Scientific Contribution in Oil and Gas Industry Vol 35, Number 1 April 2012

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Tools Name : ASTM 1266

ISSN : 2089-3361

Volume 35, No. 1, April 2012


SCIENTIFIC CONTRIBUTIONS OIL & GAS is a printing media to promote research and development
activities which have been done by LEMIGAS Research and Development Centre for Oil and Gas Technology.
Chief Editor

: Dra. Yanni Kussuryani, M.Si. (Chemist)

Managing Editor

: Ir. Daru Siswanto (Chemical Engineering)

Ass. Managing Editor

: Drs. Heribertus Joko Kristadi, M.Si. (Geophysic)

Senior Editors

: 1.
2.
3.
4.
5.
6.

Prof, Dr. Maizar Rahman (Chemical Engineering)


Ir. E. Jasjfi, M.Sc., APU. (Chemical Engineering)
Prof. Dr. Suprajitno Munadi (Geophysics)
Prof. M. Udiharto (Biology)
Prof. Dr. E. Suhardono (Industrial Chemistry)
Ir. Bambang Wicaksono T.M., M.Sc. (Petroleum Geology)

Editors

: 1.
2.
3.
4.

Dr. Ir. Usman, M.Eng. (Petroleum Engineering)


Ir. Sugeng Riyono, M.Phil. (Chemical Engineering)
Dr. Ir. Eko Budi Lelono (Palynologist)
Abdul Haris, S.Si., M.Si. (Chemistry and Environment)

Peer Group

: 1.
2.
3.
4.
5.
6.

Prof. Dr. Ir. Septoratno Siregar (Petroleum Engineering)


Prof. Dr. R.P. Koesoemadinata (Geological Engineering)
Prof. Dr. Wahjudi Wisaksono (Energy and Environment)
Dr. Ir. M. Kholil, M.Kom. (Management of Environment)
Dr. Ir. Bambang Widarsono, M.Sc. (Petroleum Engineering)
Ferry Imanuddin Sadikin, S.T., M.E. (Electrical Engineering)

Secretariat

: Publications Affairs

Publisher

: LEMIGAS Research and Development Centre for Oil and Gas Technology
Afilliation and Publication Division

Printed by

: Grafika LEMIGAS

Address
LEMIGAS Research and Development Division for Afilliation and Publication, Jl. Ciledug Raya, Kav. 109, Cipulir,
Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230 INDONESIA, STT: No. 348/SK/DITJEN PPG/STT/1987/
May 12, 1977, Phone: 7394422 - Ext. 1222, 1223, Fax : 62 - 21 - 7246150,
e-mail: management@lemigas.esdm.go.id
Scientific Contributions Oil & Gas has been published since 1977 it had been named LEMIGAS Scientific Contributions
(LSC), 3 times a year. The editor receives scientific articles about research results, related to the oil and gas
research.
Scientific Contributions Oil & Gas is published by LEMIGAS Research and Development Centre for Oil and Gas
Technology. Chief Editor : Dra. Yanni Kussuryani, M.Si. Managing Editor: Ir. Daru Siswanto

ISSN : 2089-3361

Volume 35, Number 1, April 2012

Page
CONTENTS
INTRODUCTION

iii

ABSTRACTS

iv

CHARACTERIZATION OF THERMAL PRECIPITATOR IN SMOKE


COLLECTOR BY USING PARTICLE COUNTER
Imansyah Ibnu Hakim, Bambang Suryawan, I Made Kartika D., Nandy Putra,
and Cahyo Setyo Wibowo

ii

ii

1 - 10

INHIBITION OF MILD STEEL IN 1M HCL


BY CATECHIN MONOMERS FROM COMMERCIAL
GREEN TEA EXTRACTS
Nofrizal

11 - 24

THE IMPROVEMENT OF MERCURY REMOVAL IN NATURAL GAS


BY ACTIVATED CARBON IMPREGNATED WITH ZINC CHLORIDE
Lisna Rosmayati

25 - 29

COMPARISION DEPOSIT FORMATION ON THE VALVE DIESEL


ENGINE CAUSED BY BIODIESEL AND PETROLEUM DIESEL FUELS
Maymuchar, and Ismoyo Suro Waskito

31 - 37

DILUTE ACID PRETREATMENT AND ENZYMATIC HYDROLYSIS


OF LIGNOCELLULOSIC BIOMASS FOR BUTANOL
PRODUCTION AS BIOFUEL
Devitra Saka Rani and Cut Nanda Sari

39 - 48

INTRODUCTION
Dear Readers,
Scientific Contributions Oil & Gas has a very significant role in Indonesia science community
and oil and gas industry for information dissemination in oil and gas research and studies.
Scientific Contributions Oil & Gas April 2012, Volume 35, Number 1 presents some selected results of studies and research in LEMIGAS:
1. Characterization of Thermal Precipitator In Smoke Collector by Using Particle Counte; 2.
Corrosion Inhibition of Mild Steel in 1M HCL by Catechin Monomers From Commercial Green
Tea Extracts; 3. The Improvement of Mercury Removal in Natural Gas by Activated Carbon
Impregnated With Zinc Chloride; 4. Comparision Deposit Formation on The Valve Diesel Engine
Caused by Biodiesel and Petroleum Diesel Fuels; 5. Dilute Acid Pretreatment and Enzymatic
Hydrolysis of Lignocellulosic Biomass for Butanol Production As Biofuel.
April 2012 edition Scientific Contributions Oil & Gas Editorial Team hope that Scientific
Contributions Oil & Gas can be a reference for the authors/researchers. Reader feedbacks and
inputs for development are strongly suggested and will be highly appreciated to improve next
edition of Scientific Contributions Oil & Gas.
Editorial board, Publisher and Manajemen extend highly gratitude for authors, reviewers
and editors who have worked very hard to making this edition of Scientific Contributions Oil
& Gas is possible to succesfull published.

