UTILIZATION OF Na2O/Fe3O4 AS CATALYST IN TRANSESTERIFICATION STAGE

OF OFF - GRADE PALM OIL TO BIODIESEL

ABSTRACT

Off-grade palm oil is a source of vegetable oils that utilization is not maximized yet. It has ALB
> 2% so must be process with esterification and transesterification. In general, biodiesel is
produced through transesterification reactions using homogeneous catalysts. Homogeneous
catalysts can be replaced with heterogeneous catalysts with easily separated and environmentally
friendly. Waste iron powder can be used as catalyst support and provide metallic properties for
separate product easily. This study aims to create a catalyst that has metallic properties and to
study the transesterification reaction process conditions at transesterification process.
Esterification process were reacted at 60 °C with time reaction 1 hour, molar ratio of methanol :
oil of 12:1 and 1% H2SO4-w catalyst. The esterification reaction can reduce levels of ALB from
11.95% to 1.44%. Transesterification conducted with the molar ratio of methanol : oil in a row
are 6:1, 8:1, and 10:1, the amount of catalyst modification 1% -w, 2%-w, 3% -w, a reaction
temperature of 50 °C, 60 °C , 70 °C, and the reaction time 3 hours. Processing data using
Response Surface Methodology (RSM), while the number of experiment are determined by
Central Composite Design (CCD). Yield was resulted in ranging from 22.34% to 59.92%. The
highest yield obtained at 60 °C with molar ratio of methanol : oil is 8:1 and the amount of
catalyst Na2O/Fe3O4 2%-w.

Keywords : biodiesel, heterogeneous catalyst, off-grade palm, RSM, transesterification

1. INTRODUCTION

Biodiesel is an alternative fuel for diesel engines produced by reacting oils derived from
plants or animal fats with alcohols such as methanol through transesterification reactions. The
advantages of biodiesel compared to diesel / diesel fuel are more environmentally friendly,
biodegradable, continuity of guaranteed, non-toxic raw material availability, resulting in fewer
harmful exhaust gases than diesel such as sulfur dioxide (SO2) carbon monoxide (CO), carbon
dioxide (CO2), unburned hydrocarbons and other carbon particles, and has a higher flash point
making it safer in handling and storage [Taufiq et al., 2011; Knothe et al., 2005].
Commonly used catalysts in the transesterification process are basic or acidic solutions
(such as KOH, NaOH, and H2SO4) and may be either homogeneous or heterogeneous catalysts.
The use of homogeneous catalysts has several disadvantages such as the difficulty of separating
the catalyst from the product because the homogeneous catalyst is at the same phase as the
reactants and products, and the homogeneous catalyst cannot be reused after the reaction
[Helwani et al., 2009]. The basic homogeneous catalyst can react with free fatty acids (FFA) to

1
form soap. The formation of this soap will complicate the separation of glycerol and will reduce
the yield of biodiesel. The acid catalyst can cause corrosion of the process tools and is toxic and
requires a long reaction time and requires a higher methanol and oil molar ratio [Taufiq et al.,
2011].
Such homogeneous catalysts can be replaced with heterogeneous catalysts that are more
environmentally friendly, more easily separable, and reusable. However, there is a limitation of
the use of heterogeneous catalysts, which have a slower reaction rate than homogeneous catalysts
and the surface surfaces of rapidly poisoned catalysts when exposed to the environment due to
reactions of CO2 and H2O on the surface of the site [Taufiq et al., 2011]. Thus, research on
heterogeneous catalysts is expected to be further developed.
In this research will be used heterogeneous catalyst in the form of NaNO3 / iron powder
with off grade palm as raw material. The use of iron powder as a support is to facilitate the
separation of the catalyst because iron is ferromagnetic and iron powder can prevent the
formation of hydrogen bonds that can reduce the purity of glycerol and complicate the separating
process of biodiesel. Utilization of iron powder waste as catalyst support in biodiesel production
is still in the process of development so further research is needed.
Making biodiesel using a heterogeneous catalyst is also done by Martinez et al., [2013]
with raw materials of sunflower oil. The heterogeneous catalyst is a NaX zeolite modified with
Na2O by impregnation and calcination processes. Biodiesel with maximum yield of 99.3% was
obtained at Na content in catalyst by 10%, reaction temperature 60oC, methanol molar ratio: oil
6: 1, reaction time 6 hours, and catalyst concentration 10% -b. High yields but long reaction
times and the use of NaX synthesis zeolites require the initial treatment of calcination at 500 ° C
for 10 hours before impregnation, requiring greater energy.
To overcome these problems, this research uses off grade palm oil with Na2O
heterogeneous catalyst from NaNO3 with Fe3O4 support from iron powder waste for
transesterification reaction. The operating conditions change in the ratio of methanol molar: oil,
reaction temperature, and catalyst concentration. It is expected that the separation of the catalyst
from the product will be easier and can increase the value of palm off grade and iron powder
waste.

