Analysis Ethyl ester in Biodiesel of Raw Material Waste Coconut Oil and Arak.
ANALYSIS ETHYL ESTER IN BIODIESEL OF RAW MATERIAL
WASTE COCONUT OIL AND ARAK
I Wayan Bandem Adnyana1), Ni Made Suaniti 2)
1)Department of Mechanical Engineering, Faculty of Engineering, Udayana University, Badung 80361.
2)Department of Chemistry, Faculty of mathematic and Sciences, Udayana University, Badung 80361.
e-mail: bandem.aiwa@yahoo.com
Abstract
Arak is alcoholic beverages are only allowed to contain ethanol, but unfortunate if misused its use so
that the wine can be used as a substitute of reactant in the manufacture of biodiesel. The purpose of this study
was to determine the amount of the ethyl ester is formed in product of biodiesel. The methode used cooking oils
by households and the level of wine as a reactant in the process of esterification and transesterification using
phosphoric acid. Analysis ethyl esters in biodiesel by GC-MS that the results showed ethyl laurate the maximum
produced (39.55%) at a retention time of 12.741 minutes by ethanol p.a in the process of biodiesel and ethyl
myristate each 36.33%; 48,09%; 32,62%; and 39,62% at retention time 15.008 minutes using arak destillated
one, twice, and three times.
Keywords: level of wine, ethyl ester, biodiesel
INTRODUCTION
Arak as one of the drinks in Bali, production was still in level of households with
traditional distillation. Arak is obtained from coconut and palm trees that plants richness
Indonesia which allows it to be processed to meet the energy for transportation (biodiesel).
Arak of palm and coconut are produced by the domestic industry could reach 30 to 50% [4]
depending on the habits and way of distillation performed. Enau ethanol content in wine
varies greatly depending on the customs processing or process.
Product biodiesel derived renewable because the reactants and reagents derived from
plants, namely oil. Because wine grapes are used then the ethanol processing into biodiesel is
referred to as ethyl ester, or more commonly called Fatty Acid Ethyl Ester (my face). This
was stated in a national energy policy (Instruction No. 1/2006 and Presidential Decree No.
5/2006). Oils derived from plants such as sunflower and waste, canola, soybean, olive, corn
and hazelnuts using methanol and hydrochloric acid catalyst there was no significant
difference in the biodiesel produced [3]. The use of used cooking oil and ethanol pa with GCMS, the maximum qualitative ethyl ethyl lauric Other [5, 2].
Based on this, the research is directed at the establishment of the percentage of each
ethyl esters in biodiesel made of vegetables with varied concentrations of the wine.
MATERIALS AND METHOD
Chemicals used in this study varied levels of palm wine, cooking oil, phosphoric acid 85% pa
Merck, NaOH, distilled water, calcium chloride, microfibre GF/C. The equipment used is a specific
set of reflux, analytical balance, and GC-MS. The method used for the manufacture of biodiesel is
through esterification and transesterification reaction between gin that used cooking oil with ethanol
content between 35 to 80%. Results were analyzed the percentage of biodiesel through the output
GCMS (peak area).
RESULTS AND DISCUSSION
Ethyl ester (FAEE) formed in biodiesel from waste cooking oil with ethanol than
ethanol from wine obtained using phosphoric acid catalyst in varying results with m/z 88 for
specific fragment in FAEE. Acid can be used the catalyst to make biodiesel [1,5]. The use of
ethanol is obtained ethyl laurate pro analyzes the maximum (39.55%) at a retention time of
12.741 minutes. The same results have been obtained only appear at longer retention time is
16.52 minutes [6], this means that the analysis time ethyl laurate affected by operational
conditions GC-MS. Detection of the next ester compound is ethyl myristate (retention time
15.008 minutes) and stearate (retention time 18.953 minutes) respectively 19.31%, then ethyl
palmitate (retention time 17.068 minutes) 10.84%, and other esters with a percentage of less
than 10%. However, the use of wine as a reagent (substitute ethanol pa) ethyl myristate
produce the maximum (36.33%) as shown in Figure 1 (a). Reagent wine distilled one time as
shown (48,09%) in Figure 1 (b), wine distillated twice times (32,62%) as shown in Figure 1
(c), as well as the total chromatogram biodiesel using a reagent ethanol, arak, arak distillation
first time, wine distilled twice times, and the arak distilled three times (39,62%) as in Figure
1 (d).
