J. Basic. Appl. Sci. Res.

, 1(12)2717-2723, 2011 2011, TextRoad Publication

ISSN 2090-4304 Journal of Basic and Applied Scientific Research www.textroad.com

EFFECTIVE TEMPERATURE AND METHANOL VOLUME FOR TRANSESTERIFICATION OF HEVEA BRASILIENSIS

Handono Sasmito1*, Sudjito2, Pratikto2, Bambang Dwi Argo3

1

Doctoral Program of Mechanical Engineering, Faculty of Engineering, University of Brawijaya, Malang 2 Lecturer of Mechanical Engineering, Faculty of Engineering, University of Brawijaya, Malang 3 Lecturer of Agricultural Faculty, University of Brawijaya, Malang (INDONESIA) ABSTRACT

This study intended to know the effect of temperature variation and methanol volume percentage due to the physical characteristics of biodiesel and then to perform the composition of methanol and temperature which could increase the calorific value. The physical characteristic of biodiesel was identified by density, viscosity, calorific value, cetane index, and flash point. These factors would influence the burning process of biodiesel. It had been studied experimentally. Result showed that increasing temperature at 30% volume of methanol would increase calorific value, however, it decreased others physical characteristics of biodiesel. KEY WORDS: temperature, methanol, physical characteristic, biodiesel. INTRODUCTION Biodiesel was produced from rubber seed oil in many countries and to be used as alternative fuel. Rubber seed oil had potential high velocity for engine works. However, if it was injected and combusted in engines it would cause any problems. These problems could be minimized by converting it into biodiesel. Biodiesel was an alternative energy source. It was produced from vegetable oil or animal fatty matters. Biodiesel was produced from the reaction between triglyceride and alcohol by using hydroxide catalyst at the certain temperature and composition. The results of this reaction were methyl ester or biodiesel and glycerol. Process of the reaction was named as transesterification [1] Fruit of rubber plant (Hevea brasiliensis) was formed from three or four squares and the fruit would ripe and hatch after six months, so that rubber seed was released from the shell. The shape of rubber seed was ellipse with 2.5 3 cm of length and its weight was 2 4 gram per-seed. Rubber seed was included 40-50% brown hard skin and 50-60% yellow white kernel. Kernel of rubber seed was included 45.3 % oil, 2.71% ash, 3.71% water, 22.1% protein, and 24.21% carbohydrate. Therefore, rubber seed had great potential use as raw material of biodiesel. But the water content was so high and it could accelerate triglyceride hydrolysis into fatty acid. Therefore, rubber seed was needed to be dried before being taken its oil [2] Process of transesterification was needed to produce biodiesel. The process could use any kind of alcohol such as methanol, ethanol, and buthanol for converting triglyceride into biodiesel. Previous researcher had expressed that this method produced biodiesel until 98% of raw material came from vegetable oil [3]. Process of transesterification was influenced by some factors. Methanol volume percentage was the most important factor because methanol gave very high impact in breaking molecule bonds of long branched chain into fewer molecule of short straght chain. Alcohol used in this process was methanol of 90%, because methanol had the lightest molecule mass and it was easy to be recoveried. Effective temperature was needed to produce available biodiesel [4]. Therefore, the current research studied the two important factors, i.e. temperature and methanol volume with an aim to improve biodiesel performance. MATERIALS AND METHODS This research used experimental method. It was observed at 4 laboratories for getting empirical data. The 4 laboratories were Research Laboratory of Chemical Engineering (Politeknik Negeri Malang), Combustion Motor Laboratory of Mechanical Engineering (Engineering Faculty, Brawijaya University), Research Laboratory of Chemistry (Public University, Malang), and Laboratory of Pelumas Pertamina Production Unit Surabaya). The materials used in this research were as follow:

*Corresponding Author: Handono Sasmito, Doctoral Program of Mechanical Engineering, Faculty of Engineering, University of

Brawijaya, Malang , INDONESIA . E-mail: handonosasmito@gmail.com

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1. 2. 3. 4. 5.

Rubber seed oil ( 7.5 l). Rubber seed oil was used as raw material of biodiesel in esterification reaction. Methanol volume percentage of 95% ( 3 l). Methanol was used at 10%, 20%, and 30% of total volume of methanol and rubber seed oil. Potassium hydroxide (KOH) 200 gram. Potassium hydroxide was used as catalyst because it could accelerate the velocity of transesterification reaction. Mineral water was used as cooling liquid media which would evaporate at transesterification reaction in reflux so that the liquid could react again in round pitcher and it was as cooler at distillation process for biodiesel purification. Sulfuric acid (H2SO4, 50 ml). It would accelerate esterification reaction.