Jakarta, April 2012

Redaction

iii

ABSTRACTS
The descriptions given are free terms. This abstract sheet may be reproduced without permission or charge
Imansyah Ibnu Hakim 1), Bambang Suryawan 1),
I M a d e K a r t i k a D . 1), N a n d y P u t r a 1),
and Cahyo Setyo Wibowo2)
1)
Department of Mechanical Engineering, Faculty of
Engineering Universitas Indonesia
Kampus UI Depok 16424 Jawa Barat. Phone: 62-217270032, Fax: +62-21-7270033, E-mail: imansyah@eng.ui.ac.
id
2)

Researcher at LEMIGAS R & D Centre for


Oil and Gas Technology Jl. Ciledug Raya, Kav.
109, Cipulir, Kebayoran Lama, P.O. Box 1089/
JKT, Jakarta Selatan 12230 INDONESIA. Tromol
Pos: 6022/KBYB-Jakarta 12120, Telephone:
62-21-7394 422 , Fa x si m i le: 62-21-7246150
C H A R A C T E R I Z AT I O N O F T H E R M A L
PRECIPITATOR IN SMOKE COLLECTOR BY
USING PARTICLE COUNTER
Scientific Contributions Oil & Gas, April 2012,
Volume 35, Number 1, p. 1 - 10
ABSTRACT
Air pollution in major cities in many countries
has reaching a very concerning level. One of the
cause of air pollution is pollution caused by smoke
aerosol. Smoke aerosols that has an average particle
diameter of 0.1 m 1 m can be found in cigarette
smoke, diesel vehicle fume, industrial fume and many
else. This condition will be worsen by the increase in
the number of smokers, motor vehicles and industry.
Therefore we need to pursue the control method for
that kind of air pollution. In the literature study, its
found that the cleaning method of air filtration for
fine particle with dimension of 0.01 5 m are by
using thermal precipitator. Thermal precipitator is
one method of air filtration based on thermophoretic
force, which is if there is a temperature difference
between two plates, it will cause the force that will
push the particles between the two plates toward
the plate that has lower temperature. In the effort
to help control and reduce the air pollution, for this
study we made a thermal precipitator test equipment
to deposit the particles in the air with the use of

iv

thermophoretic force. That force is the force applied


to the particles that suspended in the fluid flow. The
temperature difference between two plates is set
at T=5, 10, 15, and 20oC. This study utilized gas
sensors to observe the characterization of thermal
precipitator. From the experiment and analysis can
be concluded that thermal precipitator can be applied
as a smoke collector.
(Author)
Keywords: thermal precipitator, smoke collector, gas
sensor
Nofrizal (Researcher at LEMIGAS R & D Centre
for Oil and Gas Technology)
Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran
Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230
INDONESIA. Tromol Pos: 6022/KBYB-Jakarta
12120, Telephone: 62-21-7394422, Faxsimile: 62-217246150
CORROSION INHIBITION OF MILD STEEL IN
1M HCL BY CATECHIN MONOMERS FROM
COMMERCIAL GREEN TEA EXTRACTS
Scientific Contributions Oil & Gas, April 2012,
Volume 35, Number 1, p. 11 - 24
ABSTRACT
The inhibitory effect of two Indonesian green
tea extracts (containing various catechins) were
investigated on the corrosion of mild steel (MS) in 1M
HCl medium. The anticorrosion effect was evaluated
by conventional weight loss method, potentiodynamic
polarisation, electrochemical impedance spectroscopy
(EIS) studies and scanning electron microscopy (SEM)
technique. The results evidenced that both the tea
extracts act as a good corrosion inhibitor and the
inhibition efficiencies (% IE) were in good agreement
for all the studies. Adsorption of green tea extract
constituent was found to follow Langmuir adsorption
isotherm and the calculated Gibbs free energy values
indicated the physisorption of inhibitor over the mild
steel surface. SEM - EDX studies show the adsorption
of catechin monomers which forms a protective layer

the steel
mils surface.
steel surface.
High performance
overover
the mils
High performance
liquid
liquid chromatography
(HPLC)was
analysis
chromatography
(HPLC) analysis
carriedwas
out
carried
outthe
to catechin
quantify fractions
the catechin
in
to
quantify
in thefractions
tea extract
the
tea
extract
and
it
was
found
that
eight
catechin
and it was found that eight catechin monomers were
monomers
weretea
present
in both
tea extracts.
From all
present
in both
extracts.
From
all of monomers,
of was
monomers,
wasfour
found
that four monomers
were
it
found it
that
monomers
were identifi
ed
identifi
ed
as
components
responsible
for
controlling
as components responsible for controlling the
the dissolution
of mild
M HCl
medium.
dissolution
of mild
steelsteel
in 1in
M1HCl
medium.
(Author)
Keywords:mild
mildsteel,
steel,corrosion
corrosion
inhibition,
green
Keywords:
inhibition,
green
tea,
tea, HPLC,
potentiodynamic,
HPLC,
potentiodynamic,
EIS EIS
Lisna Rosmayati (Technological Assessor at
LEMIGAS R & D Centre for Oil and Gas
Technology)
Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran
Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230
INDONESIA. Tromol Pos: 6022/KBYB-Jakarta
12120, Telephone:
Telephone:62-21-7394422,
62-21-7394422,Faxsimile:
Faxsimile:
6262-2121-7246150
7246150
THE IMPROVEMENT OF MERCURY REMOVAL
IN NATURAL GAS BY ACTIVATED CARBON
IMPREGNATED WITH ZINC CHLORIDE
Scientific Contributions Oil & Gas, April 2012,
Scientific
Volume 35, Number 1, p. 25 - 29
ABSTRACT
Natural gas being produced from gas fields
around Indonesia areas, along with a large number
of other harmful substances (CO22,H22S, RSH,COS
etc) often contains mercury. Even in small amounts,
mercury and its compounds have an extremely
harmful effect on human health. Mercury content in
the natural gas should be removed to avoid equipment
damage in the gas processing plant or the pipeline
transmission system from mercury amalgamation and
embrittlement of aluminium. Mercury can be removed
by using adsorption processes such as activated
carbon that is impregnated with chlor, iodine or
sulfur. This research is dealing with the process
of mercury removal from gas based on principle
of adsorption and of chemisorption of mercury by
means of activated carbon impregnated with ZnCl22.
Time of impregnation is a significant variable that

can
can effect
effect adsorption
adsorptioncapacity.
capacity.The
Theexperiment
experimentresults
results
showed
impregnation time
time of
of 12
12 hours
hours
showed that
that ZnCl
ZnCl22 impregnation
signifi
significantly
cantly enhanced
enhanced the
the adsorptive
adsorptive capacity
capacity for
for
mercury
vapour.
mercury vapour.
(Author)
(Author)
Keywords:
mercury
removal,
activated
Keywords: mercury removal, activated carbon,
carbon,
impregnated
impregnated zinc
zinc chloride
chloride
1)
2)
Maymuchar
and Ismoyo
Ismoyo Suro
Suro Waskito
Waskito2)
Maymuchar1),, and
1)
1)Researcher, 2)
Researcher, 2)Litkayasa,
Litkayasa, at
at LEMIGAS
LEMIGAS R
R&
&D
D Centre
Centre