2
2. METHODS
The materials used in this research are off grade palm oil derived from extraction,
distilled water, methanol pa (MERCK EMSURE CAS 67-56-1), iron powder waste, NaNO3
(MERCK EMPLURA 7631-99-4), H2SO4 98 % (MERCK EMSURE CAS 7664-93-9), aquadest,
technical ethanol (BRATACO), KOH (MERCK EMSURE CAS 1310-58-3), PP indicator, and
oxalic acid (MERCK EMSURE CAS 6153-55-6)
The extraction process of palm oil off grade is done by using spindle hydraulic press,
stove and cage, and separating funnel. The catalyst preparation process consists of 500 ml
erlenmeyer, heater, thermometer, oven, and furnace. In the process of making biodiesel from off
grade palm oil using a three-neck flask with a capacity of 500 ml as a batch reactor equipped
with a condenser and thermometer. For heating and stirring process use a heating mantle with
magnetic stirrer. As for the separation and purification of biodiesel using separating funnel.
2.1 Research Procedures
The manufacture of biodiesel from off grade palm oil is carried out in several stages
including off grade palm oil extraction process, making NaNO3 / iron powder catalyst, biodiesel
manufacture, biodiesel separation and purification. The constantly guarded process conditions
are 100 g oil weight, for esterification reactions including 1 hour reaction time, 1% b catalyst
concentration, ratio molar of methanol : oil 12: 1 and 60oC reaction temperature. [Naluri et al.,
2015]. In the transesterification reaction the reaction time is 3 hours. The process conditions
varied were catalyst concentrations of 1% b, 2% b and 3% b, methanol molar ratio: oil 6: 1, 8: 1,
and 10: 1 and reaction temperatures of 50°C, 60°C and 70°C. For more details, the procedure for
making biodiesel from off grade palm is shown in Figure 1
Biodiesel separation and purification
After transesterification is complete, the catalyst is separated from biodiesel by attaching
a magnet outside the reactor wall so that the catalyst is attracted and separated from the biodiesel
[Liu et al., 2010]. The solution of the transesterification reaction which has been separated from
the catalyst is then inserted into the separating funnel and allowed to form two layers. The top
layer of crude biodiesel and the remaining methanol of the reaction are separated from the lower
layers of glycerol. Crude biodiesel is purified by washing with aquadest to clear wash water. The
biodiesel was dried in a 105oC temperature oven for 60 minutes to evaporate the reaction and
water remaining methanol, then weighed to determine the yield of biodiesel produced and the

3
yield calculated by 1 [Hayyan et al., 2011]. Biodiesel is analyzed to know its characteristics as
acid number, density, viscosity and flash point [Budiawan et al., 2013].

