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Procedia Chemistry 9 (2014) 139 – 150

International Conference and Workshop on Chemical Engineering UNPAR 2013, ICCE UNPAR
2013

Synthesis of Renewable Diesel Through Hydrodeoxygenation Using

Pd/zeolite Catalysts
Bambang Heru Susantoa*, Mohammad Nasikina, Sukirnoa, Andri Wiyoa
a
Chemical Engineering Department-Universitas Indonesia, Kampus Baru Universitas Indonesia, Depok 16424, Indonesia

Abstract

Hydrodeoxygenation of oleic acid as model compound of vegetable oils over Pd/zeolite catalysts was investigated under
conditions of 375−400°C and 15 bar in a semi batch stirred autoclave reactor. Pd/zeolite-1 and Pd/zeolite-2 catalysts were
prepared using microwave polyol method with different treatment conditions. The liquid hydrocarbon products named
Renewable Diesel have suitable density and viscosity, and quite high cetane index in accordance with standard commercial
diesel and ASTM D-975. The IR spectrum of Renewable Diesel products have similarities with commercial diesel. The
oxygenation removal pathway of oleic acid over Pd/zeolite 1 catalyst was primarily compiled through decarboxylation at 375oC.

©©2014
2014The
TheAuthors. Published
Authors. by by
Published Elsevier B.V.B.V.
Elsevier This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection and peer-review under responsibility of the Organizing Committee of ICCE UNPAR 2013.
Peer-review under responsibility of the Organizing Committee of ICCE UNPAR 2013
Keywords: Hydrodeoxygenation ; oleic acid; Pd/zeolite ; Renewable Diesel

* Corresponding author. Tel.: +6285624202530 ; fax: +62217863515.

E-mail address: bambanghs@che.ui.ac.id

1876-6196 © 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of ICCE UNPAR 2013
doi:10.1016/j.proche.2014.05.017
140 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150

1. Introduction

Biodiesel production from trans-esterification of vegetable oils is currently the primary route for production of
biofuels from vegetable oils. Biodiesel as a type of oxygenated fuels is renewable fuel, biodegradable and non-
toxic, and has a higher flash point than petroleum diesel [2]. Furthermore, it has lower sulfur and aromatic
content, higher combustion efficiency, and higher lubricity than petroleum diesel [6]. However, biodiesel also has
higher viscosity, higher cloud point and pour point, higher nitrogen oxides (NOx) emissions, lower energy density,
and higher injector/engine wear [7]. With the inherent disadvantages of Biodiesel, it would be advantageous to
make a renewable fuel with the benefits of a biofuel (i.e., renewable, low sulfur, low aromaticity) but exhibiting
petroleum Diesel-like properties (lower cloud and pour points, lower NOx emissions, higher energy density, lower
engine wear). To avoid the disadvantageous physical properties of oxygenated fuels, hyrodeoxygenation of
vegetable oil has been investigated as an alternative pathway of biofuel production.
Hydrogeoxygenation belongs to a group of hydrotreating reactions and it means removal of oxygen from an
oxygen- containing compound under hydrogen pressure at high temperatures with the help of catalyst.
Hydrodeoxygenation includes a number of other reactions such as hydrogenation, cracking, decarbonylation and
decarboxylation. Hydrodeoxygenation can be a very expensive process due to the temperature and pressure
requirements to deoxygenate of 300-400oC with hydrogen pressure up to 200 bar. However, aromatic structures
can be preserved which yields a high octane fuel [10]. In hydrogenation process, C-O bond will be cut using H2
gas, the carboxylic functional group is disconnected into form of CO2 compound by decarboxylation process, and
CO and H2O compounds were released through decarbonylation process. Metal in catalyst and pressured hydrogen
is useful for saturation process of unsaturated carbon chains in triglycerides.
Forming reaction of Renewable Diesel involves catalyst to decrease the activation energy of the reaction and
increase its selectivity. The type of catalyst used in this study is Pd/zeolites catalyst which synthesized through
microwave polyol method. In recent time, microwave polyol method has been successfully used to produce nano-
sized catalysts for Pd/C and Pt/C catalysts. Several studies using microwave polyol method are: Boyas et al. [12]
synthesizing Pt/zeolite catalysts for the production of Renewable Diesel, He Li et al. [4] synthesizing Pd/C catalysts
for methanol electro-oxidation reaction, Amin et al. [1] synthesizing Pt/C catalysts for Fuel Cell applications, and
Feng Wu et al. [3] who observe the effect of the use of ethylene glycol in synthesizing nano-catalysts using
microwave polyol method. Studies above were using the same method but with different treatments. This study will
use the treatment performed by Jie Zhao et al. [5] and He Li et al. [4] to obtain the Pd/zeolite catalyst which will be
named as the Pd/zeolite-1 and Pd/zeolite-2 catalysts. Both of these catalysts will be observed and tested its activity
in hydrodeoxygenation reaction to produce Renewable Diesel.

