The 2nd Indonesia Chemical Engineering Paper Competition - ITS - 2017 1

Geothermal Sludge-Derived Calcined Sodium Silicate

as Heterogeneous Catalyst for Biodiesel Production
from Waste Cooking Oil
Reza Hendy Djoerkaeff, Agnes Martha .L, I Made Bendiyasa*
Department of Chemical Engineering, Universitas Gadjah Mada
Jl. Grafika 2, Bulaksumur, Yogyakarta 55281, INDONESIA
e-mail: reza.hendy.d@mail.ugm.ac.id

Abstract. As one of the most important renewable resources, palm oil has significant advantages in terms of our environment
protection. Trans-esterification process used to produce biodiesel from palm oil (waste cooking oil), bears a large potential for the
substitution of fossil diesel. Biodiesel is proved to be the best replacement for diesel because of its unique properties like significant
reduction in greenhouse gas emissions, non-sulfur emissions, non-particulate matter pollutants, low toxicity and biodegradability.
Therefore, the employment of waste oils as feedstock for biodiesel production are presented as the best alternative. However, the
presence of free fatty acids (FFA) in these oils is undesirable for biodiesel production due to the trans-esterification reaction
performance is reduced. Hence, in this paper, the adsorption as treatment for reducing or removing FFA from oils prior to trans-
esterification reaction for biodiesel production is examined using a strong anion-exchange resin. The use of solid base catalyst in
biodiesel production is becoming preferable because of their superiority advantages over the conventional homogeneous catalyst.
Calcined Sodium silicate is applied to catalyze trans-esterification reaction of palm oil with methanol. A strong base catalyst of
sodium silicate synthesized from geothermal sludge of Dieng Geothermal Power Plant (Indonesia), which has 55% of silica content
by gelation method. Sodium silicate catalyst was activated by calcination process at 400C, temperature ramp of 20C/min, and 3
hours detention time. The trans-esterification was carried out at varying temperature in the range of 50C - 70C with a methanol-
palm oil molar ratio of 9:1 and 3% (w/w) catalyst for 60 minutes. To investigate kinetics of reaction, the sample were taken
consecutively (0, 3, 5, 10, 15, 20, 25, 40 and 60 minutes) during the reaction after pouring waste cooking oil that have been pre-
treatment to reduce of free fatty acid content into the reactor. Experimental results showed that the sodium silicate was very active
in the trans-esterification of palm oil with methanol. Reaction temperature at 60C was sufficient to reach a conversion level as high
as above 85% in a relatively short reaction period. Results of the present work suggested that sodium silicate synthesized from local
resources of geothermal sludge would become potential solid base catalyst in biodiesel synthesis.