Palm off grade

Ecstraction Oil cake

Oil
(FFA > 2 %)
Methanol H2SO4

Esterification

Excess methanol,
Separation
H2SO4, water

Oil
(FFA <2%) Na2O/
Methanol Fe3O4
Transesterification

Glycerol and
Catalyst Separation
residual methanol

Crude
Biodiesel

Purification Aquadest

Glycerol,
Separation aquadest, and
residual methanol

Biodiesel

Figure 1. Procedure of Making Biodiesel from Palm Off grade

4
3. RESULTS AND DISCUSSION
This chapter contains an analysis of the results of Na2O / Fe3O4 utilization as a catalyst
for off grade palm transesterification reaction to biodiesel, catalyst preparation and discussion of
catalyst characteristics including basal values and X-RD analysis, biodiesel yield, biodiesel
characteristics, and optimum conditions obtained.
3.1 Off Grade Palm Extraction
Palm off grade used is a type of fruit palm through mature and rotten. Loose fruits off
grade palm that has been separated from the bunches washed and steamed first. After steaming,
the fruit is extracted using a spindle hydraulic press tool. Oil obtained then analyzed levels of
FFA and water content. The analysis is necessary to determine the initial treatment required for
the biodiesel manufacturing process.
The results showed that the water content of palm oil off grade was 1.58% higher than
the tolerance limit of SNI 01-2901-2006 standard which is small from 0.5%. The high water
content of the feedstock can cause hydrolysis of the oil to be one of the causes of increasing FFA
levels and water can react with the catalyst causing the catalyst to decrease so as to reduce the
yield of biodiesel [Ulfayana and Helwani, 2014]. FFA levels of off grade palm oil are analyzed
very high i.e. 11.95%, thus requiring pretreatment of oil before proceeding to the
transesterification process that is by esterification.
3.2 FFA Conversion on Esterification Reactions
The esterification reaction is performed to decrease FFA levels in off grade palm oil. The
esterification reaction uses the operating conditions adopted from Naluri et al. [2014] and
Budiawan, et al. [2013]. The reaction runs at a temperature of 60°C with a molar ratio of
methanol: 12: 1 oil and 1% b H2SO4 catalyst can decrease FFA to 1.44%. FFA on off grade palm
oil has been converted to methyl ester by 87.95%. The results are almost the same as the research
done Naluri, et al. [2015] capable of converting 89.8% FFA of palm oil off grade to methyl ester
under the same operating conditions.
3.3 Catalyst Preparation and Catalyst Characteristic Test
The analyzed catalyst was analyzed by using Hammet indicator, then crystallinity test
using X-ray Diffraction (XRD) tool. basicity analysis using Phenolptalein indicator with H_ =
9.3. The results obtained purple color. This indicates that the basicity of the catalyst is H_> 9.3

5
and proves that the catalyst obtained is basic so that it can be used in the off grade palm oil
transesterification reaction [Helwani et al., 2013; 2016].
This modified crystallization catalyst test used X-ray Diffraction (XRD) tool at
Universitas Negeri Padang (UNP). XRD pattern of catalyst after calcination at 550oC for 4 hours
is shown in Figure 6. The result of the analysis in Figure 2 shows that some peaks show FeNaO2
in accordance with data from JCPDS (Joint Committee on Powder Diffraction Standards). 74-
1351 i.e. at position 2 = 19.94o, 20.69o, 26.04o, 29.71o, 31.58o, 33.92o, 38.06o, 46.45o, 51.19o,
54.74o, 60.01o and 65.73o with the highest peak at position 2 = 29.71o. The formation of
FeNaO2 indicates that NaNO3 on the surface and Fe3O4 matrix change to FeNaO2 during the
activation process. Fe3O4 is formed in the position of 2 = 18.3o, 30.03o, 35.4o, 36.99o, 42.93o,
53.47o, 56.82o, and 62.75o with the highest peak at 2: 35.4o (JCPDS No. 19-0629). The α-Fe2O3
phases are formed at the position of 2 = 24.19o, 33.06o, 35.53o, 40.88o, 49.63o, 54.3o, 57.64o,
and 64.1o with the highest peak at 2 position: 33.06o (JCPDS No. 80-2377). The formation of α-
Fe2O3 due to Fe3O4 was oxidized after calcination at 550°C for 4 hours [Tang, et al. 2012].
While the Na2O phase formed at the position of 2 = 32.12o, 46.27o, and 67.61o with the highest
peak in the position of 2: 32.12o (JCPDS No. 23-0528).