Vegetable oil Biodiesel could be made from vegetable oil or animal oil, but vegetable oil was generally used as raw material of biodiesel. Vegetable oil and biodiesel was a big class of organic mixture. Vegetable oil was as fatty acid tri-Esther with glycerol or triglyceride, but biodiesel was as fatty acid mono-esther with methanol. Some important consequences due to the both raw materials of diesel mechanic were as follow: 1. Vegetable oil (triglyceride) had big molecule weight. It was bigger than biodiesel (name as methyl esther) . Therefore, triglyceride was easy cracking into the kind of little molecule if it was heated without contact to oxygen. 2. Vegetable oil had higher viscosity than diesel oil/ solar or biodiesel, so that injection pump of raw material in diesel mechanic was not able to produce better atomization when vegetable oil was sprayed to combustion room. 3. Molecule of vegetable oil had more branches than methyl esther of fatty acid. Therefore, cetane index of vegetable oil was lower than methyl esther. Cetane index was defined as the standard of combustion ease on raw material in diesel mechanic. Composition in vegetable oil Vegetable oil was included triglycerides of fatty acid (its content was about 95%), free fatty acid or FFA, mono- and diglyceride, and others components like phosphoglycerydes, vitamine, mineral, or sulfur. The raw materials of biodiesel were as follow [5]: 1. Triglycerides. They were the main variation component of fatty and oil-fatty. 2. Fatty acids. They was as side production on refining industry of fatty and oil-fatty. Table 1 described the content of oil in any seeds. Table 1 Content of oil in any seeds [6]
Seed Rubber Castor-oil-plant Grated coconut Sesame seed Peanut Weight percentage (%) 40.50 54 47-52 33-57 46-52

Biodiesel Biodiesel was a fuel produced from vegetable oil by converting tri-glyceride oil to methyl or ethyl esters with a process known as transesterification.. This kind of fuel was included biodiesel, bioethanol, and bio-oil. Transesterification of vegetable oil would produce a kind of biodiesel that could change the position of solar or diesel oil. The exeedance of biodiesel compared with solar was as follow: 1. Production of biodiesel could supply the production of vegetable oil or animal oil in great number. 2. There was no content of sulfur and benzena which had the characteristic of carsinogen and natural description. 3. Low intensity of poison. number on casting off gas emision compared to diesel oil was CO decreased into 7.43%, CO 2 decreased into 3.33%, O2 increased into 6.25%, NOx decreased into 11.32%, and SO2 decreased into 16.65% [5] 4. Point of turning on was high. Point of turning on was occured at the lowest temperature which could cause the diesel vapour would turn on too. Therefore, biodiesel was saver from burning dangerous than solar. Transesterification reaction using hydroxide catalyst was as in Figure 1 and flow of change process was described as in Figure 2 below.

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J. Basic. Appl. Sci. Res., 1(12)2717-2723, 2011

ROH + B RO- + BH+ RCOO CH2 RCOO CH RCOOH C 2OCR CH RCOO CH OR RCOO CH2 + -OR RCOO CH OR

(1)

(2)

RCOOH C 2O C R CH RCOO CH
RCOOH C 2O CH

+ ROOCR

(3)

RCOOH C 2O C R CH RCOO CH H C O+ BH+

RCOO CH

+ B

(4)

H C OH Figure 1 Mechanism of transesterification [7] Catalyst

TG + 3ROH Stepwise reactions are: k1 TG + ROH DG + RCO2R k2 k2 DG + ROH MG + RCO2R k3

3RCO2R + GL

(1)

(2)

Figure 2 Flow of Trans-estherification Reaction [7]

(3)

Figure 2 Flow of Transesterification Reaction [8]

Conversion velocity was influenced by time and temperature of reaction [9]. Variation of time at transesterification with variation of temperature could cause the change of conversion value from vegetable oil into biodiesel as described in Figure 3

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60C 40C 32C Reactions Conditions: 1% Catalyst (Sodium

Figure 3 Influence of temperature at transesterification to biodiesel conversion [10]

Viscosity Fluid viscosity was defined as a value which described the difficulty of fluid to flow. The formula of viscosity was as follows [11]:

v=
Note: V

(1).

