BIODIESEL PRODUCTION FROM WASTE SUNFLOWER COOKING OIL AS AN ENVIRONMENTAL RECYCLING PROCESS AND RENEWABLE ENERGY Abstract

HOSSAIN, A.B.M.S. and A.N. BOYCE, 2009. Biodiesel production from waste sunflower cooking oil as an environmental recycling process and renewable energy. Bulg. J. Agric. Sci., 15: 312-317
Comparison of the optimum conditions of alkaline-catalyzed transesterification process for biodiesel produc-tion from pure sunflower cooking oil (PSCO) and waste sunflower cooking oil (WSCO) through transesterification process using alkaline catalysts was studied. To obtain a high quality biodiesel fuel that comply the specification of standard methods (ASTM D 6751 & EN 14214), some important variables such as volumetric ratio, types of reactants and catalytic activities were selected. The highest approximately 99.5% biodiesel yield acquired under optimum conditions of 1:6 volumetric oil-to-methanol ratio, 1% KOH catalyst at 40C reaction temperature and 320 rpm stirring speed. Result showed that the biodiesel production from PSCO and WSCO exhibited no consid-erable differences. The research demonstrated that biodiesel obtained under optimum conditions from PSCO & WSCO was of good quality and could be used as a diesel fuel which considered as renewable energy and environmental recycling process from waste oil after frying.

Key words: Biodiesel, Transesterification, Sunflower oil, Waste cooking oil

Introduction
Biodiesel is advised for use as an alternative fuel for conventional petroleum-based diesel chiefly be-cause it is a renewable, domestic resource with an environmentally friendly emission profile and is readily biodegradable (Zhang et al., 2003) . The amount of greenhouse gas emissions, generating energy from renewable resources is being possessed a high prior-ity gradually to decrease both over-reliance on im-ported fossil fuels (Blanco-Canqui and Lal, 2007). In accordance with the US Standard Specification for
E-mail: sharif@um.edu.my

Biodiesel (ASTM 6751), biodiesel is defined as a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats (Vicente et al., 2007) . It has similar physico-chemical proper-ties of conventional fossil fuel and can consequently, entirely or partially substitute fossil diesel fuel in com-pression ignition engines (Pasqualinoa, 2006).

The high viscosity and poor volatility are the major limitations of vegetable oils for their utilization s fuel in diesel engines. Because high viscous vegetable oils deteriorate the atomization, evaporation and air-fuel mixture formation characteristics leading to improper

Biodiesel Production from Waste Sunflower Cooking Oil as an Environmental

combusti on and higher smoke emission. Moreove r this high viscosity generates operation al problems like difficulty in engine starting, unreliabl e ignition and deterioration in thermal efficienc y. Converti ng to biodiesel is one of the options to reduce the viscosity of vegetable oils (Paugazh abadivu et al., 2005). The current feed

stocks of producti on of biodiesel or monoalkyl ester are vegetabl e oil, animal ft and micro algal oil. In the midst of them, vegetabl e oil is currently being used as a sustainab le commerc ial feedstock. Among more than 350 identifie d oilbearing crops, only sunflowe r, safflower , soybean, cottonsee d, rapeseed, and peanut oils are consider

ed as potential alternativ e fuels for diesel engines (Demirb as, 2006). Sunflow er (Heliant hus annus) is one of the leading oilseed crops cultivate d for the producti on of oil mainly used for human consump tion and can also been considered as an importan t crop for biodiesel producti on (Niotou et al., 2008). Among them, vegetabl e oils are now being used as a sustainab le commerc ial feed-

stock. Paradoxi cally, the higher cost of solid vegetabl e oil affects the producti on cost of biodiesel . However , large amount of waste cooking oil is produced from restauran ts, eatering establish ments and food industries, etc, every year. Having probabili ty of contaminating environ mental water, discardin g of this waste cooking oil can be challengi ng (Hubera et al., 2007).