Figure 2. XRD Pattern Na2O / Fe3O4 Catalyst After Calcined at 550oC, 4 hours

6
3.4 Yield and Biodiesel Characteristics
a. Yield of Biodiesel
The yields ranged from 22.34% to 59.92%. The largest yield is produced under 60oC
temperature process conditions, molar ratio of methanol and oil 8: 1 and 2% catalyst weight w/w.
This result is much smaller than the yield of biodiesel from NaOH / Al2O3 catalyst with palm
kernel raw material that is 99% [Taufiq et al, 2011]. This is due to the amount of NaNO3 catalyst
impregnated with Fe3O4 small. According to Liu et al. [2010] the amount of catalyst implanted
has an effect on the yield produced, if too little, the active site of the catalyst is less so the
resulting yield is small. Therefore, further research on the proportion of Na2O from NaNO3 in
Fe3O4 is required in order to obtain a catalyst which can produce a large yield. In addition,
Taufiq et al [2011] used a larger ratio of methanol molar:oil of 15: 1 while this study used a
molar ratio of methanol and oil 8: 1.
b. Biodiesel Characteristics
The obtained biodiesel was tested to determine its characteristics to compare with
predetermined standards to be commercially marketed. Characteristics tested were density,
kinematic viscosity, acid number and flash point. Test results of biodiesel characteristics with
characteristics based on SNI 04-7182-2006 are shown in Table 1
Table 1 Characteristics Comparison of Biodiesel Research Results with Biodiesel
SNI 04-7182-2006
Biodiesel Research SNI
Characteristic Unit
Results 04-7182-2006
Density Kg/m2 887,59 850 – 890
Kinematic Viscosity mm2/s 5,11 2,3 – 6,0
Acid Number mg-KOH/g-biodiesel 0,42 Maks. 0,8
o
Flash Point C 173 Min. 100

The characteristics shown in Table 1 indicate that the resulting biodiesel meets the
quality requirements set by the National Standards Agency/ Badan Standar Nasional (BSN).
Density is related to the amount of oil that is measured on the machine system. The machines
circulating in the community have a system volume setting so that if the biodiesel oil density
passes or is less than standard then the fuel injected is not appropriate and this will cause damage
to the engine. Viscosity is a parameter that indicates the performance of the fuel at the engine
injection. Viscosity that exceeds the standard will cause the difficulty of fuel flowing in the

7
injection so that there is a blackout during burning on the machine. The acid number is a measure
of the amount of acid present in the fuel. Figures below the standard acid that is a maximum of
0.8 mg-KOH / g-biodiesel indicates the biodiesel is not corrosive so as not to cause damage to
the injector engine. Test results obtained flash point from biodiesel products are173oC. The high
flash point of SNI makes biodiesel safe in storage and handling. The biodiesel SNI establishes a
minimum of 100°C to eliminate methanol contamination from the imperfect conversion of
vegetable oils [Knothe et al., 2005].
In addition to the analysis of biodiesel characteristics in Table 1 there is an analysis of the
chemical properties of biodiesel that is composition of methyl ester compounds. The oil
produced from various sources will give each specification so that the biodiesel produced will
have different characteristics. This difference is due to the fatty acid composition and the type of
fatty acids present in the raw material [Budiawan et al., 2013]. Fatty acid composition of CPO
can be seen in Table 2
Table 2 Fatty Acid Composition of CPO
Fatty Acid Percentage (%)
Myristic 0,9
Palmitic 47,6
Stearic 2,5
Oleic 41
Linoleic 8
Other (Unknown) 2,3
Sumber: Suppalakpanya, dkk. 2011

From Table 2 it can be concluded that the largest fatty acid composition is palmitate acid
and oleic acid. Some fatty acids such as linoleic, stearate and myristate are also detected with a
small percentage.
Table 3 Result of GC-MS Analysis Chemical Composition Biodiesel Research Results
Retention Time
Peak Compund Area Area (%)
(minute)
1 26.900 Methyl Myristate 299,136 1.19
2 31.094 Methyl palmitate 14,397,883 57.16
3 35.010 Methyl stearate 504,539 2.00
4 35.512 Methyl oleic 8,105,072 32.17
5 36.631 Methyl Linoleic 1,884,177 7.48