for
for Oil
Oil and
and Gas
Gas Technology
Technology

Jl.
Jl. Ciledug
Ciledug Raya,
Raya, Kav.
Kav. 109,
109, Cipulir,
Cipulir, Kebayoran
Kebayoran
Lama,
Lama, P.O.
P.O. Box
Box 1089/JKT,
1089/JKT, Jakarta
Jakarta Selatan
Selatan 12230
12230
INDONESIA.
INDONESIA. Tromol
Tromol Pos:
Pos: 6022/KBYB-Jakarta
6022/KBYB-Jakarta
12120,
12120, Telephone:
Telephone: 62-21-7394422,
62-21-7394422, Faxsimile:
Faxsimile: 62-2162-217246150
7246150
C
O M PA R I S I ODEPOSIT
N D E P OFORMATION
S I T F O R M AT
ON
COMPARISION
ONITHE
O
N T DIESEL
H E VA
LV E CAUSED
D I E S E BY
L BIODIESEL
ENGINE
VALVE
ENGINE
C
A UPETROLEUM
S E D B Y DIESEL
B I O DFUELS
IESEL AND
AND
PETROLEUM
DIESEL
FUELS
Scientific Contributions Oil & Gas, April 2012,
Scientific
Oil- &
Volume 35,Contributions
Number 1, p. 31
37 Gas, April 2012,
Volume
35, Number 1, p. 31 - 37
ABSTRACT
ABSTRACT
The research on the influence of the biodiesel to the
The
research
on the infl
of the
to the
formation
of deposits
onuence
the intake
andbiodiesel
exhaust valves
formation
of
deposits
on
the
intake
and
exhaust
valves
diesel engine has been carried out by means analysis
diesel
engine
has
been
carried
outthis
by study
meansare
analysis
of merit
rating.
The
fuels
used on
FAME
of
merit rating.
The of
fuels
used
on this
study
FAME
(B-100),
a mixture
50%
(v)of
FAME
in are
diesel
fuel
(B-100),
a mixture
of 50%
FAME
diesel fuel
48 (B-50),
and diesel
fuel (v)of
48 (B-0).
Theinobjective
of
48
(B-50),
and
diesel
fuel
48
(B-0).
The
objective
of
this research is to obtain data which represent the
this
research
is biodiesel
to obtaintodata
which represent
the
influence
of the
the formation
of deposits
infl
of the
biodiesel
the diesel
formation
of deposits
on uence
the intake
and
exhaust to
valve
engine.
The test
on
theaintake
exhaust
valve
engine. The
test
used
dieseland
engine
driving
5 diesel
KVA generator
which
used
a
diesel
engine
driving
5
KVA
generator
which
is operated for 100 hours with 1.000 Watt electrical
is
operated
for 100ofhours
with 1.000
electrical
load.
The results
the study
show Watt
that the
use of
load.
The
results
of
the
study
show
that
the
use
of
either FAME or biodiesel as alternative fuel in the
either
FAME
or
biodiesel
as
alternative
fuel
in
the
diesel engine generator 5 KVA has a positive effect
diesel
engine the
generator
KVA
a positive
effect
on reducing
deposit5on
thehas
intake
and exhaust
on
reducing the deposit on the intake and exhaust
valves.
valves.
(Author)
(Author)
Keywords: Biodiesel, intake valve, exhaust valve,
Keywords:
Biodiesel, intake valve, exhaust valve,
diesel engine
diesel engine

Devitra Saka Rani 1) and Cut Nanda Sari1)


1)
Researcher at LEMIGAS R & D Centre for Oil
and Gas Technology
D I L U T E A C I D P R E T R E AT M E N T
A N D E N Z Y M AT I C H Y D R O LY S I S O F
LIGNOCELLULOSIC BIOMASS FOR BUTANOL
PRODUCTION AS BIOFUEL
Scientific Contributions Oil & Gas, April 2012,
Volume 35, Number 1, p. 39 - 48
ABSTRACT
Biobutanol is one of the promising biofuel for substituting gasoline. Biobutanol produced from biomass
fermentation using solventogenic clostridia which are
able to convert a wide range of carbon sources to fuels
such as butanol. Therefore, lignocellosic biomass
has great potential as fermentation substrate for
biobutanol production. Lignocellosic biomass should
be hydrolized before fermentation by a pretreatment
process and enzymatic hydrolysis. The various
lignocellulosic biomass pretreatment will influence
in butanol production depending on fermentable
sugars content. The objective of this research is to
get potential lignocellulosic biomass using dilute
acid pretreatment and enzymatic hydrolysis process

vi

for biobutanol production. Eight types of biomass


from sugarcane bagasse, rice straw, rice husk, empty
fruit bunch (EFB) of palm oil, corn cob, pulp waste,
traditional market organic waste, and microalgae
were used in this experiment. After hydrolysis,
the high result of total fermentable sugars in corn
cobs, bagasse, rice straw, and rice husk, shows
good opportunity of these biomass to be used as
fermentation feedstocks for biobutanol production. In
addition, pulp waste, organic waste, and microalgae
are prospective as raw material but require more
appropriate treatment either for to break down the
cellulose/hemicellulose or to enhance reducing sugar
content. Fine milling and delignification have no
significant effect on cellulosic biomass conversion
into fermentable sugars. Therefore, the production
cost can be reduced. In order to enhance the sugar
content and reduce the formation of inhibitor product,
it is necessary to examine dilute acid pretreatment
variations and appropriate operating conditions of
enzymatic hydrolysis process.
(Author)
Keywords: biofuel, biobutanol, lignocellulosic
biomass, dilute acid pretreatment, enzymatic hydrolysis

CHARACTERIZATION OF THERMAL PRECIPITATOR


IN SMOKE COLLECTOR
BY USING PARTICLE COUNTER
Imansyah Ibnu Hakim1), Bambang Suryawan1), I Made Kartika D.1), Nandy Putra1),
and Cahyo Setyo Wibowo2)
1)

Department of Mechanical Engineering, Faculty of Engineering Universitas Indonesia


Kampus UI Depok 16424 Jawa Barat
Phone : 62-21-7270032, Fax: +62-21-7270033, E-mail : imansyah@eng.ui.ac.id
2)
Researcher at LEMIGAS R & D Centre for Oil and Gas Technology
Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230 INDONESIA
Tromol Pos: 6022/KBYB-Jakarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150
First Registered on November 30th 2012; Received after Corection on April 18th 2012
Publication Approval on : April 30th 2012

ABSTRACT
Air pollution in major cities in many countries has reaching a very concerning level. One of the
cause of air pollution is pollution caused by smoke aerosol. Smoke aerosols that has an average
particle diameter of 0.1 m 1 m can be found in cigarette smoke, diesel vehicle fume, industrial
fume and many else. This condition will be worsen by the increase in the number of smokers, motor
vehicles and industry. Therefore we need to pursue the control method for that kind of air pollution.
In the literature study, its found that the cleaning method of air filtration for fine particle with
dimension of 0.01 5 m are by using thermal precipitator. Thermal precipitator is one method of
air filtration based on thermophoretic force, which is if there is a temperature difference between
two plates, it will cause the force that will push the particles between the two plates toward the
plate that has lower temperature. In the effort to help control and reduce the air pollution, for this
study we made a thermal precipitator test equipment to deposit the particles in the air with the use
of thermophoretic force. That force is the force applied to the particles that suspended in the fluid
flow. The temperature difference between two plates is set at T=5, 10, 15, and 20oC. This study
utilized gas sensors to observe the characterization of thermal precipitator. From the experiment
and analysis can be concluded that thermal precipitator can be applied as a smoke collector.
Keywords: thermal precipitator, smoke collector, gas sensor
I. INTRODUCTION
Air pollution in major cities in many countries
has reaching a very concerning level. This condition
is also happened in Indonesia, particularly in the
capital city of Jakarta, which became a barometer for
other cities in Indonesia, has reached a concerning
level so it caused the drop in air quality and
environmental support capacity. Smoke aerosol
is one of the air pollution. Smoke aerosol with
submicron-micron sized particle (0.01 5 m) are
often found in cigarette smoke, diesel vehicle fumes,
industrial fumes and many others. Efforts to control
air pollution are limited in the form of pamphlets,

