
chemical and biological wastewater treatment plant. The process Ingredients Magnitude for the production of refined
flow diagram with sources of wastewater discharged is shown soya edible oils (tones/month)
in Fig. 2. The Principle parameters of concern are pH, oil and Edible oil 1500.00
grease (solvent extractable), suspended solids and organic con- Bleaching earth 51.64
stituents expressed as 5-day biochemical oxygen demand (BOD5 ) Sulphuric acid 40.10
Caustic 15.00
and chemical oxygen demand (COD). Other wastewater compo-
Phosphoric acid 2.05
nents of concern are sulphates, phosphates and chlorides. The Total products (tones/month) 1175.20
wastewater treatment plant, like any other, is to reduce the pollu-
tion level prior to discharge to the environment to avoid breaking
the eco-balance.
such as pH, TDS, COD ect. were monitored at inlet and outlet. All
The high costs associated with the plant and its operation
the samples were analyzed using analytical grade chemicals and all
require a wise optimization of the process. A typical ETP is usually
the analyses were performed in accordance with adopting standard
defined by a primary treatment, a secondary treatment and in some
methods (APHA, 1995).
cases a tertiary treatment. The primary treatment is a physical pro-
cess which aims to eliminate the gross solids and grease, so avoiding
the blocking up of the secondary treatment. As its cost does not 3. Results and discussion
depend Considerablly on the characteristics of the wastewater, we
chose not to include it in the optimization procedure. The sec- 3.1. Process details
ondary treatment is a biological process and is the most important
treatment in the plant because it eliminates the soluble pollu- The specific raw material requirement and process details with
tants. Major opportunities for wastewater reuse exist in industry respect to manufacture of refined edible oil are presented in Table 1.
because most water is used for processing activities (washing, rins- In short, soya edible oils are individually pre-refined with caustic
ing, etc.). In recent years various systematic design approaches to soda to remove free fatty acid (FFA) and with citric acid or phos-
wastewater reuse across complex manufacturing operations have phoric acid to remove gummy matters. The oils are then bleached
been developed (Wang and Smith, 1994; El-Halwagi, 1997; Kuo with bleaching earth to remove the colour and residual matter.
and Smith, 1998; Almato et al., 1999; Dunn and Wenzel, 2001). The main wastewater generating sources are from vat house
Because economic benefits are undoubtedly a major driver for after soap splitting (60 m3 /day), floor washing (10 m3 /day) and
industry to implement wastewater reuse programs, recent research domestic use (5 m3 /day). The vat house drain carries the major
in this area has focused on the economic optimization of wastewa- portion of the wastewater, which is acidic in nature. The pooled
ter reuse systems (Hallale and Fraser, 1998; Jodicke et al., 2001; wastewater from the industrial unit is also by and large acidic. The
Parthasarathy, 2001; Koppol et al., 2003). Bruggen and Braeken pH of the raw wastewater from the process and floor washing is
(2006) cited suggest that reusing wastewater streams as an input acidic in nature and is yellowish in colour. The COD of the pro-
for less demanding installations is a step towards a zero discharge cess wastewater was 17000 mg/l with total dissolved solid (TDS)
system. concentration of 6520 mg/l. The wastewater had fatty substances
Hence, we aimed to characterize the wastes generated from soya in dispersed and non-dispersed forms respectively and it also con-
edible oil refinery and the objective of this study was to evaluate tained high levels of oil and grease resulting in high COD as evident
the physico-chemical treatment process removal of the mentioned from the results presented in Table 2.
parameters and to assess the biodegradability of the wastewater
and also to recycle and reuse the waste for economic profits. 3.2. Generation of solid wastes and their characteristics

Major sources of solid waste generation in the edible oil refin-


2. Materials and methods ery were from bleaching unit and the ETP. The magnitude of spent
bleaching earth generated from bleaching section ranged from 400
2.1. Waste samples to 500 kg/day, the quantity of chemical and biological sludge from
clariflocculator and secondary clarifier of the ETP ranged from 25
Wastewater samples from vat house, soap splitting, solvent to 50 kg/day and from 100 to 200 kg/day, dry basis respectively.
extraction, floor washing, boiler and cooling system were collected The chemical lime sludge generated from clariflocculator in the
together as received finally by the ETP through a single drain. Sam- industry was grey to grayish white in colour and alkaline in nature.
ples of solid waste (spent earth) were also collected. The parameters The characteristics of biological sludge generated from the ETP are

Table 2
Characteristics of the wastewater generated at soya edible oil refinery.

