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UTILIZATION OF SODIUM SILICATE CATALYST

FROM GEOTHERMAL SLUDGE AS A RAW MATERIAL
FOR BIODIESEL PRODUCTION

Background

For decades, science is striving to optimize its energy resources for the
sake of human prosperity. Further step toward modernized technology always
correlated with the usage of non-renewable hydrocarbon fuel such as fossil fuel,
coal, and natural gas. Below is presented information regarding Indonesias non-
renewable energy outlook.

Increase in Remaining usage

Energy Type Reserved
Consumption per Year period
Coal 31,35 billion ton 13,10 % 72 years
Natural Gas 100,3 TCF 2,80 % 34 years
3,6 billion
Fossil Fuel 1,95 % 13 years
barrel
(Sources: Pusat Teknologi Pengembangan Sumber Daya Energi dan Direktorat
Jendral Minyak dan Gas)

Based on the table, growing energy consumption along with the decrease
of reserved energy will force government to begin the search of alternative energy
resources, such as geothermal energy. Located in Ring of Fire area, Indonesia
experiences high volcanic activity that results in massive storage of geothermal
energy, almost 40% of the world geothermal energy is under Indonesias
ownership. These potentials are capable of producing 28,000 Watts energy per
year. United States Energy Information Administration stated that Indonesia were
the 3rd ranked country for its ability to produce energy from geothermal.

Considering its sustainability, geothermal is rapidly renewed without any

special effort due to continuous volcanic activity happening below the earth
surface. The vast opportunity for geothermal exploration also emits minimal air
pollution because of the absence of combustion in the whole process. Indonesia

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GHG Abatement Cost Curve also reported that geothermal energy production will
reduce 27MtCO2 per year.

Problem

History has proven that every single exploration toward natural wealth will
results in minor or major environmental consequences. One of resulting effect
from the exploration is metal contaminant that is brought along during geothermal
mining. One of the most perilous materials is silica mineral that were found in
geothermal sludge. Silica (silicone dioxide) is naturally occurring material that
makes up 90% of the earth crust. The road of exposure of this materials vary from
aerial route, or direct consumption through drinking water that were previously
contaminated. Repeated and prolong exposure over many years to relatively high
concentration of crystalline silica in the air is known to cause lung disease called
silicosis.
Governmental policy has identified the disease as the main factor of
disability and death due to lack of safety in working field and adjacent
environment (refer to Keputusan Presiden Republik Indonesia Nomor 22 Tahun
1993). Various facts have supported the making of the policy, one of them is
stated by the National Institute for Occupational Safety and Health (NIOSH) and
the Department of Labor (DOL) that at least 1.7 million U.S. workers are exposed
to crystalline silica and each year more than 250 of them die with silicosis.
The early symptoms are shortness of breath, a dry cough, and general
feeling of illness. As the disease progress the symptoms may become more severe
(including heart failure and tuberculosis). Inhalation of crystalline silica particles
has also been associated with other diseases such as bronchitis, tuberculosis, auto-
immune diseases, nephrotoxicity, and even the lung cancer. The effective
treatment for the disease hasnt found yet, thus it is better to eliminate the silicate
from the after-process product
Therefore, the purpose of this writing is to offer more effective solution to
prevent the massive impact of silica by converting it into catalyst for biodiesel
formation.

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Utilizing Silica for Biodiesel Catalyst

The usage of the silica derivative starts from the production of biodiesel
which reacts triglycerides and methanol. Catalyst addition has an important role to
generate high conversion into this process. Oil trans-esterification process
commercially utilizes homogeneous base catalysts such as KOH or NaOH.
However, the utilization of the catalyst has a problem in the part of separation.
The most difficult procedure in separating the catalyst from the reactant and
product encourages to develope the utilization of heterogeneous base solid
catalyst as the solution of the problem. The solid catalyst is expected to provide
good catalytic activity, high conversion in low temperature, not corrosive, cheap,
and easy to be separated from the reactant and product of reaction. Those
characteristics are fulfilled in the heterogeneous base catalyst of sodium silicate
(Na2SiO3) which is made by reacting the solution of strong base of the sodium
hydroxide (NaOH) with silica (SiO 2). Silica can be found in the sludge waste of
Geothermal
Silica is contained in the sludge waste of Geothermal Power Plant as the
exploration result. The sludge contains the amorphous silica which can be utilized
as eco-friendly alternative raw material. One of the Geothermal Power Plants
which operate in Indonesia is PT. Geodipa Energi in Dieng with the power of 60
Mwe. In the research of Riyanto, et.al (2010) mentions the content of the
amorphous silica in the sludge of geothermal reaches 55%. After the extraction,
silica is obtained in the purity of 97% (Perdana, dkk, 2015).
Sodium silicate is made by the reaction of NaOH and silica by gelation
method, then the catalyst is activated by calcination in the temperature of 400 oC,
the increase rate of calcination temperature is 20oC/hour and detention time about
3 hours (Chendrika, 2013). The activation is verified by using the catalyst for the
process of trans-esterification of the corn oil with methanol to produce biodiesel.