50
40
Biodiesel Etanol pa
Biodiesel Arak
35
B. Et.pa
B. Arak
B. A.Des 1x
45
40
30
35
Peak Area
Peak Area
25
20
15
30
25
20
15
10
10
5
7,92 (7,19%)
5
0
0
-5
6
8
10
12
14
16
18
20
22
24
-5
26
6
8
10
Retention Time (Minutes)
14
16
18
20
22
24
26
Retention Time (Minutes)
(a)
(b)
50
50
B. Et.pa
B. Arak
B. A Des 1x
B. A Des 2x
45
40
35
B. Et. pa
B. Arak
B. A Des 1 x
B. A.Des 2 x
B. A Des3 x
45
40
35
30
30
Peak Area
Peak Area
12
25
20
15
25
20
15
10
10
5
5
0
0
-5
6
8
10
12
14
16
18
Retention time (Minutes)
(b)
20
22
24
26
-5
6
8
10
12
14
16
18
20
22
24
26
Retention Time (Minutes)
(d)
Figure 1. Percentage of Ethyl Ester in biodiesel with varies ethanol level (a) Ethanol p.a and arak; (b)
Ethanol, arak, and Arak destilated one time; (c) ethanol p.a, arak, arak destillated one, twice times;
dan (d) etanol p.a, arak, arak destillated one, twice, and three times.
FAEE with m/z 88 fit or continuation of previous studies that the FAME for using
methanol appeared at m/z 74 and 87 are specific, it is submitted in the National Engineering
Hospitality Conference 2014 and has not shown a determining effect of type of ester of the
engine [7,9]. Alleged ionic compounds with m/z 88 in FAEE are formed in this study is -+CCOOC2H5 as ethyl carboxylate, that all biodiesel from waste cooking oil with ethanol varies
above can form esters, only the percentage varies depending on the levels of ethanol used.
Ethanol content in wine is 39.24%; Arak distilled once (60.19%); Gin distilled twice
(64.61%); and Arak distilled three times (79.32%) in before studying by Adnyana and
Suaniti. This study supported that use waste cooking oil as biodiesel feedstock using an acid
catalyst can be formed biodiesel without significant differences of the various types of oil
such as sunflower oil and waste, soybean oil, and others. Analysis biodiesel from different
oils have been worked on chromatographic and reviewed [3,8].
One form of mass chromatogram spektrometry ethyl laurate according Entry 131. 473
Wiley7.LIB library with a mass 260 and the base peak (m/z) 88 as shown in Figure 2. The
other name is dodecanoate acid, ethyl ester (CAS) Ethyl Laurate with molecular formula
Me(CH2)10C(O)OEt and the formula C14H28O2 CAS 106-32-2, the molecular weight of 228.
other allegations according Entry 164.499 Library Wiley7 LIB by any other name is
tetradecanoate acid, ethyl ester (CAS) Ethyl myristate with molecular formula
Me(CH2)12C(O)OEt and the formula C16H32O2 CAS 124-06-1, molecular weight of 256.
Fragment specific of
FAEE biodiesel
Fragment specific of
FAEE biodiesel
Fragment specific of
FAEE biodiesel
CONCLUSIONS
Ethyl ester in biodiesel has made from waste coconut oil and ethanol p.a.; arak; arak
has destilled one, twice, and three times. The results showed that ethanol p.a. formed
maximum of ethyl laurate (39.55%) at a retention time of 12.741 minutes, ethyl myristate
(retention time 15.008 minutes) and stearate (retention time 18.953 minutes) respectively
were 19.31%, then ethyl palmitate (retention time 17.068 minutes) was 10.84%, and other
esters with a percentage of less than 10%. The next analysis showed that arak and detillated
one, twice, and three times showed maximum of ethyl myristate produce the maximum, each
36.33%; 48,09%; 32,62%; and 39,62%.
ACKNOWLEDGEMENTS
Thanks to the Rector of Udayana University through LPPM Chairman replied as the person in
accordance with the letter of Research Activities Assignment Agreement Implementation PNBP
Research Fund (Grant-seeded Udayana) Fiscal Year 2015 No. 246-323 /UN14.2/PNL 01-03-00 / 2015
for all the facilities provided. 246-323 /UN14.2/PNL 01-03-00/2015.
REFERENCES
[1] Fadhil, A.B., Dheyab, M. M., Ahmed, K.M., and Yahya, M., H., Biodiesel Production from Spent
Fish Frying Oil Through Acid-Base Catalyzed Transesterification,J. Anal. Environ. Chem., 2012,
Vol. 13, No. 1, p.09-15, ISSN-1996-918X.