banners, etc. Even if there are rules that provide


sanction to air pollution, but the implementation in
the field is not optimum.
Thermophoresis plays an important role in
the mechanism of movement of submicron-sized
particle in the aerosol technology. Thermophoresis
phenomenon describes the movement of particle
caused by temperature difference around the particle.
If there is any temperature difference around the
particle between two regions (e.g plate), it will cause
the force and the particle between two plates will
move toward the plate that has lower temperature.
This thermophoresis effect was first studied by

CHARACTERIZATION OF THERMAL PRECIPITATOR

SCIENTIFIC CONTRIBUTIONS OIL & GAS

IMANSYAH IBNU HAKIM, ET AL.

VOL. 35, NO. 1, APRIL 2012 : 1 - 10

Tyndal in 1870 and later by Aitken in 1884. They


clarified, that particles must be driven away from hot
surface. This occurs due to a net force, acting in the
opposite direction to the gradient temperature, toward
the low-temperature region and is a direct result of
the differential bombardment of the gas molecules
that comes from the relatively hot and relatively cold
regions in the vicinity of the particles. A phenomenon
referred now to as thermophoresis. Deposit that
accumulated in heat exchanger equipments is caused
by thermophoresis, studied by Nishio et al. Byres
et al. and Romay et al.
Standford Research Institute (Figure 1) in
1961 stated that the cleaning method for particle
with dimension of 0.01 5 m are by using
thermal precipitation particle separation by using
heat. Thermophoresis in a laminar tube flow has
been studied thoroughly. Stratmann et al. (1989)
experimentally studied thermophoretic deposition
using 0.005 0.1 m monodisperse aerosol in a
laminar tube flow. Montassier et al. (1990) carried
out experiment with an experimental set-up that was
similar to that employed by Stratmann et al. except

for the direction of the flow and the measuring


technique. A. Messerer, et al. in 2003 using
thermophoresis to deposit soot aerosol particles in
the exhaust system of diesel engine. Byung Uk Lee,
et al. in 2006 conducted a similar study to A Messerer
and stated that thermophoresis is a dominant factor
to deposit the particle with 0.02 0.05 m of size
in the vehicle exhaust system. Later in 2008 Zhou
Tao et al. conduct an experiment to visually prove
that thermophoresis has a great influence to make a
1 30 m particle deposit, but a little for the particle
larger than 30 m. Earlier in 2004, Gallis M.A., et al.
thermophoresis force can be used as thermal
precipitator that can be applied more broadly in life,
especially for pollution control. The same thing was
observed by Gonzales D. et al. in 2005. K.K. Dinesh
et al. studied the thermophoretic deposition in natural
convection flow through a parallel plate channel
with heat sources. Effect of thermophoresis particle
deposition from a horizontal flat plate embedded in
a porous medium was studied by Adrian Postelnicu
(2007). Not only experimentally, thermophoresis
in annular flow theoretically studied by D.P. Healy
et al. in 2010.

Figure 1
Particle size and character

CHARACTERIZATION OF THERMAL PRECIPITATOR

SCIENTIFIC CONTRIBUTIONS OIL & GAS

IMANSYAH IBNU HAKIM, ET AL.

VOL. 35, NO. 1, APRIL 2012 : 1 - 10

3
Stainless
steel gauze

GAS
RS SENSOR

4
VH

Metal
cap

RH

VC

GAS
2

RL

Lead pin

Vout

(-)

Figure 2
Gas sensor figaro 2600

Deposit of fine particle is not only influenced


by thermophoresis. Chi-Chang Wang studied a
combined effects of inertia and thermophoresis on
particle deposition onto a wafer with wavy surface.
Other researchers like Iman Zahmatkesh clarified
that, deposition particle ~ 100 m mainly occurs by
inertial impaction. Thermophoresis is the dominant
deposition mechanism for particles ~ 10 m.
Brownian diffusion contribute on the deposition of
10 nm. On the another hand, Changfu You studied
the effect of electrostatic field and thermophoresis on
inhalable particulate matter. Effect of thermophoresis
and electrophoresis on particle deposition onto a
vertical flat plate was studied by R. Tsai et al.
Many research about thermophoresis has been
conducted and it is said that thermophoresis is the
driving force for the deposit accumulation. But, research
regarding thermal precipitator is rare. Therefore the smoke
collector device has been conducted. That is the reason
why we are conducting this research by conducting experimental study of thermal precipitator test equipment to
deposit the particles in the air by utilizing thermophoretic
force. Therefore, first thing to do is by investigating and
characterizing the thermal precipitator itself.
II. THEORY

Thermophoresis force was studied by M. Eipstein


in 2005 by assuming spherical particle and the fluid
is ideal gas, stated that thermophoretic force:




.. (1)

Where Fx is Thermophoresis force, Kn is Knudsen


number = 2/Dp, is particle distance, K = k/kp,
where k is fluid thermal conductivity, k = (15/4) R,
kp = particle thermal conductivity, Cs = 1,17; Ct =
2,18; Cm = 1,14, T = local fluid temperature, =
fluid viscosity.
In this paper, an experimental study was
conducted. the particle concentration or smoke
deposited on the plate was measured by using gas
sensor and particle counter. The type of the gas
sensor is Figaro TGS 2600 (Figure 2). It is designed
to measure concentration of pollution that prevalent
in the room such as cigarette smoke. This sensor is
commonly used to detect the presence of gas. This gas
sensor can be applied as an alarm and also to measure
gas concentration depends on the microcontroller
circuit that is used. This gas sensor consist of a
resistance value (Rs) that will respond when exposed
to gas and has a heater that is used to clean sensor
in internal chamber from air contamination from the
outside.
Output voltage signed at the resistor RL (Vout)
is used as an input to microprocessor. The material
of gas sensor is metal oxide, particularly SnO2

CHARACTERIZATION OF THERMAL PRECIPITATOR


IMANSYAH IBNU HAKIM, ET AL.

