International Journal of Engineering & Technology, 7 (4.

5) (2018) 552-555

International Journal of Engineering & Technology

Website: www.sciencepubco.com/index.php/IJET

Research paper

Estimation of properties of mixed waste cooking oil for

production of biodiesel
B. S. V. S. R. Krishna 1 *, Shivaraj B. K.1
1 Professor, Department of Chemical Engineering
2M Tech, Chemical Engineering MIT, MAHE, MANIPAL-576104
*Corresponding author E-mail: [email protected]

Abstract

The major drawback of production of biodiesel in large scale is the cost of raw materials. Raw material source of biodiesel is mostly plant
oil (Jatropha, Pongamia, Mahua, Neem, Cotton seed oil etc.) which requires large land area to grow. One of the best methods to reduce the
production cost of biodiesel is to employ low quality feedstock, for instance waste cooking oil (WCO). This also solves the disposal
problem of WCO. This is socioeconomic and environment friendly, it does not compete with edible oil resources. This study represents
the biodiesel production from mixed waste cooking oil. Waste cooking oil collected from different hotels around Manipal, Udupi district
of Karnataka State, and India. Collected WCO from various sources (from palm oil and sunflower oil users) have different physical and
chemical properties. These WCO has mixed in different ratios ie. 50:50, 75:25 and 25:75 to reduce free fatty acid content of WCO without
any chemical pre-treatment. Physio-chemical properties of mixed WCO has been carried out.

Keywords: Waste Cooking Oil (WCO); Free Fatty Acid (FFA); Low Quality Feed Stock; Biodiesel.

used in blends and also increases engine life due to its superior lu-
1. Introduction bricity over petrodiesel. Usage of biodiesel will allow a balance to
be sought between agriculture, economic development and the en-
Raising uncertainty about global energy production and supply, en- vironment.
vironmental concerns due to the use of fossil fuels and the high & Biodiesel produced from fresh vegetable oils costs much more than
uncertain price of petroleum based products are the main rea-sons diesel, this is a major drawback to the commercialization of bio-
for invention of alternatives to petroleum based products. The diesel in the market. Therefore, it is necessary to find the ways to
global supply of oil and natural gas from the conventional sources minimize the total production cost of biodiesel. In this context,
is improbable to meet the growth in energy demand over the next methods that can reduce the costs of raw materials as well as the
25 years [1]. One of the main driving force for biodiesel wide- energy consumption are of special concern. The use of waste cook-
spread is the emission of greenhouse gases (CO2 being the major ing oils (WCO) is one of attractive options to reduce the raw mate-
one). The use of waste cooking oil as biodiesel feedstock reduces rial cost. Moreover, many harmful compounds are produced during
the cost of biodiesel production since the feedstock costs consti- the frying of vegetable oils, therefore EU banned the use of waste
tutes approximately 70-95% of the overall cost of biodiesel pro- cooking oils in the composition of animal feed in 2002. Most of the
duction [2], [3]. Hence, the use of waste cooking oils and non-edible toxic compounds in the waste cooking oil are oxida-tion products
oils should be given higher priority over the edible oils as biodiesel from fatty acids, especially from polyunsaturated fatty acids [6],
feedstock to protect the food safety. [7].
Moreover, biodiesel fuel has become more attractive because of its Chemically the oils/fats consist of triglyceride molecules of three
environmental benefits, due to the fact that plants and vegetable oils long chain fatty acids that are ester bonded to a single glycerol mol-
and animal fats are renewable biomass sources [1]. Biodiesel rep- ecule. Because different fatty acids have different physical and
resents a largely closed carbon dioxide cycle (approximately 78%), chemical properties, the fatty acid profile is probably the most im-
as it is derived from renewable biomass sources. Compared to pe- portant parameter influencing the corresponding properties of a
troleum diesel, biodiesel has lower emission of pollutants; it is bio- vegetable oil or animal fat. Thus, biodiesel refers to lower alkyl es-
degradable, nontoxic, has carbon neutrality, it enhances the engine ters of long chain fatty acids, which are synthesized either by trans-
lubricity and contributes to sustainability [4-5]. Biodiesel has a esterification with lower alcohols or by esterification of fatty acids.
higher cetane number than diesel, and no aromatics, no sulfur; sec- Low-grade oil, typically waste cooking oil can be a better alterna-
ondly, it contains 10–11% oxygen by weight [2]. tive; however, the high free fatty acids (FFA) content in waste cook-
According to ASTM D6751, biodiesel is composed of mono-alkyl ing oil has become the main drawback for this potential feedstock.
esters of long-chain fatty acids derived from plant oils or animal Waste cooking oil (WCO) as biodiesel feedstock
fats. Biodiesel is chiefly made by transesterification of oils or by Huge quantities of waste cooking oils and animal fats are available
esterification of free fatty acids with alcohols. Biodiesel is a suita- across the world, especially in the developed and developing coun-
ble outlet for the big hotels and restaurants and vegetable oil in- tries. Such oils and fats set a significant challenge because of their
dustry requiring little or no changes in current diesel engines when disposal problems and possible contamination of the water and land
resources. Even though some of this waste cooking oil is used for
Copyright © 2018 B. S. V. S. R. Krishna, Shivaraj B. K. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
 International Journal of Engineering & Technology 553