Keywords: palm oil, transesterification, geothermal sludge, sodium silicate

1 INTRODUCTION
1 Background
Indonesia, a country with a predicate of 4 th most populous in
the world with amount of 252.164.800 living peoples
(bps.go.id). Dewan Energi Nasional Republik Indonesia (2014)
shows that, along with population growth, Indonesias energy
consumption increase of average 5.5% per year. Industrial
drawback that happened since June 2014, forced Indonesias
government to alter the direction in energy generation business
[1]. Dewan Energi Nasional Republik Indonesia (2014) decide
to apply Energy Mix Indonesia as one of the energy planning
for Indonesia, the use of renewable energy must be increase to
about 6% in 2025. Geothermal energy becomes an
environmentally friendly energy source that could be the
alternative for the huge energy demand. Biodiesel also plays
along in the pool of renewable energies. Currently, those two
are not fully utilized due to accessibility and technical
problems.
Geothermal exploration problem occurs in the process of
reinjection brine into the earth. Brine in PT. Geo Dipa Energy
contains high concentration of silica that affect to plants
efficiency (pipe clogging). PT. Geo Dipa produce geothermal
waste about 165 ton million/year which is disturbing for natural
environment due to high silica content (55%) [7] that can be
purified until 97% [6].
The production of biodiesel uses homogenous catalyst that
result in challenging separation of products and former
reactants. Besides that, the use of homogenous catalyst will
produce emulsion as a side product (due to saponification
reaction) that can be problems in separation process [3]. To
solve the problem of difficult separation and environmental
exposure to silica, it is tactical to use sodium silicate as
heterogeneous catalyst for biodiesel production.
Biodiesel can be produced by reacting triglycerides and
alcohol with catalyst. The process is called trans-esterification
process. Thus, to solve emerging problem in a creative way, the
research will produce new kind of catalyst in solid phase. Thus,
solid catalyst can give good catalytic activity with high
conversion value on low temperature. It is also non-corrosive,
inexpensive, and easy to be separated from the reactants and
products. The catalyst will be made by reacting sodium
hydroxide (vast utilized catalyst in biodiesel production) with
silicate that was found in abundant amount within the waste
material of geothermal exploration. Not only solving the
problem of biodiesel production, the research will also reduce
the amount of threat in the containment of silicate particle at
the sludge waste.
2 Literature Review
The ASTM describes the biodiesel as esters mono-alkyl of
fatty acids of long chain that are produced from vegetable oil,
animal fat, or waste cooking oils in a chemical reaction known
as trans-esterification. Originally, the trans-esterification of
triglyceride is aided by sodium hydroxide to produce biodiesel
product [4]. All the substance involved was in liquid phase that
requires highly consuming water process for the separation
process, thus ignite the formation of soap. Guo has already
performed the research with heterogeneous catalyst (sodium
silicate) to convert soybean oil into biodiesel via trans-
esterification [2]. The result was exceptional as it reaches 100%
in term of conversion.
WCO, as the main material is mainly a palm oil product that
needs to go through few treatment processes before being
utilized in an optimum reaction. WCO is a product of
decomposition that impairs the oil quality causing reduction in
productivity in the trans-esterification reaction and may also
generate undesirable by-products which hurt the final product
[8]. This is due to high Free Fattty Acid (FFA) that present due
to gradual degradation of the material. For these reason, it is
important to refine the WCO for biodiesel production. For the
treatment of adequacy of WCO, the operations that can be
applied are filtration, de-acidification, or neutralization and
whitening. The process of degumming and deodorization arent
needed because the oils have already been treated prior to use
 The 2nd Indonesia Chemical Engineering Paper Competition - ITS - 2017
and although during the degradation odors occur, the removal is
not essential for biodiesel production. As a matter of fact, it is
known that WCO has different FFA rate for every waste
generated. Thus, it is very important to standardize the quality
of the product. Standardization will be done through resin
adsorption [5]
2 METHOD
1 Pretreatment of Waste Cooking Oil Using Anionic
Resin
The main equipment thats used in the research is ion-
exchange apparatus with anion-exchange resin, volumetric
analysis kit, gravimetric analysis kit, pH-meter, and
spectrophotometer. The goal of the procedure is to reduce Free
Fatty Acid (FFA) in the WCO. FFA analysis done by titration
with alcoholic oil. Moisture analysis is done by gravimetric
analysis. Impurities is treated by filtration with Whatman filter
paper.
Figure 1. Ion-Exchange Apparatus
V NaOH ( mL ) M NaOH 28.2(mg)
%FFA= 100
sample mass (mg)
2 Production of sodium silicate (Na2SiO3) catalyst
Geothermal sludge from PLTP Dieng was mixed with
aquadest by volume ratio of 1:2 for 30 minutes. The mixture
was filtered and dried in the oven at 150C for 16 hours. The
dried geothermal sludge was grinded with mortar for 2 hours
and screened with 60 mesh screen. Geothermal powder was
reacted with NaOH at constant reaction temperature 90C for
120 minutes. The mixture was filtered and sodium silicate
filtrate obtained. The filtrate titrated by HCl and stirred until it
forms gel. The gel then filtered and remained for 18 hours, then
dried with oven at 150C for 6 hours. The gel washed with
aquadest and washing procedure was repeated until pH = 7.
The neutralized gel was dried with oven at 120C for 4 hours.
The product is called xerogel.
Xerogel was added into solution NaOH solution, stirred and
heated at 60C. The deactivated solid catalyst product was
dried in the oven at 120C for 5-6 hours until it forms gel
phase. To be activated, it goes through calcination at 400C for
3 hours with rate of temperature increase 20C/minutes.
3 Evaluation of catalytic activity
Methanol and sodium silicate catalyst was heated to 60C
and stirred for 1 hours. Waste cooking oil at 60C was added
into the mixture with stirring rate 410 rpm. Each sample was
taken at 5, 10, 20, 40, and 60 minutes since addition of the corn
oil. The sample centrifuged 5-10 minutes and remained until it
forms two phases. The heavy phase was taken and analyzed
with iodometric method to determine the composition of
gliserol in the sample.
The formula to determine the conversion of the reaction:
free gliserols
x= 100
total gliserols
2
RESULTS AND DISCUSSION
In the present work, the activity of sodium silicate catalysts
in trans-esterification of palm oil with methanol was studied.
The ratio of catalyst-palm oil was varied at 1%, 3% and 5%
(w/w) while other parameters i.e. temperature, agitation speed
and palm oil-methanol molar ratio were kept constant at 60 0C,
410 rpm and 8.8:1, respectively. The usage of excess methanol
is to bring the equilibrium toward the formation of the product,
and the vice versa reaction is disregarded in the system. Beside
that, the gliserol that is formed will be absorbed by methanol,
thus, it can be assumed that the product will be continuously
harvested and the equilibrium of the reaction is directed toeard
the formation of the product. The end result shows that the
most optimum ration to be applied lies on the 3% percent ratio
of catalyst and palm oil. The conversion of the reaction at the
mentioned condition is 91,67%.
The utilization of sodium silicate catalyst is due to the goal of
higher conversion in biodiesel production. Waste cooking oil is
treated at prior by utilizing anion resin in an ion exchange
apparatus. The result of this phase will produce palm oil with
lower amount of fatty acid. The effectivity of the process has
reported to reach 70% percent of FFA removal. Thus, the
process will prevent the formation of emulsion due to
saponification reaction.
This improvement, will support a more efficient separation
process of the product. As known, the separation process of
emulsion that requires high amount of water and also need
more energy like heat. The using of calcined sodium silicate as
heterogeneous base catalyst that derived from geothermal
sludge will make the separation process easier such as decanter
and centrifuge to get biodiesel product. Various temperatures
are analyzed to obtain the optimum conversion of WCO into
fatty acid methyl ester and glycerol. Ratio of treated oil and
methanol that present is 1:9. Calcined Sodium silicate as
catalyst is present at 3 percent weight of waste cooking oil
mass.
CONCLUSION
Calcined Sodium silicates synthesized from silica rich
geothermal sludge used as a solid base catalysts was found very
active in transesterification of palm oil with methanol. The
utilization of geothermal sludge to catalyst the formation is a
very feasible method to gain high conversion of
transesterification reaction in the level of 91,67% for a brand
new catalyst in the relatively short period. The enhancement of
the coversion also contributed by pretreatment of waste
cooking oil as the nabatic oil utilized in the reaction.A lumped
reversible reaction kinetics model assuming that the catalyst is
always saturated with methanol is sufficient to approach
reaction conversion profile.
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