O2
SnO2-x

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 1 - 10

O2

SnO2-x

E
eVs
in Air

Figure 5
Gas sensor and microcontroller

Figure 3
Illustration of oxygen absorbtion by the sensor

Figure 6
Graph showing the relationship
between Rgas/Rair vs consentration

1 / 2O2 + ( SnO2 )* O ad ( SnO2 )


Figure 4
Illustration when Gas is Detected

compound. In Figure 3 and Figure 4 are shown the


illustration of Oxygen absorbtion by the gas sensor,
when crystal metal oxide (SnO2) is warmed at given
temperature, oxygen will be absorbed in the crystal
surface and oxygen will be negatively charged. The
absorbed oxygen by the sensor can be seen from the
following chemical equation:

This will occur because the crystal surface donate


electrons to the oxygen contained in outer layer,
so that the oxygen will be negatively charged and
positive charge will be formed on the outer surface
of the crystal. Formed surface tension will inhibit the
rate of electron flow.
In the sensor, current flows through the junction
area (grain boundary) of SnO2 crystal. At the junction,
oxygen absorption prevents the charge to move
freely. If the gas concentration decreases, deoxidation
process will occur, surface density of negatively

CHARACTERIZATION OF THERMAL PRECIPITATOR

SCIENTIFIC CONTRIBUTIONS OIL & GAS

IMANSYAH IBNU HAKIM, ET AL.

VOL. 35, NO. 1, APRIL 2012 : 1 - 10

acrylic, and at this position one gas sensor is placed


to measure the smoke density in the air. Through the
inlet section, smoke flows to the test section consists
of 2 stainless steel plate. One of the plate is attached
to a heater in order to maintain the temperature on
the hot side. To have the variation of the temperature
on the hot side, voltage regulator is applied. The
test plate section dimension is 15 cm x 50 cm and
distance between two plates is 5 mm. To measure
the air velocity, we use a hot wire anemometer. The
average air velocity in the test section is 5 cm/s.
To maintain the temperature of the cold side of the
plate stable, cooling water is flowed into the plate.
Temperature is maintained at 26.850C. Then smoke
will be deposited in the cold side of the plate so the
level of the smoke that coming out from test section

charged oxygen will be reduced, and resulting in the


decreasing of the barriers height in the junction area.
If there is presence of CO gas that is detected, then
chemical equation as follow.
CO + O ad ( SnO2 X ) CO2 + ( SnO2 x )*

Obtained value from the gas sensor are still in


the form of voltage ratio (Rgas/Rair), then to get the
number of particle, Rgas/Rair value must be converted
to ppm (part per million) by using graph as shown
in Figure 6.
The signal data from the sensor will be sent to
the microcontroller which is then displayed to the
LCD screen in digital form. The picture of the gas
sensor system and the microcontroller can be seen
in Figure 5.
Clean room standard issued by US FED STD
209E and ISO 14644-1 FED STD 209E are using
particle/m3 or particle/ft3 as the unit. Therefore the
data to particle/m3 or particle/ft3 were converted using
particle counter P-TRACK 8525. P-TRACK 8525
that have the following specification: concentration
range: 0-5x105 particles/cm3, particle size range :
0.02 2.5 m, operation temperature range : 0 38
o
C, and level of accuracy: 0.01%. Calibration process
from the gas sensor to the particle counter were done
in same condition at the time of experimentation. The
graph in Figure 7 shows the result of the calibration.
From the calibration we obtain the
following equation:
y = - (3e+7)x3 + (7e+7)x2 (6e+7)x +
Pt/cc
(2e+7) ... (2)

Table 1
Test particle specification
No

Parameter

Aerosol type

Aerosol name

Particle diameter

Density

Molecular mass

Boiling point

Value

Unit

Smoke
0.01 ~ 1

1.1

g/cm3
g/mol

162.23

247

Ref.:BritishAmericanTobacco(www.batscience.com)

500000

with a deviation R2 = 0.994.


III. EXPERIMENTAL SETUP
Particle used in this study is cigarette
smoke type with the specifications as
shown in Table 1.
In general, as shown in Figure 8, the
experimental apparatus consist of a inlet
and outlet smoke container box, test
section is equipped by a heater in order to
keep the hot side of the plate and cooling
water to keep the cold side of the plate,
gas sensor TGS 2600, microcontroller,
and LCD display. Cigarette smoke is
stored in the container box made of

450000
400000
350000
300000
250000
200000
150000
100000
500000
0
0,60

0,65

0,70

0,75

0,80

0,85

0,90

0,95

1,00

1.05

Rgas/Rair

Figure 7
Particle calibration to pt/cc

CHARACTERIZATION OF THERMAL PRECIPITATOR


IMANSYAH IBNU HAKIM, ET AL.

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 1 - 10

Figure 8
Testing scheme

through gas sensor that placed in the


outlet section can easily be known. Data
received by the gas sensor was sent to the
microcontroller then displayed t in the
LCD screen in digital form. 7 pieces of
gas sensor (G1 G7) is mounted in the
test section as shown in Figure 9.
The variation of temperature
difference (T) between hot plate
and cold plate are set as follow: 0o,
5o, 10o, 15o, and 20oC. But to avoid
the misinterpretation of temperature
difference (T) in thermophoresis for
example if hot plate temperature (T2)
= 50oC and cold plate temperature (T1)
= 27oC, then T will be T = T2 T1
= 23oC. This T = 23oC can also be
6

Figure 9
Test section

CHARACTERIZATION OF THERMAL PRECIPITATOR

SCIENTIFIC CONTRIBUTIONS OIL & GAS

IMANSYAH IBNU HAKIM, ET AL.

VOL. 35, NO. 1, APRIL 2012 : 1 - 10

interpreted T2 = 100oC and T1 = 77oC, where


both of them have a different radiation and
convection effect. Therefore we create new
non-dimensional parameter for temperature,
namely T*. Where T* = (Thot Tcold)/Thot or T*=
(T2 T1)/T2. Temperature is measured using
Type-K thermocouple and data collection was
carried out using a data acquisition system
(NI cDAQ-9174). In this research 5 (T1 T5)
thermocouples type-K were used and mounted
on the surface of the plate as shown in Figure
9. Photo of the experiment equipment can be
seen in Figure 10.
To clarify the effect of gravity on this
research, the position of hot plate are arranged so
that may be positioned above and below. Other
factors affecting the particle movement will be
discussed in the result and discussion.