8
 Analysis of biodiesel characteristics of the composition of methyl esters formed by Gas
Chromatography-Mass Spectrometry (GC-MS) at the Organic Chemistry Laboratory - UGM is
shown in Table 4 GC-MS analysis of Table 4shows some of the organic compounds contained in
the biodiesel sample. It can be seen that there are 2 fatty acids in the most converted oil to
biodiesel and the overall peak in Figure 7 is a methyl ester compound indicating the purification
of biodiesel is done well. Based on peak area percentage, it can be interpreted that most of the
methyl ester compounds formed by using Na2O / Fe3O4 catalyst are Methyl Palmitate (57,16%)
and Methyl Oleic (32,17%). These esters are fractions of the fatty acid constituents of
triglycerides in CPO according to the composition of fatty acid constituent CPO in table 3

Figure 3. Result of GC-MS Analysis of Biodiesel Research Results

Effect of Process Conditions and their Interaction on Biodiesel Yields

a. Effect of Process Conditions on Biodiesel Yields
Based on P-value testing, reaction temperature is a process condition that has a
significant influence on biodiesel yield. Figure 4 (a) shows that the higher the reaction
temperature the higher yield the biodiesel produces. Increased reaction temperature can cause the
number of collisions between particles getting bigger so that the reaction is faster and produce
high biodisel yield [Hikmah and Zuliana. 2010]. However, the increase in biodiesel yields is only
up to 60 ° C when the reaction temperature is increased biodiesel yield decreases.

9
 Taufiq et al., [2011] and Naluri et al., [2015] obtained the highest biodiesel yield at 60oC
reaction temperature and when the reaction temperature was increased the yield of biodiesel
became reduced. This occurs because at this temperature has passed the boiling point of
methanol 65oC, so some methanol undergoes phase change from liquid to gas. The occurrence of
this methanol phase change causes the amount of methanol in the liquid phase to decrease so that
the number of effective collisions to produce biodiesel is reduced [Taufiq et al., 2011].

Figure 4 Relation (a) Reaction Temperature, (b) Methanol Molar Ratio: oil, and (c) Number of Catalysts
on Biodiesel Yield.

Figure 4 (b) shows that the graph increases the molar ratio of methanol: oil is
proportional to the yield of biodiesel. The increased yield on the addition of the methanol molar
ratio: oil from 6: 1 to 8: 1 increases drastically biodiesel yields. However, the addition of

10
methanol molar ratio: 10: 1 oil does not significantly affect the yield of biodiesel. According to
Taufiq et al., [2011] the addition of excess methanol aims to move the reaction toward the
product because the transesterification reaction is an equilibrium reaction. Naluri et al., [2015]
using the molar ratio of methanol: oil of 8: 1 obtained biodiesel yield of 96.99%. Taufiq et al.,
[2011] using molar ratio of methanol: oil of 15: 1 obtained biodiesel yield of 99%.
Taufiq, et al. [2015] conducted a study using NaOH / Al2O3 catalyst with catalyst
concentration variations of 1% b, 2% b, 3% b, 4% b and 5% b. From the results of his research
showed the highest yield of biodiesel obtained at concentration 3% b. Naluri, et al. [2015]
varying the catalysts of 2% b, 4% b, and 6% b, obtained maximum yield on the addition of 4%
catalyst b. In this study obtained maximum yield on the addition of 2% catalyst b. Increasing the
amount of catalyst to 3% b causes the yield to fall. This is because the greater the concentration
is given the more soap that is formed that causes the yield biodiesel decrease. Soaping will make
separation of biodiesel by glycerol more difficult thereby causing emulsion forming. Some
biodiesel is trapped in the emulsion so that when the purification of trapped biodiesel is wasted
along with washing water.