[2] McCurry, J.D. GC/MS Analysis of Trace Fatty Acid Methyl Esters (FAME) in Jet Fuel Using Energy
(tt), Institute method IP585. Application Note Fuels. Agilent Technologies, Inc. 2850. Centerville
road Wilmington, DE. 19808. USA.
[3] Sagiroglu, A., Isbiler, S.S., Ozcan H.M., Paluzar, H., Toprakkiran, N.M. Comparison of Biodiesel
Productivities of Different Vegetable Oils by Acidic Catalysis, Journal C1&CEO, 2011, Vol. 17
No.1, p. 53-58.
[4] Suaniti, N.M., Perbedaan Kadar Etanol dalam Arak Enau dan Arak Kelapa Hasil Industri Rumah
Tangga yang diproduksi di Bali dengan Kromatografi Gas. Seminar Nasional Kimia. Surabaya, 28
Juli 2009. Jurusan Kimia F.MIPA ITS, 2009.
[5] Suaniti, N.M., Adnyana, I W.B. Percentage of free Fatty Acid and Characteristics of Biodiesel Fuel
in Waste Coconut Oil (WCO). Conference Proceedings, HKICEAS Hong Kong International
Conference On Engineering and Applied Science, 2013, ISBN: 978-986-87417-4-4,
[6] Suaniti, N.M., Adnyana, I W.B. Pemanfaatan Jelantah Minyak Kelapa Sebagai Energi Alternatif:
Fatty Acid Ethyl Ester.Prosiding Seminar Nasional Sains dan teknologi, Denpasar 18-19
September 2014a, ISBN 978-602-294-018-0.
[7] Suaniti, N.M., Adnyana, I W.B., Sintesis dan Uji Angka Ester Biodiesel Jelantah Minyak Kelapa.
Prosiding Konferensi Nasional Engineering Perhotelan, 2014b, Vol. 1, No.2, Juli 2014, ISSN 2338414X
[8] Yahaya, M.F., Demshemino, I., Nwadike, I., Sylvester, O.P., and Okoro, L.N., A review on the
Chromatographic Analysis of Biodiesel, International Journal of Education and Research, 2013,
Vol 1, No. 8, p.1-12.
[9] Zajac G., Pickarski, W., Kizaczek, P., Comparison of an Effect FAME and FAEE Addition to Diesel
on Energetic Parameters of an Engine, Journal TEKA Kom. Mot. Energ. Roln-Ol PAN, 2008, 217223.
WASTE COCONUT OIL AND ARAK
I Wayan Bandem Adnyana1), Ni Made Suaniti 2)
1)Department of Mechanical Engineering, Faculty of Engineering, Udayana University, Badung 80361.
2)Department of Chemistry, Faculty of mathematic and Sciences, Udayana University, Badung 80361.
e-mail: bandem.aiwa@yahoo.com
Abstract
Arak is alcoholic beverages are only allowed to contain ethanol, but unfortunate if misused its use so
that the wine can be used as a substitute of reactant in the manufacture of biodiesel. The purpose of this study
was to determine the amount of the ethyl ester is formed in product of biodiesel. The methode used cooking oils
by households and the level of wine as a reactant in the process of esterification and transesterification using
phosphoric acid. Analysis ethyl esters in biodiesel by GC-MS that the results showed ethyl laurate the maximum
produced (39.55%) at a retention time of 12.741 minutes by ethanol p.a in the process of biodiesel and ethyl
myristate each 36.33%; 48,09%; 32,62%; and 39,62% at retention time 15.008 minutes using arak destillated
one, twice, and three times.
Keywords: level of wine, ethyl ester, biodiesel
INTRODUCTION
Arak as one of the drinks in Bali, production was still in level of households with
traditional distillation. Arak is obtained from coconut and palm trees that plants richness
Indonesia which allows it to be processed to meet the energy for transportation (biodiesel).
Arak of palm and coconut are produced by the domestic industry could reach 30 to 50% [4]
depending on the habits and way of distillation performed. Enau ethanol content in wine
varies greatly depending on the customs processing or process.
Product biodiesel derived renewable because the reactants and reagents derived from
plants, namely oil. Because wine grapes are used then the ethanol processing into biodiesel is
referred to as ethyl ester, or more commonly called Fatty Acid Ethyl Ester (my face). This
was stated in a national energy policy (Instruction No. 1/2006 and Presidential Decree No.
5/2006). Oils derived from plants such as sunflower and waste, canola, soybean, olive, corn
and hazelnuts using methanol and hydrochloric acid catalyst there was no significant
difference in the biodiesel produced [3]. The use of used cooking oil and ethanol pa with GCMS, the maximum qualitative ethyl ethyl lauric Other [5, 2].