Figure 10
Thermal precipitator test equipment

IV. RESULT AND DISCUSSION


Data from testing results can be seen in
Table 2., while the test graph can be seen in
Figure 11- 15.
Figure 11 shows the graph of the test result
for T = 0oC or T* = 0 when the heater is not
operated so the test equipment works in the
ambient temperature. The average number
of particle in the inlet section is 14,160 pt/cc
and in the outlet section is 13,328 pt/cc, so the
average difference is 833 pt/cc. It means that the
deposited particles are very small, so it can be
said that the thermophoretic force did not occur,

Figure 11
Deposited particles at T*=0

Table 2
The number of deposited particle

'T

10

15

20

Thot

25

30

35

40

45

Tcold

25

25

25

25

25

T*

0,00

0,17

0,29

0,38

0,44

IN OUT
IN OUT
IN OUT
IN OUT
IN OUT
(pt/cc)
(pt/cc)
(pt/cc)
(pt/cc)
(pt/cc)
(pt/cc)
(pt/cc)
(pt/cc)
(pt/cc)
(pt/cc)
14.160,99 13.328,08 15.536,47
Deposited
Particle

832

6.524,99 15.954,46

9011

6.974,51 16.092,46

8979

6.795,21 16.922,06 13.084,78

9297

3837

CHARACTERIZATION OF THERMAL PRECIPITATOR


IMANSYAH IBNU HAKIM, ET AL.

its mean no deposited particles.


The graph in Figure 12 shows the number
of particle when entering and exiting the test
section for the temperature difference between
hot plate and cold plate at 5oC or T* = 0.17. In
the first 5 seconds, the effect of thermophoresis
is cannot be observed yet but in the next second
and so on, there is a very significance difference
in the particle number. The average number of
particles in the inlet is 15,536 pt/cc (particles per
cubic centimeter) and in the outlet is 6,524 pt/
cc, so the average difference is 9,011 pt/cc. This
amount is the particle that deposited on the cold
side of the test section. The similar result was
obtained if the cold side of the test section in
placed on the top. This means there is no gravity
that influences the particle. So, how about the
influence of buoyancy force, Shafmann lift
force, Brownion motion and electrostatic force,
will be described below.
Bouyancy force arises because of the
viscosity difference in a fluid. In a gaseous
fluid, viscosity will decreases with increasing
temperature. The influence of buoyancy force
in a fluid can be known from the heat transfer
mechanism experienced by the fluid. Bouyancy
force only appears on the convection that occurs
naturally. To determine the type of convection
that occurs, we can compare its Grasshoff value
and Reynolds square value (Gr/Re2) of the fluid.
In this experiment, the comparison between
Grasshoff value and Rayleigh square is so
small, so the Bouyancy force can be ignored.
Saffmann lift force is a lift force on a particle
caused by the friction between particle and fluid
flow. Due to extremely fine particle diameter,
the particle will be lifted against the force of
gravity. In this experiment, the air velocity is
very low at 5 cm/s, therefore the Shafmann lift
force can be ignored and if Shafmann lift force
does exist, it would be very little.
According to Brownion motion, this
motion occurs in submicron-sized particle
(d < 0.01m), because of the inter-particle
momentum. Brownion motion is a random
motion of suspended solid particle in a fluid.
Brownian motion occur when an imbalance
force that generated from the movement of

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 1 - 10

Figure 12
Deposited Particles at T* = 0,17

Figure 13
Deposited Particles at T*=0.29

Figure 14
Deposited Particles at T*=0.38

CHARACTERIZATION OF THERMAL PRECIPITATOR

SCIENTIFIC CONTRIBUTIONS OIL & GAS

IMANSYAH IBNU HAKIM, ET AL.

fluid particles that are much smaller than the


solid particle and impacted the solid particle
repeatedly. Due to very small dimension of
the particle, therefore to be able to produce
Brownian motion, solid particle dimension
must be very small. Brownion motion applies
to the sub-micron particle in laminar flow.
In this study, the particle that used is the
smoke with size large than 0.01 m, so that
the influence of Brownion motion can be
ignored.
The influence of electrostatic force do not
exist because this force happened if there is the
difference in inter-particle electrical charge.
This force occurs in a particle if the particle
is placed in electrical field which has voltage
difference of E = 104 V. Based on Changfu
You et.al (2010), electrostatic force will be
effective and have a big impact for the particle
size larger than 10 m. While the smoke particle only
have the size up to 2.5 m.
The Graph in Figure 13 shows the number of
particles when entering and exiting the test section
for temperature difference between hot plate and
cold plate at 10oC or T* = 0.29. In the first 3 seconds
the effect of thermophoresis is cannot be observed
yet but after 5 second, there is a very significance
difference in the particle number. The average
number of particles in the inlet is 15,954 pt/cc and
in the outlet is 6,974 pt/cc, so the average difference
is 8,979 pt/cc.
Similar thing also happened in the graph in Figure
14 for temperature difference between hot plate and
cold plate at 15oC or T* = 0.38. Themophoretic
force can be observed after 3 seconds. This is indeed
happened because the distance between test section
and inlet section is 15 cm and the air velocity is 5
cm/s. The average number of particle in the inlet
section is 16,092 pt/cc, while in the outlet section
is 6,795 pt/cc, so the average difference is 9,297 pt/
cc.
If we see the average difference of the particle, for
T 5oC, 10oC and 15oC, they tend to have similar thermophoretic capabilities. The average number of particle that
deposited is 9000 pt/cc. If we refer the clean room standard,
ISO 14644-1 FED STD 209E, This equipment is not

yet meet the standard when operated at T 15oC.

VOL. 35, NO. 1, APRIL 2012 : 1 - 10

Figure 15
Deposited particle at T*=0.44

A rather odd thing happed at T = 20oC or T* =


0.44. As shown in Table 2. and graph in Figure 15,
average number of particle in the inlet is 16,922 pt/cc
and the outlet is 13,084 pt/cc, so the average number
of particle is 3,837 pt/cc. This is occurs because
the influence of convection on the hot plate, so the
thermal boundary layer that is former is greater than
the distance between two plates (larger than 5mm).
V. CONCLUSION
The characterization of thermal precipitator as an
alternative device for smoke collector has been conducted.
The particle that is used as sample is a cigarette smoke.
Their diameter range of 0.01 1 m. The average number
of particle in the inlet section is 16,000 pt/cc and in the
outlet section is 7,000 pt/cc, then the average number of
deposited particle is 9,000 pt/cc. We can conclude that
thermophoresis is the driving force for the accumulation
of the deposit or it may be said that the thermal precipitator
is potential to be used as smoke particle collector with
average efficiency of 56%. Thermal precipitator can be
used as particle collector device like diesel vehicle fume
and industrial fume. If we look at the range of particle
diameter that can be collected, this thermal precipitator
has a potential to be applied as an aerosol collector.