One possible solution and simultan eously generate economi cal profit. The most studied process to obtain biodiesel from feed stocks is transeste rification of triglyceri des with low molecula r weight alcohols catalyzed by homogenous catalysts (Aranda et al., 2007). Apply of base catalysts may cause problems due to the side saponification reaction which creates soap and consume

s catalyst. These problems occur because of higher content of fatty acids and water in used cooking oil (Issariya kul et al., 2007). Notwiths tanding these drawbacks, transeste rification process using base catalyst has some benefits like low producti on cost, faster reaction speed and mild reaction condition s (Aranda et al., 2007). Recent researche s have concentr ated on heteroge neous catalysts

for decrease of the processing costs related to homogen eous calcium carbonat e

rock, EST-4 and EST-1 catalysts and Na/NaO H/Al2O3 (Trakarn pruk and Porntan gjitlikit, 2008). The first objectiv e of this study aims to compare the optimum conditio ns of fatty acid methyl ester (FAME) or biodiesel producti on from pure and waste sunflow er oil through transeste rificatio n process using alkaline catalyst. In this work, the quality of

biodiesel from both solid and used edible palm oil has been also analyzed and compare d.

Mater ials and Metho ds

Mat erial s
Pure Sunflow er cooking oil (PSCO) was purchased from local grocery shop. The waste cooking sunflow er oil (WSCO) was obtained from restaura nts next to Universi ty of Malaya campus.

To remove impurities the WSCOs were filtered under vacuum pressure (11 bar) Potassiu m hydroxid e, sodium hydroxide, magnesi um sulfate anhydro us, methano l, ethanol was purchase d from SYSTE RM/ Classic Chemica ls Sdn Bhd, Malaysi a.

Tra nses terifi catio n reac tion

The transeste rificatio n reaction perform

ed at different volumetr ic ratio of oil to methano l, varying from 4:1, 3:1, 1:3, 1:4 and 1:6 at 40C and 350 rpm. The reaction time was kept constant at 3 hours for all experiment s. Two types of catalysts have been used NaOH and KOH at a range of 0.5 -2.0% wt. of oil. After transeste rificatio n reaction the biodiesel was separate d from glycerol using separatin g funnel and finally

washed with 5% water followed by magnesium sulfate anhydro us to remove the water. Several basic variables , namely, catalyst type and concentr a-tion, methano l to oil ratio and reaction temperat ure of transeste rificatio n were investiga ted as they play a significant differenc e in biodiesel produce d (Ma and Hanna, 1999).

Biod iesel anal ysis

Sever al paramet ers have

been analyzed by specific method to verify whether the products fulfill the specifica tion of standard methods (ASTM

D 6751 & EN 14214). An atomic emission (AE) specifica tion multielement oil analyzer (VIOA) was used to de-

termine the group I metals (Na, K), group II metals (Ca, Mg) and phospho rus content. Viscosit y was measure d in mm/s at 40 C using houillon viscome ter (France) with ISL software version 2.1. Total value was measure d using titration method.

Result and Discus sion

Two importan t propertie s of PSCO &

WSCO are compiled in Table 1. The acid values expose the low amount of free fatty acids (FFA) in both types of oils. In contrast, WSCO has significa ntly high viscosity than PSCO. Both oils can be utilized as fuel in diesel engines, but the main barrier to employ the oil as fuel is its high viscosity (Table 1) which creates troubles in

Table 1 D e t e

r m i n a t i o n o f a c i d v a l u e a n d v i s c o s i t y o f P S C O

a n d W S C O Properties Acid value, mg KOH/g oil Viscosity, mm/s at 40C PSCO 0.1 5.8 WSCO 1.6 9.5

atomizat ion of the fuel spray and function of the fuel injectors . The results also show that viscosit y and acid value of WSCO are significa ntly higher than pure one. In two recent studies (Turkan and Kalay, 2006; Oliveira and

Rosa, 2006), it has been found that almost 90% of the total fatty acids of commer cial sunflower oil are compos ed of two double bonds containing oleic acids. Oliveira and Rosa (2006) have reported that the percenta ges of these two free fatty acids in sunflow er oil are 23.9% and 66.1% consecu -tively. Effe ct of volu metr ic ratio
Meth

anol, ethanol, propanol, butanol and amyl al-cohol can be used in the transester ification reaction, amongst these alcohols methanol is applied more frequently as its cost is low and it is physicall y and chemically advantag eous (polar and shortest chain alcohol) over the other alcohols (Demirba s, 2005). Accordin g to Demirba s (2007), in contrast, ethanol is also preferred alcohol for using