Parameter Influent Final Standard for treated effluent for inland water discharge (MoEF)

Colour Yellowish Colourless

Temperature, (◦ C) 45 32 Should not exceed 5 ◦ C above the receiving water temperature

pH 4.2 7.4 5.5–9.0


Total suspended solids (mg/l) 450 42 100
Total dissolved solids (mg/l) 6250 260 2100
Oil and grease (mg/l) 1550 ND 10
BOD5 (20 ◦ C) (mg/l) 4340 10 30
COD (mg/l) 17000 40 250
Sulphide (mg/l) 2.6 ND 2
Sulphate (mg/l) 1.2 ND –

MoEF, Ministry of Environment and Forest, Government of India, New Delhi; ND, not detectable.
K. Rajkumar et al. / Resources, Conservation and Recycling 54 (2010) 752–758 755

Table 3 3.4. ETP unit performance


Physico-chemical characteristics of chemical sludge from clariflocculator and bio-
logical sludge from secondary clarifier at ETP.
The wastewater generated by the industry was optimally equal-
Parameter Chemical sludge Biological sludge ized in a basin. The floated oil was skimmed out manually and
Appearance Gray Brownish black reused in the process. After removal of oil, the wastewater was
Odor Odorless Odorless pumped into lime unit for neutralization at a constant flow rate of
pH 9.5 7.2 2.7 m3 h−1 over a period of 24 h. The neutralized wastewater was
Moisture (%) 28.2 19.2
subjected to biological treatment in aeration basin units of the ETP.
Organic matter (%) 25.1 74.5
Inorganic matter (%) 74.6 24.2 The COD of the influent to the ETP was 17000 mg/l, while the value
Oil and grease (mg/g) 17.5 1.0 of COD in the treated effluent was 40 mg/l. The BOD in the inlet of
Total nitrogen (mg/g) 13.1 147.0 the ETP was 4340 mg/l, while the treated effluent contained BOD
Total phosphate (mg/g) 11.3 63.2
with a mean value of 10 mg/l. Thus, the removal efficiency of the
Potassium (mg/g) 1.64 34.2
COD and BOD in the ETP was 99.76 and 99.77%, respectively. The oil
and grease be removed to the levels below detection limit of less
than 1.0 mg/l (Table 2).
also presented in Table 3. The biological sludge was rich in carbon,
nitrogen and phosphorous.
3.5. Operational costs of aeration system

3.3. Details of the ETP units operation


The biological treatment system has two surface aerators (each
25 hp, 1 horsepower hour = 0.746 kWh−1 ). The energy consumption
The ETP comprises of the following units, viz. equalization
of aerators 37.3 kW h−1 , the activated sludge process most efficient
basin, neutralization unit, clariflocculator, primary clarifier, aer-
technology for the removal of pollutants depends on the nature
ation basin and secondary clarifier. The schematics of the ETP
of the pollutant and, usually, ETP required the physical chemical
along with dimensions are depicted in Fig. 2. The wastewater is
and biological treatment at lowest cost. However, the cost of the
first pumped into an equalization basin, where the floating oil is
treatment terms of electrical units (kWh m−3 ). In the case of ETP,
skimmed out. The wastewater is neutralized with addition of lime
the estimation of the price per unit (oxygen added), as the aeration
(15 kg/day) and is pumped to a clariflocculator where alum is added
is directly related to the specific energy consumption of aerators
at a rate of 5 kg/day. The addition of alum results in fast formation
(kWh m−3 ), tank volume 100 m3 and the energy consumption can
of lime sludge then passed through DAF, where the floating oil and
be obtained from this value by using Eq. (1), Once the energy con-
soap are skimmed out. The overflow of supernatant from the DAF is
sumption has been calculated, the price of the power unit permits
supplemented with diammonium phosphate (4.0 kg/day) and urea
the price of the oxygen transfer dose to be calculated:
(2.0 kg/day) as a nutrient and let into aeration basin for biological
treatment. The surface aerators are provided in aeration basins for (HP) (0.746 kW/hp) (DAY)
power (W) =
oxygen transfer and mixing of biomass with wastewater. The over- motor efficiency (0.9)
flow from aeration basin passes through a secondary clarifier. The
= 994.66 kWh m−3 /day (1)
settled sludge from secondary clarifier is partly re-circulated (acti-
vated sludge process) to aeration basin in order to maintain mixed
liquid suspended solid (MLSS) a proper food/micro-organism (F/M) The costs incurred for electricity are highly dependent on the
ratio and the excess activated sludge produced in the process is particular country. The electricity cost for industrial use in India
taken to the (sand filter) sludge bed. is around Rs. 4.50 kW h−1 (1 U$ dollar = Rs. 46). The aeration sys-