REFERENCE
1. A d r i a n P o s t e l n i c u , 2 0 0 7 , E f f e c t o f
thermophoresis particle deposition in free
convection boundary layer from a horizontal
flat plate embedded in a porous medium,
International Journal of Heat and Mass Transfer
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CHARACTERIZATION OF THERMAL PRECIPITATOR


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50 (2981-2985).
2. A. Messerer, R. Niessner, U. Poschl, 2003,
Thermophoretic deposition of soot aerosol
particles under experimental conditions relevant
for modern diesel engine exhaust gas systems,
Journal of Aerosols Science, 34 (1009-1021).
3. Byers, R.L., & Calvert, S., 1969, Particle
deposition from turbulence streams by means
of thermal force, Industrial and Engineering
Chemistry, Fundamentals, 8 (4), (646-655).
4. Byung Uk Lee, Du Sub Byun, Gwi-Nam Bae,
Jin-Ha Lee, 2006, Thermophoretic deposition
of ultrafine particles in turbulence pipe flow:
Simulation of ultrafine particle behaviour in
automobile exhaust pipe, Journal of Aerosols
Science, 37 (1788-1796).
5. Changfu You, Xiaohua Wang, Ruolei Liu,
ruichang Yang, 2010, Simultaneuos effects of
electrostatic field and thermophoresis on inhalable particulate matter removal, Journal of
Powder Technology 202 (95-100).
6. Chi-Chang Wang, 2006, Combined effects of
inertia and thermophoresis on particle deposition
onto a wafer with wavy surface, International
Journal of Heat and Mass Transfer 49 (13951402).
7. D.P. Healy, J.B. Young, 2010, An experimental
and theoretical study of particle deposition due
to thermophoresis and turbulence in an annular
flow, International Journal of Multiphase Flow
36 (870-881).
8. Gallis M.A., Rader D.J., Torczynski J.R.,
2004, A Generalized Approximation for the
Thermophoretic Force on a Free Molecular
Particle, Journal of Aerosols Science and
Technology, 38 (692-706).
9. Gonzalez D. et al, 2005, A New Thermophoretic
Precipitator for Collection of Nanometer-Sized
Aerosol Particles, Journal of Aerosols Science
and Technology, 39 (1064-1071).
10. Iman Zahmatkesh, 2008, On the importance
of thermophoresis and Brownian diffusion for
the deposition of micro and nanoparticles, International Communications in Heat and Mass
Transfer 35 (369-375).
11. J. Aitken, 1884, On the formation of small clear
space in dusty air, Transactions of the Royal

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Society of Edinburgh (239-272).


12. J. Tyndall, 1870, On dust and disease,
Proceeding of the Royal Institution of Great
Britain 6, (1-14).
13. K.K. Dinesh , S. Jayaraj, 2009, Augmentation of
thermophoretic deposition in natural convection
flow through a parallel plate channel with heat
sources, International Communications in Heat
and Mass Transfer 36 (931-935).
14. M. Epstein, G.M. Hauser, R.E. Henry, 1985,
Thermophoretic Deposition of Particles in Natural Convection Flow From a Vertical Plate``,
ASME J. Heat Transf;. Vol. 107 (272-276).
15. Montassier, N., Bouland, D., and Renoux, A.,
1990, Experimental study of thermophoretic
deposition of particles in laminar tube flow,
Proceedings of the third international aerosol
conference, (pp. 395-398). Kyoto, Japan.
16. Nishio, G., Kitani, S., & Takahashi, K.,
1974, Thermophoretic deposition of aerosol
particles in a heat exchanger pipe, Industrial
and Engineering Chemistry Process Design
Development, 13 (4), (408-815).
17. Romay, F.J., Takagaki, S.S., Pui, D.Y.H., &
Liu, B.Y.H., 1998, Thermophoretic deposition
of aerosol particles in turbulent pipe flow,
Journal of Aerosol Science, 29, (943-959).
18. R. Tsai, J.S. Huang, 2010, Combined effect of
thermophoresis and electrophoresis on particle
deposition onto a vertical flat plate from mixed
convection flow through a porous medium,
Chemical Engineering Journal 157 (52-59).
19. Stanford Research Institute Journal, 1961,
Characteristics of Particles and Particle
Dispersoids, Thrird Quarter, California.
20. Stratmann, F., Fissan, H., 1989, Experimental and theoretical study pf submicron
particle transport in cooled laminar tube flow
due to combined convection, diffusion, and
thermophoresis, Journal of Aerosol Science, 20,
(899-902).
21. Zhou Tao et al, 2009, Visual experiment
research of the inhaled particle thermophoresis
deposition rule in the rectangle turbulence flow
tube, Journal of Applied Thermal Engineering,
29 (1138-1145).

CORROSION INHIBITION OF MILD STEEL IN 1M HCL


BY CATECHIN MONOMERS FROM COMMERCIAL
GREEN TEA EXTRACTS
Nofrizal
Researcher at LEMIGAS R & D Centre for Oil and Gas Technology
Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230 INDONESIA
Tromol Pos: 6022/KBYB-Jakarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7 246150
First Registered on January 30th 2012; Received after Corection on March 16th 2012
Publication Approval on : April 30th 2012

ABSTRACT
The inhibitory effect of two Indonesian green tea extracts (containing various catechins) were
investigated on the corrosion of mild steel (MS) in 1M HCl medium. The anticorrosion effect was
evaluated by conventional weight loss method, potentiodynamic polarisation, electrochemical
impedance spectroscopy (EIS) studies and scanning electron microscopy (SEM) technique. The
results evidenced that both the tea extracts act as a good corrosion inhibitor and the inhibition
efficiencies (% IE) were in good agreement for all the studies. Adsorption of green tea extract
constituent was found to follow Langmuir adsorption isotherm and the calculated Gibbs free
energy values indicated the physisorption of inhibitor over the mild steel surface. SEM - EDX
studies show the adsorption of catechin monomers which forms a protective layer over the mils
steel surface. High performance liquid chromatography (HPLC) analysis was carried out to
quantify the catechin fractions in the tea extract and it was found that eight catechin monomers
were present in both tea extracts. From all of monomers, it was found that four monomers were
identified as components responsible for controlling the dissolution of mild steel in 1 M HCl
medium.
Keywords: mild steel, corrosion inhibition, green tea, HPLC, potentiodynamic, EIS

I. INTRODUCTION
Tea is one of the most frequently consumed
beverages in the world, dating back to more than
5000 years ago. Numerous studies have recorded
the beneficial effects of tea, e.g., reducing the risk of
cancer, preventing arteriosclerosis (Kakuda, 2002),
antiallergic action (Sano et al., 1999), antimicrobial
properties (Hamilton-Miller, 1995), lowering the
risk of stomach cancer (Setiawan et al., 2001),
oesophagus (Hara, 2006), and lung cancer (Zhong
et al., 2001). Previous studies have shown that green
tea consists predominantly of flavan monomers
namely (+)-catechin, (+)-epicatechin and alkaloids
(Taniguchi et al., 2007). Interestingly, catechin also
exhibits anti-oxidative activity which could reduce
oxidation, corrosion, deterioration and discolouration
processes (Kyung & Yinzhe, 2006).
Corrosion is a common phenomenon in industries
and it attracts considerable amount of interest because

of its hazardous nature on metals (Bothi et al., 2010).