b. Effect of Process Condition Interaction on Biodiesel Yield

The result of P-value test shows that the interaction between temperature and the number
of catalyst (X1X3) has significant effect on biodiesel yield. The interaction between temperature
and number of catalysts against biodiesel yields is shown in Figure 10 in the form of three-
dimensional graphs (3D) (a) and two-dimensional contours (b).
The 3D graph and contour in Fig. 5 show the effect of reaction temperature interaction
and the amount of catalyst on the molar ratio of methanol and oil of 8: 1. In a 2% b catalyst, the
yield of biodiesel produced is greater at the reaction temperature of 50oC to 60oC when
compared to the larger reaction temperature. So it can be concluded that the higher reaction
temperature does not have a positive effect on the biodiesel manufacturing process. While the
influence of the amount of catalyst did not contribute significantly, but greater yield was
obtained in the addition of 2% catalyst.

11
Figure 5 Effect of Interaction between Temperature and Number of Catalysts on Biodiesel Yield
in 3D Graphic Form (a) and Contour (b).

Prediction of Optimum Biodiesel Yield

Determination of optimum process conditions is determined by the coefficient of
equation 1. The optimization process is done by finding the stationary point by assuming that the
stationary point as the optimum process conditions. From the calculation result (Appendix C),
obtained stationary point value for reaction process temperature conditions (x1.0) = 0.26; molar
ratio of methanol: oil (x2.0) = 0.53; and the amount of catalyst (x3.0) = -0.07. The predicted yield
of maximum biodiesel is at point Y = 58.11% at optimum reaction process temperature 57.4oC,
methanol molar ratio: oil 6.94: 1, and amount of catalyst 2.07%. The optimum value equation for
the optimum biodiesel yield prediction is shown in equation 1
Y = 56.04 + 0.26X1 + 0.53X2 - 0.07 X3 .............................................. (1)

CONCLUSIONS
Based on the results of research conducted, it can be concluded as follows:
1) XRD results show that FeNaO2 catalysts can be prepared using iron powder waste as a
source of Fe3O4 and NaNO3 as the precursors of Na2O.
2) The esterification reaction under 60oC operating conditions with methanol molar ratio: 12: 1
oil and 1% of H2SO4 catalyst can decrease FFA levels in off-grade palm oil from 11.95% to
1.44%.

12
3) Transesterification reaction yields biodiesel yields ranging from 22.34% to 59.92%. The
highest yield was obtained at 60°C with the molar ratio of methanol: oil of 8: 1, and the
amount of 2% w/w Na2O / Fe3O4 catalyst.
4) P-value test results show that operating conditions that have significant effect are reaction
temperature (50oC, 60oC, and 70oC) and molar ratio of methanol: oil (6: 1, 8: 1 and 10: 1).
While the amount of catalyst (1%, 2%, and 3%) did not give a significant effect.

Suggestions
Based on the results of the research, further research on catalyst and carrier composition
and the preparation of Na2O / Fe3O4 catalysts prior to use in the transesterification reaction to see
the effectiveness of catalyst performance