2. Methodology

2.1. Materials

The following chemicals were commercially available and used as received : oleic acid (Bratachem Indonesia)
as a model compound of triglyceride, PdCl2 salt (Merck) and zeolite-Lampung (clinoptilolite type), HCl (Merck),
KBr (Merck), NaOH (Merck), KOH (Merck), ethylene glycol or EG (Merck) and glycerol (Bratachem Idonesia).

2.2. Catalyst Preparation (Treatment 1)

Pd/zeolite-1catalysts with the Pd loading of 5% were prepared by microwave polyol method in the solution of EG
polyols with PdCl2 as a precursor salt. 0.05 M H2PdCl4 at 50 ml was prepared by dissolving 0.2 M PdCl2 25 ml with
25 ml of 0.4 M HCl. The solution was then added to 50 ml of ethylene glycol. The mixture was added with 10 grams
of zeolite- Lampung (activated with 3 M HCl) and 0.8 M KOH. These mixture were then dispersed with ultrasonic
for 45 minutes. After ultrasonic treatment, the solution was put into a household microwave oven and then heated at
a temperature of 200°C for 3 hours.
 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150 141

2.3. Catalyst Preparation (Treatment 2)

Pd/zeolite-2 catalysts with the Pd loading of 5% were prepared by microwave polyol method in the solution of
EG polyols and glycerol. Zeolite-Lampung was impregnated with 25 ml of 0.196 M PdCl2 and added with 1.6648
M KBr 25 ml. After ultrasonic treatment for 1 hour, the mixture was added with 0.2 M NaOH at 25 ml. The mixture
was put into a household microwave oven and then heated for 2 minutes at 800W. Finally, the mixture was filtered,
washed with distilled water and ethanol and dried in oven for 12 hours at 60 oC.

2.4. Catalyst Characterization

The catalysts were characterized by XRD to determine the nature and type of crystal catalyst, Autosorb-6B BET
to determine area, pore size and pore volume of catalyst and SEM-EDX (JED-2300 Analysis Station JEOL) to
determine the morphology and composition of the catalyst.

2.5. Hydrodeoxygenation of Oleic Acid

The Hydrodeoxygenation of oleic acid was carried out in a 330 mL semi batch stirred reactor. The ratio of oleic
acid as model compound of vegetable oils and Pd/zeolite as catalyst was 100:1 The reactions were performed at
temperature between 375°C and 400°C and H2 pressure of 15 bar in batch stirred autoclave reactor. Every 15
minutes, the resulting gas was analyzed online by GC-TCD with adsorption column 6’ x 1/8’ SS packed with
molecular sieve to identify the carbon dioxide, carbon monoxide and methane. The bottom product was
distillated using Koehler Model K 45090 and characterized its physical properties such as : density (ASTM D86
using Stadbinger Densitometer), viscosity (ASTM D7042-04 using Viscometer SVM 3000) and cetane index. FT-IR
(Shimadzu) and GC-MS (Agilent) were used to identify functional groups and components in the
hydrodeoxygenation products respectively.

3. Result and Discussion

3.1. Results of Catalysts Characterizations

X-ray diffraction (XRD) pattern of Pd/zeolite-1 and Pd /zeolite-2 catalyts synthesized by microwave polyol
method is shown in Figure 1. The peaks that appear in both catalyst is in the same 2ߠ values. The peak which first
appears is the top constituent zeolite components such as SiO2 and Na(AlSi3O8) at a value of 2 θ=21.66 deg and 2
θ=22.42 deg of cristobalite and albite structures.

Fig. 1. Diffractogram of (a) Pd/zeolite-2 and (b) Pd/zeolite-1.