soap production, a major part of WCO’s are discharged into the en- Freedman and Pryde (1982) [12] reported that the oil should not
vironment. According to a study performed in USA, 40% of the contain more than 1% FFA for alkaline–catalyzed transesterifica-
sewerage system blockages are caused by the waste frying oils tion reactions. If the FFA level exceeds this amount, the formation
poured into kitchen sink [8]. Moreover, waste frying oils have eco- of soap will inhibit the separation of the ester from the glycerin and
toxic properties. If they are spilled onto ground, they will contami- also reduce the ester conversion rate.
nate the soil and so damage plants. Waste cooking oil, which is oth- FFA content in oil feedstock should be as low as possible (ranging
erwise wasted, is one of the most economical choices to produce from less than 0.5 wt. % to less than 2 wt. %) for base-catalyzed
biodiesel. Since one of the major concerns on biodiesel production transesterification reaction. Thus, if waste cooking oil with an av-
is the price of feedstock, utilization of waste cooking oil signifi- erage FFA content more than 6 wt. %, base catalyst is definitely not
cantly enhances the economic viability of biodiesel pro-duction. suitable to be used (Lotero et al., 2005) [9]. If FFA of waste cooking
The following table provides the major producers of WCO, which oil is more than 1 wt%, then it should be treated prior to transester-
can be converted to biodiesel. ification reaction to reduce FFA level less than 1 wt %. So many
Biodiesel is commonly produced using homogeneous alkaline cat- methods are available to reduce FFA value including acid catalyzed
alyst, such as sodium hydroxide (NaOH) or potassium hydrox-ide reaction, two step acid-base catalyzed reaction, acid esterification,
(KOH). These catalysts are very commonly used in the indus-tries esterification with methanol, esterification with glycerol and utili-
due to following reasons: (i) Operates at low reaction temper-ature zation of acid heterogeneous catalysts, utilization of adsorbents to
and atmospheric pressure; (ii) High conversion can be achieved in reduce FFA. All these methods require high cost and energy re-
a minimal time, (iii) Widely available and more eco-nomical quirement. This leads to the increase in production of biodiesel.
(Lotero et al., 2005) [9]. In fact, it was reported that the transester- Best method to reduce the FFA of WCO is mixing of high FFA
ification reaction rate for base-catalyzed reaction would be 4000 value WCO with low FFA value oil in different ratios. This method
times faster compared to acidic catalyst (Fukuda et al., 2001 [9], significantly reduces the FFA of oil, without using any chemicals.
Kulkarni and Dalai, 2006 [7]. The main objective of this study was characterisation of waste
cooking oil and mixed waste cooking oil, reduction of FFAs of col-
Table 1: Quantity of Waste Cooking Oil Produced In Selected Countries lected waste cooking oil without any chemical treatment, just by
(Gui Et Al. 2008) [11] mixing the waste cooking oil in different ratios for biodiesel pro-
Country Quantity (million tonnes/year) duction.
India 9.2
China 4.5
European 0.7–1.0 3. Experimental
Canada 0.12
Taiwan 0.07
United States 10.0 3.1. Materials
Malaysia 0.5
Japan 0.45–0.57 Different waste cooking oils were obtained from the various ho-tels
around Manipal, Udupi district, India. A total of 10 kg of waste
cooking oil was collected for the optimization of the bio-diesel pro-
2. Literature survey duction process. The oil collected in two containers, specific pref-
erence is given for collection process such way that in container one