in the transester ification pro-

( % ) Y i e l d B i o d i e s e l

10 0 95 90
85

PSC O Biodi es el Yield

(%)
80

75 70

WSC O Biodi es

4.0 : 1.0

3.0 : 1.0

1.0 : 1.0 : 1.0 : 3.0 4.0 6.0

el Yield (%

Oil and Metha nol Ratio

Fig . 1. Eff ect of vol um etic rati o of sun flo wer oil to met han ol (M eO H) on bio

die sel yiel d (Re acti on con diti ons : te mp era tur e= 40 C, cat aly st KO H =1 wt. %, RP M = 350 , rea ctio n tim e= 180 mi n)
Y i e l d B i o d i e s e l
10 0 95 90 85 80 75 70 4.0 :

1.0

1.0

3.0

4.0

6.0

(%)

Oil and Ethan ol Ratio

Fig. 2. Effec t of volu metri c ratio of sunfl ower oil to etha nol (EtO H) on biodi esel yield (Rea ction condi tions : temp eratu re = 40C , catal yst KOH =1 wt. %, RPM = 350, react

ion time = 180 min)

cess compare d to methanol since it is derived from agricultu ral products and is renewabl e and biologically less offensive in the environ ment. The effect of volumetr ic ratio of methanol and ethanol to oil was studied. Results exhibit that highest biodiesel yield is nearly 99.5% at 1:6 oil/meth anol (Figures 1 and 2). In

comparis on, biodiesel yield using methanol continuously increases with the raise of methanol molar ratio. Converse ly, in Figure 2, despite a decrease in 3:1 oil/ethan ol (83% biodiesel yield) the trend shows similarit y with methanol /oil molar ratio yield. In this case yield at 3:1 oil/ethan ol is lower than yield at 4:1 oil/ethan ol most probably as a result of emulsific ation during separatin

g and washing process. Notwiths tand-ing this exceptio n, in overall results provide evidence that increase of both type of alcohol ratio improve the yield of biodiesel . The further study such as effect of catalyst was performe d applying methanol as yield

1. 1

M = 3 5 0 , r e a c t i o n

y i e 1 l d B 0. 9 i o d i e s e l 0.
8 0. 7

Catalyst

Fig. 3. Effect of differen t catalyst s on ester yield (Reactio n conditio ns: tempera ture = 40C, oil: methan ol = 1:6, catalyst = KOH, RP

t i m e = 1 2 0 m i n ) . V e r t i c

a l b a r s i n d i c a t e S E ( n = 3 )
10 0

Yi eld Bi od ies el

99 98 97 96 95 0.00%

cat aly st co nc en tra tio n (R ea cti on co nd iti on s: te m pe rat ur e= 40 C , oil : me th an ol = 1: 6,

Catalyst

Fi g. 4. Ef fec t of

cat aly st = K O H, R

P M = 35 0, re act io n ti me = 12 0 mi n). Ve rti cal ba rs in dic ate SE (n = 3)

using this alcohol (oil: methan ol = 1:6) has achieve d the highest percent age.
Previ ous study (Knothe et al., 1996) shows that producti on of biodiesel

from waste frying vegetabl e oil used catalyst potassiu m hydroxid e with the reaction carried out at ambient pressure and temperat ure, the conversi on rate of 80 to 90% were achieved and in two steps the ester yield were 99%. From Figure 3, it can be seen that highest biodiesel yield (98.4%) has been achieved using NaOH at 400C. Paradoxi -cally, during separatin g washing

of biodiesel the emulsification phenome na have been observed . Although

the basic catalysts are the most common as the pro-cess using them is quicker and the reaction condition s are moderate d (Freedm an. et al., 1984), these cata-lysts have some drawbac ks: they must be neutraliz ed giving rise to wastewat ers and can not be reutilized , they create difficulti es to separate the methyl esters (biodiese l) by formatio n of stable emulsion s, the byproduc t glycerol

is obtained as an aqueous solu-tion of comparat ively low purity and the reaction becomes very sensitive to the presence of water and free fatty acids (Arzame ndia et al., 2007). In this study it has been observed that this emulsific ation can be alleviate d reducing shaking intensity during washing and separatio n of biodiesel from glycerol. In spite of higher yield, using NaOH

causes more emulsion than KOH and makes complica ted to separate biodiesel from glycerin. For this reason, KOH has been screened as a catalyst to study the effect of catalyst concentr a-tion and above discusse d effect of molar ratio on biodiesel yield. In Figure 4, The biodiesel yield shows a continuo us rise from about 96% to 99% when the catalyst KOH concentr ation increases

from 0.5% wt to 2.0% wt, but the yield producti on is not significa nt.