142 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150

The XRD shows that Pd/zeolite formed are crystalline. Crystal diffractograms which construct Pd/zeolite-1 has a
narrow peak and a high intensity compared with the diffractogram peak of Pd/zeolite-2. It shows that a well-
formed crystals of zeolite-metal crystals and Pd-metal crystal in the catalyst Pd/zeolite-1 are much more
crystalline than Pd/zeolite-2. This is caused by the low heating temperature of the Pd/zeolite-2 catalyst (60°C for 12
hours) so that the rate of solvent evaporation occurs only on the surface. This can allow the solvent trapped in the
pores of the zeolite, it is not entrained perfectly and imperfect crystals formed. The size of Pd nanoparticle
supported on zeolite (Pd/zeolite-1 and Pd/zeolite-2) estimated from the Debye–Scherrer formula are 23.40 nm and
90.94 nm.

Table 1. Testing Result of Catalyst Using BET

Surface Area (m2/g) Pore Size (Å) Pore Volume (cc/g)

Zeolite-Lampung 51.9 10.53 0.0045
Pd/zeolite-1 27.26 9.91 0.0139
Pd/zeolite-2 20.45 9.64 0.0098

BET shows that pore volume of the catalyst (Pd/zeolite-1 and Pd/zeolite-2) is greater than the unactivated natural
zeolite-Lampung. This result shows that the activation process on the physical and chemical pre-treatment of zeolite
successfully removed salts and alkaly-metal impurities which trapped in the pores of the catalyst. In catalysis
reaction, large volume is needed to achieve the complete reaction, as the pore volume is the site of the reaction
medium and can be regarded as a mini reactor. Furthermore, Table 1 shows the differences in the area of zeolite
before Pd metal embedded and zeolite after Pd metal embedded. zeolite had a very large area before embedded by
Pd metal, and slowly decreased after Pd metal entered into zeolite pores. This result is similar to the research
performed by Therdthianwong et al. [9].
Pd/zeolite-1 catalyst at heating temperature 200°C for 2 hours, had a surface area, pore size and pore volume
larger than Pd/zeolite-2 catalyst given heat treatment at a temperature of 60°C for 12 hours. This indicates that the
heating at low temperatures can not vaporize impurities and polyols solvent which were still trapped in the pores of
the zeolite. The obtained surface area of the catalyst was able to produce a fraction of collisions needed for the
hydrodeoxygenation reaction. This is confirmed later through several physical test of Renewable Diesel product
which show that the product was almost similar to the diesel specification.
From Figure 2, it can be seen that the Pd/zeolite-1 catalyst is still forming clots formed from a number of single
particles. Number of single particles dispersed on the surface was very little. This shows that the catalyst obtained
had a difference size. In general, the morphology of the resulting zeolite support in this study is similar to that
produced by the morphologic Maroufi et al. [11] with the same type of zeolite (clinoptilolite type).
For confirming the core content of the active Pd and other metals in the catalyst, it was identified using EDX.
The test result shows that the average yield active core Pd content in the catalyst was 4.09 wt%. This number is
almost close to the number of active nuclei were added during preparation. The test results can be seen in Table 2.
 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150 143

(a)

(b)

Fig. 2. Catalyst Morphology of Pd/zeolite-1 (a) 1000xMagnification and (b) 10000xMagnification

Table 2. Measuring Result of Pd/zeolite-1 Catalyst Using EDX.

Element Wt (%) Wt (%) Average

Particle A Particle B Particle C
Pd 3.90 6.14 2.25 4.09
O 47.83 38.68 50.51 45.67
Al 9.10 7.82 7.87 8.26
Si 39.17 47.35 39.37 41.96
144 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150

3.2. Renewable Diesel Synthesis With Hydrodeoxygenation Process

Activity catalyst test with hydrodeoxygenation process of oleic acid consisted of two main phases, namely
activation of the catalyst and hydrodeoxygenation reaction stages. The activation of catalysts was carried out
in order to provide selectivity performance during the reaction. Hydrodeoxygenation reactions were carried
out after the catalyst activation completed and the reactor temperature reaches 100oC. In this study, there were
produced 4 different liquid hydrocarbon products of Renewable Diesel, respectively are RD 1 (Pd/zeolite-2 at
375°C), RD 2 (Pd/zeolite-2 at 400°C), RD 3 (Pd/zeolite-1 at 375oC) and RD 4 (Pd/zeolite-1 at 400oC). The
resulting products can be seen in Table 3.

Table 3. Hydrodeoxygenation Reaction Products.