Based on this, the research is directed at the establishment of the percentage of each
ethyl esters in biodiesel made of vegetables with varied concentrations of the wine.
MATERIALS AND METHOD
Chemicals used in this study varied levels of palm wine, cooking oil, phosphoric acid 85% pa
Merck, NaOH, distilled water, calcium chloride, microfibre GF/C. The equipment used is a specific
set of reflux, analytical balance, and GC-MS. The method used for the manufacture of biodiesel is
through esterification and transesterification reaction between gin that used cooking oil with ethanol
content between 35 to 80%. Results were analyzed the percentage of biodiesel through the output
GCMS (peak area).
RESULTS AND DISCUSSION
Ethyl ester (FAEE) formed in biodiesel from waste cooking oil with ethanol than
ethanol from wine obtained using phosphoric acid catalyst in varying results with m/z 88 for
specific fragment in FAEE. Acid can be used the catalyst to make biodiesel [1,5]. The use of
ethanol is obtained ethyl laurate pro analyzes the maximum (39.55%) at a retention time of
12.741 minutes. The same results have been obtained only appear at longer retention time is
16.52 minutes [6], this means that the analysis time ethyl laurate affected by operational
conditions GC-MS. Detection of the next ester compound is ethyl myristate (retention time
15.008 minutes) and stearate (retention time 18.953 minutes) respectively 19.31%, then ethyl
palmitate (retention time 17.068 minutes) 10.84%, and other esters with a percentage of less
than 10%. However, the use of wine as a reagent (substitute ethanol pa) ethyl myristate
produce the maximum (36.33%) as shown in Figure 1 (a). Reagent wine distilled one time as
shown (48,09%) in Figure 1 (b), wine distillated twice times (32,62%) as shown in Figure 1
(c), as well as the total chromatogram biodiesel using a reagent ethanol, arak, arak distillation
first time, wine distilled twice times, and the arak distilled three times (39,62%) as in Figure
1 (d).
50
40
Biodiesel Etanol pa
Biodiesel Arak
35
B. Et.pa
B. Arak
B. A.Des 1x
45
40
30
35
Peak Area
Peak Area
25
20
15
30
25
20
15
10
10
5
7,92 (7,19%)
5
0
0
-5
6
8
10
12
14
16
18
20
22
24
-5
26
6
8
10
Retention Time (Minutes)
14
16
18
20
22
24
26
Retention Time (Minutes)
(a)
(b)
50
50
B. Et.pa
B. Arak
B. A Des 1x
B. A Des 2x
45
40
35
B. Et. pa
B. Arak
B. A Des 1 x
B. A.Des 2 x
B. A Des3 x
45
40
35
30
30
Peak Area
Peak Area
12
25
20
15
25
20
15
10
10
5
5
0
0
-5
6
8
10
12
14
16
18
Retention time (Minutes)
(b)
20
22
24
26
-5
6
8
10
12
14
16
18
20
22
24
26
Retention Time (Minutes)
(d)
Figure 1. Percentage of Ethyl Ester in biodiesel with varies ethanol level (a) Ethanol p.a and arak; (b)
Ethanol, arak, and Arak destilated one time; (c) ethanol p.a, arak, arak destillated one, twice times;
dan (d) etanol p.a, arak, arak destillated one, twice, and three times.
FAEE with m/z 88 fit or continuation of previous studies that the FAME for using
methanol appeared at m/z 74 and 87 are specific, it is submitted in the National Engineering
Hospitality Conference 2014 and has not shown a determining effect of type of ester of the
engine [7,9]. Alleged ionic compounds with m/z 88 in FAEE are formed in this study is -+CCOOC2H5 as ethyl carboxylate, that all biodiesel from waste cooking oil with ethanol varies
above can form esters, only the percentage varies depending on the levels of ethanol used.
Ethanol content in wine is 39.24%; Arak distilled once (60.19%); Gin distilled twice
(64.61%); and Arak distilled three times (79.32%) in before studying by Adnyana and
Suaniti. This study supported that use waste cooking oil as biodiesel feedstock using an acid
catalyst can be formed biodiesel without significant differences of the various types of oil
such as sunflower oil and waste, soybean oil, and others. Analysis biodiesel from different
oils have been worked on chromatographic and reviewed [3,8].