= kinematic viscosity of fluid (m2/s) = dynamic viscosity of fluid (kg/m/s) = density of fluid (kg/m3)

Cetane Index Cetane index was defined as the standard of combustion ease on raw material in diesel mechanic. The formula of Cetane index was as follow: CCI =454, 741641, 416 D+774, 74 D2 0,554 B + 97,803 (log B)2 (ASTM D976) (2.6) .. (2) Note: CCI = Calculated Cetane Index D = density at 15C (kg/m3), due to D test of 1298 or D 4052 B = distillation temperature at recovery of 50% volume (C), due to D test of D 86 RESULTS AND DISCUSSION Figure 4 described the relation between temperature and density of biodiesel. It showed that variation of temperature at transesterification and methanol volume percentage had given real influence to the density of biodiesel. The curve described the relation between transesterification of rubber seed oil with methanol volume percentage variation of 10%, 20%, and 30% due to biodiesel density. From the curve, it could be shown that the highest density was 920.1 kg/m3. It was produced from transesterification with temperature of 40 o C and methanol volume percentage of 10%. But the lowest density was 895.2 kg/m3. It was produced from transesterification with temperature of 60o C and methanol volume percentage of 30%.

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J. Basic. Appl. Sci. Res., 1(12)2717-2723, 2011

925 920

y (10%)= 0,004x2 - 0,688x + 940,2 R = 0,930 10% metanol 20% metanol 30% metanol Poly. (10% metanol) Poly. (20% metanol) Poly. (30% metanol) 80 90

Massa Jenis (Kg /m3 )

D e n s i t y

915 910 905 900 y (30%) = 0,001x2 - 0,298x + 907,9 R = 0,809 30 40 y (20%)= 0,008x2 - 1,181x + 941,2 R = 0,710

(kg/ 895 3 m)

890

Temperatur Transesterifikasi (0 C) Transesterification Temperature (oC)

50

60

70

Figure 4 Relation between temperature and density of biodiesel

Figure 5 described the relation between temperature and viscosity of biodiesel with methanol volume percentage variation of 10%, 20%, and 30%. The curve showed that the highest viscosity was 13.23 mm2/s. It was produced from transesterification with temperature of 40o C wand methanol volume percentage of 10%. But the lowest viscosity was 7.31%. It was produced from transesterification with temperature of 60 o C and methanol volume percentage of 30%.

15
V i c o s i t y (mm /s)

13

y(10%) = 0,000x2 - 0,004x + 12,70 R = 0,859 y (20%)= 0,000x2 - 0,118x + 15,35 R = 0,927

11 9 7 5 30 40 50

y (30%)= 0,001x2 - 0,230x + 16,36 R = 0,801

10% metanol 20% metanol 30% metanol Poly. (10% metanol) Poly. (20% metanol) Poly. (30% metanol)

Viskositas (mm2/s)

60

70
o

80

90

Transesterification Temperature ( Temperatur Transesterifikasi C)0 C) ( Figure 5 Relation between temperature and viscosity of biodiesel

Figure 6 described the relation between temperature and flash point of biodiesel with methanol volume percentage variation of 10%, 20%, and 30%. It was shown that the highest flash point was 220 o C. It was produced from transesterification with temperature of 40p C and methanol volume percentage of 10%. But the lowest flash point was 183o C. It was produced from transesterification with temperature of 60 o C and methanol volume percentage of 30%.

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230
F l a s h P o i n t ( C)
o

220

Titik Nyala (0 C)

y(10%) = 0,01x2 - 1,7x + 273,2 R = 0,877

210 200 190 180 30 40 y (20%)= 0,027x2 - 3,817x + 327,6 R = 0,889 y (30%)= 0,012x2 - 1,907x + 262,4 R = 0,818

10% metanol 20% metanol 30% metanol Poly. (10% metanol) Poly. (20% metanol) Poly. (30% metanol)

Temperatur Transesterifikasi (0 C) o Transesterification Temperature ( C)

50

60

70

80

90 .