Freedman and Pryde (1982) [12] investigated the effects of reac- for sunflower oil and container two for palm oil.
tion variables on transesterification using sunflower and soybean
oils. They studied different molar ratios of alcohol to oil, alcohol 3.2. Pre-treatment of waste cooking oil
types, catalyst types, and reaction temperature. In that study, ester
conversions of 90 to 97% were obtained by using alcohol to oil mo- The frying process often introduces food particles to the oil, and the
lar ratios of 4:1 and 6:1, respectively, with an alkaline catalyst. They oil must be filtered before undergoing the transesterification reac-
have used two catalysts (sodium hydroxide and sodium methoxide) tion. The collected waste cooking oil was filtered through normal
at 6:1 and 3:1 molar ratios and found that sodium methoxide (0.5%) sieve to remove food debris and unwanted solids. In addi-tion to
was more effective than sodium hydroxide (1%) at the 3:1 molar food particles, foods introduce water to the fryer oil. It was heated
ratio. At the 6:1 molar ratio, the catalysts were equally effective. to around 100 ºC to evaporate the possible water content present in
Muniyappa et al. [13] studied transesterification yield of soybean oil. The pretreated waste cooking oil was named as sample no 01
oil. Sodium hydroxide was used as a catalyst and its effect was in- and 05
vestigated by changing its concentration from 0.5 to 0.05% in a 30:1
molar ratio of methanol to soybean oil. All reactions were run at 3.3. Mixing of waste cooking oil
about 68-70°C, with a 90-minute reaction time, and with soy-bean
oil having an acid value less than 0.05 mg KOH/g. They found that Treated waste cooking oils were mixed in 50:50, 75:25 and 25:75
98% conversion could be obtained with 0.1% catalyst after only 5- ratios.
10 minutes of reaction time. a) 500 ml of sample 01 (sunflower oil) and 500ml of sample 02
The primary parameters relevant to biodiesel production by trans- (palm oil) taken in a beaker, stirred it at 600 rpm and temper-
esterification of WCO by alcohol using a base catalyst are the FFA ature was maintained at 85 ºC to mix properly and named it
content and moisture content. The FFA content of WCO will vary as sample 03.
and depends on the quality of the feed stock. Another tech-nique to b) 750 ml of sample 01 (sunflower oil) and 250 ml of sam-ple
increase the biodiesel yield is acid catalyst based esterifi-cation; 02 (palm oil) taken in a beaker, stirred it at 600RPM and tem-
however, it is much slower than the alkali catalyst based transester- perature was maintained at 85 ºC to mix properly and named
ification. it as sample 04.
Freedman and co-workers (1984) [14] compared the transesterifi- c) 250 ml of sample 01 (sunflower oil) and 750ml of sample 02
cation of crude and refined cottonseed, peanut, soybean, and sun- (palm oil) taken in a beaker, stirred it at 600RPM and tem-
flower oils. They noted that the free fatty acid level is higher in perature was maintained at 70ºC to mix properly and named
crude vegetable oils than in refined oils. The ester conversions de- it as sample 05.
creased from 95% to 67%, 98% to 83%, 93% to 84%, 97% to 81%,
for peanut, soybean, cottonseed, and sunflower oil, respec-tively, 3.4. Characterization of waste cooking oil
when crude oils were used. In that research, it was stressed that the
yields of ester were reduced significantly when the acid value was The quality of oil is expressed in terms of the physiochemical prop-
higher than 1 mg KOH/g. erties such as moisture, acid value, saponification value, io-dine
 554 International Journal of Engineering & Technology