Product Bottom Product t Condensate

Color Viscocity Color Viscocity
RD 1 Black Liquid Colorless Liquid
RD 2 Black Liquid Yellow Liquid
RD 3 Black Liquid Colorless Liquid
RD 4 Black Liquid Yellow Liquid

The bottom product of hydrodeoxygenation of oleic acid was still in mixture and had to be purified through
distillation process. Distillation was carried out at a temperature in a range of 200oC Initial Boiling Point (IBP
200), 200-300°C and 300oC End Point (EP 300). Distillation products at temperature 300 EP were carried out
to determine the physical and chemical properties of Renewable Diesel product.

3.2.1. Density of Renewable Diesel

Fig. 3. Comparation of Density (Renewable Diesel, Diesel, Biodiesel and Oleic Acid)

From Figure 3 it can be seen that the density of Renewable Diesel is less than density of general biodiesel
standard [13] and slightly higher than the density of commercial diesel. Density of oleic acid decreased due to
oleic acid converted into Renewable Diesel. It shows that the cracking and hydrodeoxygenation reaction over
Pd/zeolite catalysts occurred. Renewable Diesel produced using Pd/zeolite-1 at 3750C (RD 3) has better density
quality than biodiesel and almost meet the specification of commercial diesel. This means that the oxygenation
removal pathway of oleic acid over Pd/zeolite 1 catalyst was primarily compiled through decarboxylation at 375oC.
 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150 145

3.2.2. Viscosity of Renewable Diesel

Oleic acid used as a reactant in the synthesis of Renewable Diesel has a very high viscosity before
hydrodeoxygenation. In Figure 4 it can be seen that the viscosity of oleic acid decreased after hydrodeoxygenation
occured to convert oleic acid into Renewable Diesel. It was caused by the carboxylate bonding termination of oleic
acid containing a carbonyl group (CO) and hydroxyl (-OH). Hydroxyl group in the carboxylic bond can form
hydrogen bonds with the carbonyl group (CO) which lead to stronger bonds between the molecules and the higher
viscosity.

Fig. 4. Comparation of Viscosity (Renewable Diesel, Diesel, Biodiesel and Oleic Acid)

The viscosity of the Renewable Diesel products (RD 1 to RD 4) have already met the standards which refer to
ASTM D- 975. The average viscosity obtained was 2.4 Cst which is on the range of standard viscosity ASTM D-
975 (1.9 to 4.1 Cst). In addition, the viscosity values generated by the Renewable Diesel product is much better
comparing with the standard viscosity of biodiesel based on Standard EN 14214 with a minimum viscosity 3.5 Cst.
Similar to the density analysis above, the use of catalysts Pd/zeolite 1 at 375oC is the optimum condition to obtain
Renewable Diesel product with a viscosity approaching commercial diesel density.

3.2.3. Cetane Index of Renewable Diesel

Cetane index measurements performed to estimate the cetane number in the fuel. The cetane index value will not
change if there is an addition some additive of cetane number into the fuel. Cetane index value is determined to find
out the quality of combustion, emissions and the ability of the fuel to combust at the low temperature. The
result of cetane index measurement can be seen in Table 4.

Table 4. Cetane Number of Renewable Diesel Products

Product Cetane Index

Renewable Diesel Diesel
RD 1 44.41 Minimum 40
RD 2 46.63 Based on ASTM D-975
RD 3 44.69
RD 4 40.19

Table 4 shows that the cetane index values of Renewable Diesel produced meet the minimum cetane index of
diesel fuel (ASTM-D975). In general, the products of both types of catalysts at reaction temperatures 375oC and
400oC have a very suitable cetane index value, even better than diesel. The cetane index value was strongly
influenced by the density and vapor temperature of Renewable Diesel read at the thermocouple.
146 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150

3.2.4. Identification of Functional Groups Using FTIR

The FTIR shows that Renewable Diesel, diesel and oleic acid have the same great absorption on the wavelength
2924 cm-1 and 2854 cm-1. Absorption at a wavelength of 2924 cm-1 indicates the presence of C-H and C-C bonds.
While, the absorption at 2854 cm-1 shows a typical absorption bands of aliphatic hydrocarbons, such as stretching
vibration asymmetry and symmetry of C-H. Based on the IR spectra, it can be indicated that those three ingredients
have a dominant hydrocarbon straight-chain compounds containing atoms C and H. Renewable Diesel, diesel and
oleic acid have the same absorption at wavelength 1458 cm-1. The Absorption occur due to the stretching vibration
of functional group-C = C-which shows the presence of an aromatic ring [14].

Fig. 5. Diesel, Renewable Diesel and Oleic Acid Spectrum.