Table 4
Cost estimation summary (2009).

Item Estimated cost

Indian Rupees (Rs.) U$ dollar

(A) Total fixed capital cost


Process equipment cost 2,500,000.00 54347.82
Equipment erection 100,000.00 2173.91
Piping and insulation 100,000.00 2173.91
Instrument and control 800,000.00 17391.30
Site preparation 1,300,000.00 28260.86
Engineering and procurement 50,000.00 1086.95
Contingency 50,000.00 1086.95
Total fixed capital cost 5,000,000.00 108695.65

(B) Annual operation and maintenance cost


Aluminum sulphate 33,400.00 726.08
Lime 79,700.00 1732.60
Hydrochloric acid 6000.00 130.43
Caustic 46,500.00 1010.86
Urea 5700.00 123.91
DAP 22,200.00 482.60
Electricity (kW) 196,500.00 4271.73
Analysis 30,000.00 652.17
Labors 396,000.00 8608.69
Safety materials 7800.00 169.56
Plant maintainers 12,000.00 260.86
Total annual cost 1,035,600.00 22513.04

(C) Treatment cost per cubic meter of wastewater 82.67 1.79


756 K. Rajkumar et al. / Resources, Conservation and Recycling 54 (2010) 752–758

Fig. 3. Cost breakdown in term of percentage for the (a) total fixed capital cost, (b) annual operation and maintenance and (c) treatment cost per cubic meter of wastewater.