A n a l y z i n g b i o d i e s e l a c h i e v e d u n d e r o p t i m u m

c o n d i t i o n As above conferre d, both pure and waste cooking sunflow er oil can be consum ed as fuel in diesel engines, but the main obstacle to use the oil as fuel is its high viscosit y (consec utively 5.8 mm/s and 9.5 mm/s at 40C; Tables 1 and 2) which create problems in atomizat ion of the fuel spray

and operatio n of the fuel injectors . The obtained free fatty acid alcohol esters or biodiese l from both oil through transest erification process have lower viscosit y of 4.1 4.5 mm/ s at 40C (Table 2). The biodiesel samples produce d under optimum conditio n of 1:6 volumetr ic oil-tomethano l molar ra-tio, 1% KOH catalyst and

40C reaction temperature were analyzed concerni ng some significa nt specifications as fuel in diesel engine. These results are shown in Table 2. Most of these propertie s fulfill the restrictio ns of biodiesel standard in ASTM D 6751 and EN 14214. In contrast biodiesel obtained from WSCO has slightly higher acid value (0.44 mg KOH/

Table 2 Characteristics of produced biodiesels in contrast with standard value Standard method Viscosity Acid number Group metals(Na+ K) Group metals(Ca+ Mg) Phosphorus content engine g oil) compon than ents biodiesel (Kalam produce and d from Madjuki, PSCO 2002). (0.1 mg Addition KOH/g ally, it oil). can be Addition observed ally two from types of Table 2 the that biodiesel PSCO show biodiesel virtually has similar consider viscosity ably . higher Viscosit phospho y is the rus most concentr essential ation property than the of diesel other fuel one and because none of it these influenc fulfills es the requirem wear ent of rate of mm/s at 40C mgKOH/g oil mg/kg mg/kg mg/kg ASTMD 6751 ASTMD 6751 EN 14214 EN 14214 EN 14214 Value according to standard method 1.96.0 0.50 max 5.0 max 5.0 max 10.0 max Biodiesel (PSCO) 5.8 0.1 2.5 3.1 5.7 Biodies el (WSC O) 9.5 0.44 2.8 2.6 3.1

Property

Unit

the standard method specifica tion as well.

Concl usion
The optimum condition s for biodiesel producti on from WSCO & PSCO have been studied. Result shows optimal condition of sunflowe r oil biodiesel producti ons are 1:6 volumetr ic oil-tomethanol molar ratio, 1 wt. %KOH at 400C reaction temperat ure. This study has provided evidence that waste cooking sunflowe

r oil may be employe d as a substanti al source of biodiesel as fuel in diesel engines. Because, the produced biodiesel is of good quality within the array of standard method specifica tions and the producti on yield is apt. up to approxi mately 99% under optimum condition s. Moreove r, this research represent ed that the producti on of biodiesel from PSCO & WSCO has no significa

nt differenc es. Advance research is ongoing to reduce the producti on cost by developi ng a method to decrease the emulsific ation during basecatalytic transeste rification and aqueouswashing of the product and readily recovery of glycerin byproduc t. Biodiesel from used cooking sunflowe r oil could be used as a diesel fuel which consider ed as renewabl

energy and environ mental recyclin g process from waste oil after frying. Ack now ledg eme nts The authors acknowl edge the financia l support provide d by the Ministry of Science, Technol ogy and Innovati on (MOST) , Malaysi a, for current project. Also they are thankful to Md. Imdadul Haq for his assistan ce in written this manuscr ipt.

Refere nces
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G., I. Cam poa, E. Argu inare naa, M. Sanc hezb, M. Mon tesb and L. M. Gan dia, 2007. Synth esis of biodi esel with heter ogene ous NaO H/alu mina cataly sts: Com paris on with Hom ogeneo us NaO H. Che mical Engi neeri ng Jour nal, 134: 123-

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