Significant absorption at wavelength 3300 cm-1 occurs in oleic acid and does not occur in commercial diesel and
Renewable Diesel. Absorption at this wavelength indicates the presence of alkene group in oleic acid which was not
found in the Renewable Diesel product. This result shows that the catalytic hydrogenation reaction of oleic acid
achieved and produced Renewable Diesel which have saturated hydrocarbons. This reaction is described on the
following equation (1) [14].

(1)

IR absorption spectra in the wave number 1700 cm-1 occured in Renewable Diesel product, diesel and oleic acid.
It shows the stretching vibration absorption of carbonyl groups such as ketones, aldehydes and carboxylic acids.
Figure 5 shows that oleic acid has a wide IR absorption at these wave numbers which was indicated by the low
transmission percentage (%T = 20%). It shows that oleic acid used as a raw material still has a carbonyl group
(carboxylate group) which should be eliminated through hydrodeoxygenation. The IR absorption showed in small
quantities with high percentage transmission (%T = 50-55%) was detected in the measurements, indicated as an
aldehyde group resulting from the reduction reaction of carboxylic acids. This reaction is described in the equation
(2) [14].
 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150 147

(2)

In general, the result using FTIR shows that oleic acid used as a raw material was successfully converted into
Renewable Diesel and its IR spectra had similarities with IR diesel spectrum that was used as a standard.

3.2.5. Identification of Bottom Product Using GCMS

From Table 5, it can be seen that the liquid bottom products consist of hydrocarbon fractions (C1-C25) and
oxygenates such as acetone, alcohol, aldehyde, carboxylic acid, etc. The average mass percentage hydrocarbon
fraction was more dominant than the oxygenate fraction which was above 50%. C13-C19 fraction was the primary
hydrocarbons fraction contained in the bottom product suspected all as Renewable Diesel. The remaining oxygenate
fraction in the product could be used as an indicator in determining hydrodeoxygenation reaction. In this study,
hydrodeoxygenation of oleic acid produced the percentage of oxygenate contained in the product less than 50%

Table 5. Total Conversion, Total Hydrocarbon, Total Oxygenate and Total Percentage of Hydrocarbon Fraction (Selectivity and Yield).

Product Conversion Selectivity (%) Yield Total Total

(%) (%) Hydrocarbon Oxygenate
C5- C11- C13- C19- C5- C11- C13- C19- (%)
(%)
C11 C13 C19 C25 C11 C13 C19 C25
RD 1 91.44 9.71 11.50 40.27 6.79 8.28 9.81 34.35 5.79 56.34 43.66
RD 2 87.82 5.01 8.43 33.12 2.28 3.45 5.80 22.81 1.57 42.76 57.23
RD 3 90.23 14.88 10.78 42.70 1.03 12.15 8.80 34.87 0.84 60.81 39.19
RD 4 93.34 8.31 12.19 40.11 3.07 6.87 10.09 33.185 2.54 53.33 46.67

Sample 3 reacted at 375°C over Pd/zeolite-1 was a sample that produced the largest mass percentage of
hydrocarbon (60.81%) and smallest percentage of oxygenate (39.19%). Based on this result, it can be seen that the
operating conditions at 375°C using Pd/zeolite-1 were the appropriate conditions to produce Renewable Diesel with
the largest hydrocarbon content.
Hydrodeoxygenation produced bottom liquid product, condensate and gas. From Table 5 it can be seen that the
largest conversion of reactants occurred at RD 4 products. However, it did not guarantee that RD 4 has the largest
selectivity and yield of C13-C19 Fraction. It can be seen from Table 4 that RD 3 has the largest selectivity and yield
of C13-C19 fraction, which is 42.72 % and 34.87 %.

3.3. Effect of Temperature and Catalyst on Distribution Product

To test the dependence of the hydrodeoxygenation on temperature and catalyst, a number of reaction runs
were conducted at temperatures at 375oC and 400oC. The batch stirred autoclave reactor was charged with H2 so that
the pressure at the reaction temperature was 15 bar. The results of oleic acid hydrodeoxygenation are gathered in
Figure 6 and 7, where RD 1 (Pd/zeolite-2 at 375°C), RD 2 (Pd/zeolite-2 at 400°C), RD 3 (Pd/zeolite-1 at 375oC) and
RD 4 (Pd/zeolite-1 at 400oC).
From Figure 6 shows that with increasing temperature at the constant H2 pressure, the rate of CO2
formations (decarbocylation reaction) were more dominant than the rate of formation of CO (decarbonylation
reaction) and methane gas (side reaction/methanation). It means that in the parameter range analyzed,
decarboxylation was predominant and Pd/zeolite catalysts were selective to be used for hydrodeoxygenation of
oleic acid. The temperature of 375oC was the optimum reaction temperature to break carboxylic groups on the
reactants compared to the reaction temperature at 400 oC. It can be seen on the curve 6(a) and 6(c) where the
percentage of volume generated at the optimum temperature of 375°C is ± 60% (v/v) which is ten percent higher
than the percent volume produced at a temperature of 400 oC.
148 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150