value, unsaponified matter, peroxide value, density, specific grav-

ity, viscosity. All physiochemical properties of the waste cooking
oil were conducted according to the standard AOCS methods [15].

3.5. Transesterification reaction procedure

A laboratory scale reactor in the form of a 2000 ml three-neck round

bottom flask equipped with a reflux condenser was used for the
transesterification reactions. Out of three necks, in one neck spiral
condenser was fixed, in second thermometer was fixed, and other
neck was used to put the raw oil inside the reactor as well. The re-
actor was placed in a heating mantle equipped with a stirrer and Fig. 3: Variation of Acid Value with Sample.
temperature controller. The stirrer speed was set at 600 rpm.

Fig. 4: Variation of FFA with Sample.

Fig. 1: Experimental Setup.

4. Results and discussion

4.1. Characterization of waste cooking oil

The following Physio-chemical properties of mixed oil were char-

acterized.
i) Moisture content
ii) Specific gravity
iii) Viscosity Fig. 5: Variation of Saponification Value with Samples.
iv) Acid value and free fatty acid content
v) Saponification value Table 2: Physiochemical Properties of Waste Cooking Oil Samples
vi) Iodine value Oil samples name/ sample
vii) Peroxide value
Oil properties
viii) Unsaponifiable matter
1 2 3 4 5
The variation of Moisture content with sample is presented in Fig
2. The moisture content in sample 4 is comparatively less than other Moisture content
samples. Similarly the Acid value of the waste mixed cook-ing oil, 0.11 0.14 0.125 0.118 0.136
(%)
FFA and Unsaponification values are presented in Figs 3 to 5. One
Specific gravity 0.886 0.969 0.918 0.897 0.947
can observe that the sample 4 shows relatively low acid value, low Viscosity (cSt) 31.46 47.51 41.11 37.22 43.66
FFA and low saponification relatively with other mixed cooking Acid value
oils. The Physiochemical properties of waste mixed cook-ing oil 1.28 8.19 2.735 1.6 5.82
samples along with waste cooking oils are presented in Table 2. (mg KOH/gm)
FFA (%) 0.64 4.09 1.36 0.82 2.192
Saponification
value
121.6 187.4 150.2 133.0 173.1
(mg of KOH/g of
oil)
Molecular weight 1398 937 1142 1280 1005
Iodine number 78.50 43.18 57.99 66.8 50.8
Unsaponificable
0.18 0.98 0.36 0.28 0.64
matter (%) w/w
Peroxide value
16 36 20 26 32
(meq/kg)

Fig. 2: Variation of Moisture with Samples. From the table 2 the FFA% is more with sample 2 while the sam-
ple 1 and 5 are very close to FFA of 1%, which is desirable for
experimentation. Sample 1 is raw WCO while Sample 5 is mixed
MCO, present research was selected sample 5 of MCO [16].

4.2. Preparation of biodiesel

 International Journal of Engineering & Technology 555

50 gm of waste cooking oil sample 05 has taken in three necks Acknowledgements

round bottom flask and pre-heated oil at 60 ºC. Calculated amount
of KOH and known quantity of methanol taken in conical flask.
The authors would like to thank the KSCST for the financial sup-
Heated the mixture to prepare methanolic KOH and added to the
port extended.
treated WCO in a round bottom three necked. Started the reaction,
set the required rpm and allowed it for required time at required
temperature. After completion of the reaction, reacted mixture was References
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Fig. 6: Influence of Catalyst Concentration on Biodiesel Production.

5. Results and discussion

The waste cooking oils are good raw materials for biodiesel pro-
duction as this can solve dual problems of disposal of waste cook-
ing oils into water bodies and otherwise reduces the raw material
cost of the biodiesel. The collected raw materials properties ana-
lysed and presented to choose the suitable mixed cooking oil for the
production of biodiesel. Sample 4 shows better results in terms of
physiochemical properties and yield of biodiesel.