REFERENCES
Budiawan, R., Zulfansyah, W. Fatra and Z. Helwani, 2013, Off Grade Palm Oil as a Renewable
Raw Material for Biodiesel Production by Two-Step Processes, ChESA Conference, Banda
Aceh, 7, 40-50.
Hayyan, A., Md. Z. Alam, M.E.S. Mirghani, N.A. Kabbashi, N.I.N.M. Hakimi, Y.M. Siran and
S. Tahiruddin. 2011. Reduction of Hight Content of Free Fatty Acid in Sludge Palm Oil via
Acid Catalyst for Biodiesel Production, Fuel Processing Technology 52, 920 – 924.
Helwani, Z., M.R. Othman, N. Aziz, J. Kim, and W. J. N. Fernando, 2009, Solid Heterogeneus
Catalyst for Transesterification of Triglyerides with Methanol, Applied Catalysis A :
General, 369, 1 -10.
Helwani, Z., N. Aziz, M. Z. A. Bakar, H. Mukhtar, J. Kim, and M. R. Othman. 2013. Conversion
of Jatropha Curcas Oil into Biodiesel Using Re-Crystallized Hydrotalcite. Energy
Conversion and Management, 73, 128 – 134.
Helwani, Z., N. Aziz, J. Kim, and M. R. Othman. 2016. Improving The Yield of Jatropha
Curcas’s FAME Through Sol-Gel Derived Meso-Porous Hydrotalcites. Renewable Energy,
86, 68 – 74.
Hikmah, M.N., and Zuliyana, 2010, Pembuatan Metil Ester (Biodiesel) dari Minyak Dedak and
Metanol dengan Proses Esterifikasi and Transesterifikasi, Undergraduate Thesis,
Universitas Diponegoro, Semarang.
Ho, W. W. S., Ng, H. K., S. Gan, and S. H. Tan, 2014, Evaluation of Palm Oil Mill Fly Ash
Supported Calcium Oxide as A Heterogeneous Base Catalyst in Biodiesel Synthesis from
Crude Palm Oil, Energy Convertion and Management, 88, 1167-1178.
Kasim, R., 2010, Desain Esterifikasi Menggunakan Katalis Zeolit pada Proses Pembuatan
Biodiesel dari Crude Palm Oil (CPO) Melalui Metode Dua Tahap Esterifikasi –
Transesterifikasi, Thesis, Institut Pertanian Bogor, Bogor.
Knothe, G., J.V. Gerpen, and J. Krahl, 2005, The Biodiesel Handbook, AOCS Press, United
States of America.

13
Kumar, D., G. Kumar, Poonam, and C.P. Singh, 2010, Ultrasonic-assisted Transesterification of
Jatropah Curcus Oil using Solid Catalyst, Na/SiO2, Ultrasonic Sonochemistry, 17, 839-844.
Liu, C., P. Lv,Z. Yuan, F. Yan and W. Luo, 2010, The Nanometer Magnetic Solid Base Catalyst
for Production of Biodiesel, Renewable Energy, 357, 1531-1536.
Martinez, S.L., R. Romero, R.Natividad, and J.Gonzales, 2013, Optimation of Biodiesel
Production from Sunflower Oil by Transesterification using Na2O/NaX and Methanol,
Catalyst Today, 220-222,12-20.
Montgomery, D.C., 1991. Design and Analysis of Experiments 3rd edition. John Wiley and Sons
Inc. Singapore.
Naluri, A., H. Rionaldo, and Z. Helwani, 2015 Sawit Off Grade sebagai Bahan Baku Alternatif
Pembuatan Biodiesel melalui Proses Dua Tahap menggunakan Katalis Zeolit Alam yang
Dimodifikasi, JOM FTeknik, 2, 2.
Nugroho, D.A., Zulfansyah and Z. Helwani, 2013, Ekstrasi Sawit Off Grade Menggunakan
Metode Artisanal, Undergraduate Thesis, Universitas Riau, Pekanbaru.
Suppalakpanya, K., S. Ratanawilai, R. Nikhom, and C. Tongurai. 2011. Production of Ethyl
Ester from Crude Palm Oil by Two-Step Reaction using Continuous Microwave System.
Songklanakarin Journal of Science and Technology, 31,79-86
Tang, S., L. Wang, Y. Zhang, S. Li, S. Tian, and B. Wang. 2012. Study on Preparation of
Ca/Al/Fe3O4 Magnetic Composite Solid Catalyst and Its Application in Biodiesel
Transesterification. Fuel Processing Technology, 96, 84 – 89.
Taufiq, Y.H, N.F. Abdullah, and M. Basri, 2011, Biodiesel Production via Transesterification of
Palm Oil using NaOH/Al2O3 Catalysts, Sains Malaysiana 40, 587-594.
Ulfayana, S and Z. Helwani. 2014. Natural Zeolite for Transesterification Step Catalyst in
Biodiesel Production from Palm Oil Off Grade. Regional Confererence on Chemical
Engineering. Yogyakarta
Xie, W., and H. Li, 2006, Alumina Supported Potassium Iodide as a Heterogeneous Catalyst for
Biodiesel Production from Soybean Oil, Journal of Molecular Catalysis A: Chemical 255,
1-9.

14