One form of mass chromatogram spektrometry ethyl laurate according Entry 131. 473
Wiley7.LIB library with a mass 260 and the base peak (m/z) 88 as shown in Figure 2. The
other name is dodecanoate acid, ethyl ester (CAS) Ethyl Laurate with molecular formula
Me(CH2)10C(O)OEt and the formula C14H28O2 CAS 106-32-2, the molecular weight of 228.
other allegations according Entry 164.499 Library Wiley7 LIB by any other name is
tetradecanoate acid, ethyl ester (CAS) Ethyl myristate with molecular formula
Me(CH2)12C(O)OEt and the formula C16H32O2 CAS 124-06-1, molecular weight of 256.
Fragment specific of
FAEE biodiesel
Fragment specific of
FAEE biodiesel
Fragment specific of
FAEE biodiesel
CONCLUSIONS
Ethyl ester in biodiesel has made from waste coconut oil and ethanol p.a.; arak; arak
has destilled one, twice, and three times. The results showed that ethanol p.a. formed
maximum of ethyl laurate (39.55%) at a retention time of 12.741 minutes, ethyl myristate
(retention time 15.008 minutes) and stearate (retention time 18.953 minutes) respectively
were 19.31%, then ethyl palmitate (retention time 17.068 minutes) was 10.84%, and other
esters with a percentage of less than 10%. The next analysis showed that arak and detillated
one, twice, and three times showed maximum of ethyl myristate produce the maximum, each
36.33%; 48,09%; 32,62%; and 39,62%.
ACKNOWLEDGEMENTS
Thanks to the Rector of Udayana University through LPPM Chairman replied as the person in
accordance with the letter of Research Activities Assignment Agreement Implementation PNBP
Research Fund (Grant-seeded Udayana) Fiscal Year 2015 No. 246-323 /UN14.2/PNL 01-03-00 / 2015
for all the facilities provided. 246-323 /UN14.2/PNL 01-03-00/2015.
REFERENCES
[1] Fadhil, A.B., Dheyab, M. M., Ahmed, K.M., and Yahya, M., H., Biodiesel Production from Spent
Fish Frying Oil Through Acid-Base Catalyzed Transesterification,J. Anal. Environ. Chem., 2012,
Vol. 13, No. 1, p.09-15, ISSN-1996-918X.
[2] McCurry, J.D. GC/MS Analysis of Trace Fatty Acid Methyl Esters (FAME) in Jet Fuel Using Energy
(tt), Institute method IP585. Application Note Fuels. Agilent Technologies, Inc. 2850. Centerville
road Wilmington, DE. 19808. USA.
[3] Sagiroglu, A., Isbiler, S.S., Ozcan H.M., Paluzar, H., Toprakkiran, N.M. Comparison of Biodiesel
Productivities of Different Vegetable Oils by Acidic Catalysis, Journal C1&CEO, 2011, Vol. 17
No.1, p. 53-58.
[4] Suaniti, N.M., Perbedaan Kadar Etanol dalam Arak Enau dan Arak Kelapa Hasil Industri Rumah
Tangga yang diproduksi di Bali dengan Kromatografi Gas. Seminar Nasional Kimia. Surabaya, 28
Juli 2009. Jurusan Kimia F.MIPA ITS, 2009.
[5] Suaniti, N.M., Adnyana, I W.B. Percentage of free Fatty Acid and Characteristics of Biodiesel Fuel
in Waste Coconut Oil (WCO). Conference Proceedings, HKICEAS Hong Kong International
Conference On Engineering and Applied Science, 2013, ISBN: 978-986-87417-4-4,
[6] Suaniti, N.M., Adnyana, I W.B. Pemanfaatan Jelantah Minyak Kelapa Sebagai Energi Alternatif:
Fatty Acid Ethyl Ester.Prosiding Seminar Nasional Sains dan teknologi, Denpasar 18-19
September 2014a, ISBN 978-602-294-018-0.
[7] Suaniti, N.M., Adnyana, I W.B., Sintesis dan Uji Angka Ester Biodiesel Jelantah Minyak Kelapa.
Prosiding Konferensi Nasional Engineering Perhotelan, 2014b, Vol. 1, No.2, Juli 2014, ISSN 2338414X
[8] Yahaya, M.F., Demshemino, I., Nwadike, I., Sylvester, O.P., and Okoro, L.N., A review on the
Chromatographic Analysis of Biodiesel, International Journal of Education and Research, 2013,
Vol 1, No. 8, p.1-12.
[9] Zajac G., Pickarski, W., Kizaczek, P., Comparison of an Effect FAME and FAEE Addition to Diesel
on Energetic Parameters of an Engine, Journal TEKA Kom. Mot. Energ. Roln-Ol PAN, 2008, 217223.