(a) (b)

(c) (d)

Fig. 6. Gas Rate Formation Curve (a) RD 1, (b) RD 2, (c) RD 3, (d) RD 4

(a) (b) (c)

Fig. 7. Gas Rate Formation Curve (a) Methane, (b) Carbon Monoxide and (c) Carbon Dioxide

From figure 7 shows that utilization of Pd/zeolite-1 and Pd/zeolite-2 as catalyst in the hydrodeoxygenation of
oleic acid at temperature of 375oC and 400oC had almost the same capabilities in directing path of reaction to
decarboxylation. The difference between the two catalysts at the same temperature condition was the ability to
control the side reaction such as water gas shift and methanation. From figure 7a, it can be seen that the catalyst
Pd/zeolite-1 was able to suppress the rate of methane formation greater than Pd/zeolite-2. Similarly, the catalyst
Pd/zeolite-1 was able to control the formation rate of CO gas greater than Pd/zeolite-2 either at temperature of
375 oC or 400oC (figure 7.b). This result shows that the Pd/zeolite-1 catalyst has some characteristics that better than
Pd/zeolite-2 catalyst and has a great influence in directing the reaction path to decarboxylation during the
hydrodeoxygenation process.
The effect of temperature in the product distribution can be seen in figure 8. The results confirm that at
constant pressure (15 bar) an increase temperature, from 375 oC to 400oC, favors the production of condensate
rather than bottom liquid product. It means that product of renewable diesel at temperature of 400oC could be lower
than that at temperature of 375oC.
 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150 149

Fig. 8. Comparation of Gas, Condensate and Bottom For Each Product

Fig. 9. Comparation of Conversion, Selectivity and yield For Each Product

Figure 9 summarizes the effect of temperature and catalyst on the conversion, selectivity and yield of renewable
diesel. In general, the variation of the catalyst and the operating temperature produced high conversion even though
the selectivity and yield was still low. Selectivity and yield of the four samples were strongly influenced by the
reaction temperature. The yield and selectivity has been observed to rise at an optimum temperature of 375 oC but
with the increase in temperature yield reduces either using Pd/zeolite-1 or Pd/zeolite-2.

4. Conclusion

The Synthesis of Catalysts Pd/zeolite using treatment 1 was suitable in synthesizing Pd/zeolite catalysts
through microwave polyol method. Catalyst Pd/zeolite-1 produced from treatment 1 had a high crystalline with
Pd crystallite size 23.40 nm and has a surface area of 27.26 m2/g, pore size and pore volume 9.91 Å and 0.0139 cc/g.
FTIR shows that oleic acid used as a raw material successfully converted into the Renewable Diesel and its IR
spectra of Renewable Diesel products have similarities with IR diesel spectrum used as the standard in this study.
The average mass percentage of oxygenate in the product was less than 50%, the density and viscosity were
below the value of biodiesel standard (EN-14214) and on the range of values of commercial diesel standard
(ASTM D-975) and also, the cetane index obtained is above the lower limitation of commercial diesel cetane index
(ASTM D-975). It means the oxygenation removal pathway of oleic acid over especially Pd/zeolite-1catalyst was
primarily compiled through decarboxylation
150 Bambang Heru Susanto et al. / Procedia Chemistry 9 (2014) 139 – 150

Hydrodeoxygenation of oleic acid for synthesizing Renewable Diesel was performed on two Pd/zeolite
catalysts. The main conclusions derived from this work are the following: Both Pd/zeolite-1 and Pd/zeolite-2
catalysts show quite good performance at temperatur of 375 OC and H2 pressure of 15 bar : significantly they have
suitable density and viscosity and quite high cetane index.

Acknowledgements

Directorate General of Higher Education- Indonesia Ministry of Education and Culture through Riset Madya UI
2012 is acknowledged for the financial support to carry out the present study.

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