Sodium Silicate, Solution for Effective Catalyst

Sodium silicate is the derivative compound of silica which has a huge quantity in
Indonesia. It is obtained from the waste of geothermal power plant process

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Picture 1. The structure of Sodium Silica Molecule

Sodium silica is obtained from the reaction as follows:
2 NaOH + SiO2 Na2SiO3 + H2O
The Catalytic Activity
The utilization of homogeneous alkaline catalysts (pure dissolved NaOH)
can convert triglycerides to esters with high conversion results, in less time, and a
cheaper price. But, the separation of homogeneous catalysts from product is very
difficult. After the reaction, the catalyst must be neutralized with a huge amount of
water, so much water to be wasted. In addition, since the oil contains enormous
number of water and free fatty acid (FFA), homogeneous catalyst cannot be used
directly for this reaction because it will lead to the formation of soap as byproduct
of the reaction of FFA and catalyst (Lotero et al, 2005).
Heterogeneous catalysts can be separated easily from the product, does not
require neutralization process, so theres no required separation which wastes the
water and even reduce the production costs. Heterogeneous catalysis has complex
stages compared to homogenous catalyst. This is caused by inequally distribution
of catalyst in the reaction medium.
There are many kinds of solid catalyst which have been studied for this
trans-esterification process, but most of them are sensitive to water and FFA due
to the presence of soap characterization. Actually, the required solid catalysts
(heterogeneous) in Biodiesel formation are able to prevent the formation of soap,
even if there are much of water and FFA in the raw materials. Therefore, the
proposed solution is to use sodium silicate as the heterogeneous catalyst. Sodium
silicate is very suitable for this process to avoid the formation of soap.
One of the researches which is conducted by Guo et al (2010) is using
sodium silicate as a catalyst in the trans-esterification reaction of the biodiesel
formation. The catalyst catalyzes soybean oil into biodiesel with the conversion of
almost 100% with the following conditions: sodium silicate is used as much as
3% by mass, the ratio between methanol and oil concentration is 7.5, reaction time

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in 60 minutes, the reaction temperature is 60C and the stirring speed reaches 250
rpm. Once the reaction is complete, the catalyst which has been used will be
regenerated and tested for producing the biodiesel. The obtained results are the
catalysts can be reused up to five times the reaction without loss of performance
(Guo et al, 2010). Therefore, the using of sodium silicate catalyst is very suitable
to be used in the trans-esterification process of biodiesel formation.
Silica for Biodiesel, Another kind of Eco-Friendy Renewable Energy
Biodiesel is an alternative fuel for diesel engine which normally uses diesel
oil. Biodiesel can be used as a 100% petroleum diesel, as well as a mixture of
petroleum diesel without engine modifications. Biodiesel is eco-friendly and non-
toxic because the emissions of the combustion can be reabsorbed easily by the
plant and contains no SOx.
Table I. The Combustion Emission Comparison of Biodiesel and Diesel
Emission Compound Biodiesel Diesel
SO2, ppm 0 78
NO, ppm 37 64
NO2, ppm 1 1
CO, ppm 10 40
Particulates, mg/Nm3 0,25 5,6
3
Benzene, mg/Nm 0,3 5,01
Toluene, mg/Nm3 0,57 2,31
Xylene, mg/Nm3 0,73 1,57
Ethyl benzene, mg/Nm3 0,3 0,73
Source: chemical-engineer.digitalzones.com
Proven! Waste Can Still be Useful
At the end, this article would like to invite readers to see and realize that
even renewable energies are better solution than nonrenewable energies, both are
surely still have negative side, including geothermal. There is still much less
concerned with the harmful effects of waste from silica of geothermal and without
any guarantees, it also can occur to other wastes. As it turned out, the proposed
solution of this paper is also an effort to utilize the silica wastes which pollute the
environment. Not only that, this solution is also one of ways to support the
production of another type of renewable energy, biodiesel.
If it isnt us to think about the environment, then should anyone else?"

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BIBLIOGRAPHY
Hartwig, R.P. and Wilkinson, C. 2004. Silica Liability. Insurance Information
Institute
Pedoman Penilaian Risiko Keselamatan dan Kesehatan Kerja. 2011. Badan
Tenaga Nuklir Nasional
Hilyah, A. and Utama, W. 2016. Pengaruh Patahan Dan Induksi Seismik Pada
Sistem Geothermal Studi Kasus Lapangan Geothermal Kamojang.
Surabaya: Institut Teknologi Sepuluh November
Berita Harian Greeners.Co. Diposting pada tanggal 08 Januari 2015. Walhi
Khawatirkan Dampak Negatif Tambang Panas Bumi Di Gunung Ijen.
Jakarta
Chendrika, L., 2013, Pengaruh Suhu dan laju Kenaikan Suhu Kalsinasi Terhadap
Karakteristik Natrium Silikat sebagai Katalisator Basa Padat, Thesis
Program Studi Teknik Kimia, Magister Teknik Proses, Universitas
Gadjah Mada, Yogyakarta.
Riyanto, N., Sumardi, P. C., Perdana, I., 2010, Recovery of Micro-amorphous
Silica from Diengs Geothermal Sludge via Sol-Gel Extraction, Seminar
proceeding of Regional Seminar on Chemical Engineering (RSCE) 2010,
Bangkok, Thailand, November 2010.
Guo, F., Peng, Z. G., Dai, J. Y., and Xiu, Z. L., 2010, Calcined Sodium Silicate as
Solid Base Catalyst for Biodiesel Production, Fuel Process Technol, 91,
322-328.