Figure 6 Relation between temperature and flash point of viodiesel

Figure 7 described the relation between temperatue and calorie value of biodiesel with methanol volume percentage of 10%, 20%, and 30%. It was shown that the highest calorie value was 10,284.56 calory/gram. It was produced from transesterification with temperature of 60o C and methanol volume percentage of 30%. But the lowest calorie value was 9,990.12 calory/gram. It was produced from transesterification with temperature of 40 o C and methanol volume percentage of 10%. By being increased the temperature, the calorie value was increased too, but at the temperatue of 80 o C, the calorie value had decreased trend..

Nilai Kalor (kal/gram)

C a l o r i e V a l u e (kal/ gram)

10300 y (10%)= -0,215x2 + 30,45x + 9086, R = 0,747 10200 y(20%) = -0,433x2 + 54,99x + 8459, R = 0,809 10100 10000 9900 9800 30 40 y (30%)= -0,337x2 + 49,04x + 8423, R = 0,887

10% metanol 20% metanol 30% metanol Poly. (10% metanol) 90

Temperatur Transesterifikasi (0 C) Transesterification Temperature (oC)

50

60

70

80

Figure 7 Relation between temperature and calorie value

Figure 8 described the relation between temperatue and Cetane Index with methanol volume percentage of 10%, 20%, and 30%. The highest Centane Index was 44.34. It was produced from transesterification with temperature of 60 o C and methanol volume percentage of 30%. But the lowest Cetane Index was 37.92. It was produced from transesterification with temperature of 40 o C and methanol volume percentage of 10%. The result showed that Cetane Index had opposite relation to flash point. It meaned that it needed a long time for combustion at high flash point.

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46 y(30%) = -0,002x2 + 0,312x + 33,82 R = 0,824 C 44 e

Indeks Setana

t a n e I n d e x

10% metanol 20% metanol 30% metanol Poly. (10% metanol)

42 40 38 36 30 40

y(20%) = -0,005x2 + 0,725x + 21,30 R = 0,830 y(10%) = -0,002x2 + 0,339x + 28,33 R = 0,949

50

60

70
o

80

90

Transesterification Temperature ( ( Temperatur Transesterifikasi C)0 C ) Figure 8 Relation between temperature and Centane Index

CONCLUSION Based on the analysis as above, it could be concluded that the increasing of temperature at methanol volume percentage of 30% would cause physical characteristic (included density, viscosity, and flash point) of biodiesel to decrease, however, calorific value would increase. Results showed that the lowest density was 895.2 kg/m3 (60o C, methanol volume percentage of 30%), the viscosity was 7.31 x 10 6 m2/s (60o C. methanol volume percentage of 30%), flash point was 183o C (60 o C, methanol volume percentage of 30%), calorific value was 10,284 kkal/kg (60 o C, methanol volume percentage of 30%), and Cetane Index was 44.69 (60 o C, methanol volume percentage of 30%). REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. Fukuda, H.; Kondo, A.; and Noda, H. 2001. Biodiesel Fuel Production by Trans-etherification of Oils. Journal of Bioscience and Bioengineering. Sep 2001, 92: p. 405-416 Ikwuagwu, O.E., Onogobu, I.C., and Njoku, O.U. 2000. Production of Biodiesel Using Rubber [Hevea Brasilienses] Seed Oil. Ind Crop Prod 12: p. 57-62 Bouaid, A. 2005. Pilot Plan Studies of Biodiesel Production Using Brassia Carinata as Material. Catalysis Today Chemical Engineering Department, Faculty of Chemistry Raw, Uniersity of Complutense, Spain. Zandy, Agustinus. 2007. Intensifikasi Proses Produksi Biodiesel. ITB & PT Rekayasa Industri. Mittelbach, Martin. 2001. Biofuel from Waste and Non Edible Feedstock. Department of Renewable Resources University of Graz, Austria. Kataren, S. 1986. Pengantar Teknologi Minyak dan Lemak Pangan. UI-Press, Jakarta. A. Chairil. 2007. Biodiesel from CPO and Application as Blending Components. 3rd Asian Petroleum Technology Symposium Program. Jakarta. Schuchardt. 1998. Transestherification of Vegetable Oil, a review; Chem. Soc.; Vol. 9, No. 1: 199-210 Wardana, ING. 2008. Bahan Bakar dan Teknologi Pembakaran. PT Danar Wijaya Brawijaya University Press, Malang.

10. Mescha. 2007. Intensifikasi Proses Produksi Biodiesel. ITB & PT Rekayasa Industri. Bandung. 11. Holman, J.P. 1984. Metode Pengukuran Teknik. PT Erlangga. Jakarta.

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