tem, and power required to achieve an arbitrarily selected 98% COD 3.6.2. Soap stock
removal level for the pollutants studied in this work are shown in The degumming step is not always necessary prior to chemical
Table 4. The nature of the pollutant strongly influences the power refining. The best known and the most widely used chemical refin-
requirements, with the ratio between the aeration and the power ing process is the caustic soda process. Phosphoric acid is added to
required to be in the range 2.5 kg equivalent O2 /kWh. On the basis the crude oil in order to precipitate the phospholipids; this is fol-
of this information, an average operational cost in the range Rs. lowed by the addition of an alkaline solution. The alkaline solution
44.74 kg−1 ($—0.97) equivalent O2 was assumed (Rajkumar and neutralizes the free fatty acids Eq. (2) and any excess phosphoric
Muthukumar, 2009). acid Eq. (3). Reaction of the alkaline solution with fatty acids leads to
the formation of soap. The soap stock created is then continuously
separated from crude oil by centrifugation (O’Brien, 2004):
3.6. Recovery, recycle and reuse of the wastes treatment
RCOOH + NaOH → RCOONa (2)
Generally, the soya edible oil manufacturing units practice
recovery of lecithin, soap stock and spent earth as by-products for H3 PO + 3NaOH → Na3 PO4 (3)
reuse.
Soap stock is defined as a by-product, which results from the
alkali-refining of the edible oil, otherwise treated as waste. The
3.6.1. Lecithin basic reaction in alkali-refining is given in Eq. (4) below:
Lecithin is derived from the degummed edible oil and it is one
of the important ingredients of phosphatides. Soy lecithin con- C3 H5 (O2 CR)3 + 3NaOH → 3RCO2 Na + C3 H5 (OH)3 (4)
fat alkali sodium soap glycerol
sists of three types of phospholipids; phosphatidylcholine (PC),
phosphatidylethanolamine (PE) and phosphatidylinositol (PI). It The soap stock is produced during the refining of edible oil. The
is extracted from soybean oil and is generally used as a natu- soap stock contains 50% total fatty matter and, therefore, it has a
ral emulsifier or stabilizer in various food applications. Lecithin commercial value. The soap stock produced in the industry is sold
is a combination of naturally occurring phospholipids, which are directly to the soap manufacturers (Pandey et al., 2003).
extracted during the processing of soybean oil. Soybean oil is
extracted from the flakes through a distillation process and lecithin 3.6.3. Spent earth
is separated from the oil by the addition of water and centrifugation Spent bleaching earth (SBE) is an industrial waste generated at
or steam precipitation. the vegetable oil refining industry after the colouration (bleaching)
Soy lecithin offers a multifunctional, flexible and versatile tool. of crude oil. The annual world generation of SBE is between 1.5 and
It is probably best known for its emulsifying properties, which help 2.0 million tones based on the world edible oil production of 128.2
promote solidity in margarine and give consistent texture to dress- million metric tones in 2007 (Soystats, 2007) and 1.2–1.6 kg of SBE
ings and other creamy products. Lecithin is also used in chocolates generation per metric ton of edible oil production. SBE contains
and coatings to counteract spattering during frying. Additionally, 20–40% by weight of oil, fat and coloured pigments (Werner, 1994)
its unique lipid molecular structure makes lecithin useful for phar- and may present a fire hazard, if it is not stored or disposed properly
maceutical and cosmetic applications and various industrial uses (Taylor and Jenkins, 1999). Waste minimisation is an umbrella term
such as paints, textiles, lubricants and waxes. used to denote any process which results in a reduction of the waste
K. Rajkumar et al. / Resources, Conservation and Recycling 54 (2010) 752–758 757

stream prior to treatment or disposal (Patterson, 1989). Source of applying a range of onsite wastewater treatment techniques to
reduction, waste recovery, reuse, and recycling are examples of meet legislative standards and discharge into inland surface water.
waste minimisation strategies. The reuse of SBE and the concomi- The optimal design and operation, in terms of installation and
tant recovery of residual oil has been a recurrent focus of research operation cost, of ETP from our numerical experiences, we may con-
within the edible oil industry for nearly 50 years. Clay regenera- clude that the efficiency of the treatment influences directly and the
tion has been attempted by steam (Penninger, 1979). However, the estimate way the resulting cost of the effluent treatment plant. The
industry was suggested to reuse spent earth as substitute of coal in economic evaluation for 200 m3 /day treatment plant concluded
the boiler plant. that the fixed capital cost was Rs. 50 lakhs (U$ dollar = 108,695.65),
operation and maintenance cost was estimated Rs. 10.356 lakhs (U$
3.6.4. Wastewater dollar = 22,513.04), and the cost of treatment of 1 m3 wastewater
It was suggested, and also practiced to reuse and recycle the was Rs. 82.67 (U$ dollar = 1.79) (1 U$ dollar = Rs. 46). However, the
acidic wastewater from soap splitting tank for soap splitting. Recy- most effective approach to pollution control is one that emphasizes
cling of the cleaning water through collection tank was adopted process development to minimise losses at the source, reuse and
for reusing in the manufacturing process. The recycling of process recycle.
cooling water was adopted in bleaching, deodourizer, and green
development. Acknowledgements

3.6.5. Lime sludge The authors are thankful to Dr. N. Mahalingam, Chairman of
Lime sludge generated during the process after dewatering of Sakthi Group of Companies, Sri M. Manickam, Vice Chairman and
producing wastewater is a product that has beneficial reuses. Lime Managing Director, Sakthi Sugars Limited and Mr. M. Ponnuswami,
sludge has beneficial reuse via agricultural land application, mixing Senior President of Sakthi Sugars Limited, Tamilnadu, India.
with compost, or other application. If it is demonstrated that these
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