In many industries, acid solutions are frequently used
for acid pickling, industrial cleaning, acid descaling,
oil-well acid in oil recovery and the petrochemical
processes (Fan et al., 2002; Hosseini et al., 2007;
Shahrabi et al., 2007) which leads to corrosive attack
of metals. Generally, the inhibitors are used in these
processes to control the metal dissolution as well
as the acid consumption. Most of the inhibitors are
organic molecules (Nmai, 2004) however inorganic
molecules (Kiehl & Brendel, 2002) and polymeric
materials (Kalendov et al., 2008) are also used.
Although high anticorrosion potential was exhibited
by many organic molecules, they pollute the environment during their synthesis and applications (Raja &
Sethuraman, 2008).
Natural products are being studied for their
corrosion inhibition potential as they are more
environmentally friendly, showing good inhibition
11

CORROSION INHIBITION OF MILD STEEL IN

SCIENTIFIC CONTRIBUTIONS OIL & GAS

NOFRIZAL

efficiency with low risk of environmental pollution


(Duke et al., 2000; Rahim & Kassim, 2008). The
use of natural compounds from plant extracts rich
in tannins (Rahim et al., 2008), Rauvolfia serpentine
(Bothi Raja & Sethuraman, 2009b), black pepper
extract (Bothi Raja & Sethuraman, 2008), Lawsonia
(El-Etre et al., 2005), Opuntia extract (El-Etre, 2003)
have been widely reported by several authors.
Anticorrosion potential of tea wastes (Sethuraman
et al., 2001), as well as its constituent caffeine
(Anthony et al., 2004; Fallavena et al., 2006) had been
successfully reported earlier. These studies concluded
that the heterocyclic atoms of the caffeine molecule
are responsible for its anticorrosion potential. The
present study was inspired by the reports that green
teas are characterised by the presence of catechin
monomers that have been studied individually, which
coincidentally are effective corrosion inhibitors
(Hosseini et al., 2003; Ashassi-Sorkhabi et al., 2005).
Thus this work aims at investigating the anticorrosion
potential of a natural product viz., catechin monomers
derived from green tea extracts on MS in 1 M
HCl medium. The assessment of the corrosion
behaviour has been studied using weight loss,
EIS, potentiodynamic polarisation measurements,
IR spectroscopy and the morphology of inhibited
mild steel surface analysed by scanning electron
microscopy equipped with energy dispersive X-ray
spectroscopy (SEM-EDX). High performance liquid
chromatography (HPLC) has been utilised identify
and quantify the active components of the green tea
extracts simultaneously that are consumed during the
corrosion inhibition process.
II. EXPERIMENTAL
A. Inhibitor preparation
Two Indonesian green tea samples (Camellia
sinensis) were purchased from a local supermarket.
The green tea samples (10 g) were extracted in 100
mL acetone 70% for 24 h at 80oC by using hot plate
method (Row & Jin, 2006). The extract was cooled
and centrifuged at 4000 rpm for 5 min. The sample
was evaporated and the resulting gummy material obtained was dried and grinded. Various concentrations
of the tea extracts were prepared by dissolving known
quantities of the resultant powder in 1 M HCl.
12

VOL. 35, NO. 1, APRIL 2012 : 11 - 24

B. Specimen preparation
The MS specimens of composition (Fe: 97.57, C:
1.54, O: 0.88% weight) were taken and were polished
using different grades of abrasive paper from 400
up to 1200 before the analysis. MS specimens of
size (2.7 x 2.7 x 0.1 cm) were used for the weight
loss method and SEM analysis while specimens
with an exposed area of 3.142 cm2 were used for the
electrochemical studies.
C. Weight loss method
The experiment was carried out in a beaker
containing 100 mL test solution. A clean pre-weighed
MS specimen was completely immersed in 100 ml of
electrolyte with and without the addition of different
concentrations of GT extract at room temperature
(30o C 2). After 24 h of immersion in 1 M HCl
solution, the specimen was withdrawn, rinsed with
distilled water, washed with acetone, dried and
weighed. Triplicate measurements were performed.
The inhibition efficiency (% IE) was calculated as
follows:

Wi
% IE= 1 100
W0

............................... (1)

Where,
W0 and Wi are the weight loss of mild steel without
and with inhibitor, respectively.
D. Electrochemical method
Electrochemical studies were carried out using
Gamry Instrument reference 600 (potentiostat/
galvanostat/ZRA). A three-electrode cell system
were employed for the measurement wherein mild
steel with an exposed area of 3.142 cm2 acts as a
working electrode (WE) while platinum wire and
saturated calomel electrode acts as counter electrode
and reference electrode (SCE), respectively. The
measurements were performed in 1.0 M HCl solution
with and without the addition of different inhibitor
concentrations in an aerated environment. All
polarisation and impedance curves were recorded at
room temperature (302)o C and the electrodes were
immersed in the test solution for 30 min at natural
potential to attain steady state before measurement.
AC impedance measurements were carried out
at the corrosion potential (Ecorr) with frequency

CORROSION INHIBITION OF MILD STEEL IN

SCIENTIFIC CONTRIBUTIONS OIL & GAS

NOFRIZAL

VOL. 35, NO. 1, APRIL 2012 : 11 - 24

ranging from 0.1 to 10000 Hz at an amplitude of


10 mV. The impedance diagrams are given in the
Nyquist representation. Inhibition efficiency (% IE)
is calculated from the charge transfer resistance (Rct)
values by using equation (2):

Table 1
Effect of green tea extracts for the corrosion
of mild steel in 1.0 M HCl (Weight loss studies)

Inhibitor

Rct(o)
% IE = 1 100
Rct(i)

........................... (2)

Where, Rct(o) and Rct(i) is the charge transfer resistance


of mild steel without and with inhibitor, respectively.
The potentiodynamic current density - potential
curves were recorded by scanning the electrode
potential from -800 to -200 mV (vs SCE) with a
scanning rate of 1 mV s-1. The linear Tafel segments
of the anodic and cathodic curves were extrapolated
to corrosion potential to obtain the corrosion current
densities (Icorr). Equation (3) shows the calculation of
% IE from the Icorr values.

Icorr(i)
% IE = 1 100
Icorr(o)

........................... (3)

Where, I corr(i) and I corr(o) is the corrosion current


density of mild steel with and without inhibitor,
respectively.

E. FTIR spectroscopic analysis


The green tea extracts were analysed by Fourier
transformed infrared (FTIR) spectroscopy for the
identification of the functional groups. The FT IR
study was carried out by using the Perkin Elmer
System 2000 FT IR instrument in the IR range
400-4000 cm-1. The pellet for the solid sample was
prepared by using KBr pellet method with the ratio
of the sample to KBr was 1:10. The mixture was then
pressed with 8-ton pressure to obtain a palette. The
acquiring of the spectra and peaks assignment was
performed using FTIR software Spectrum Version
3.02.01.

GT 1

GT 2

Concentration Weight loss % IE


(ppm)
(g)
(wt%)
0

0.0448

50

0.0231

48.44

100

0.0184

58.93

150

0.0144

67.85

200

0.0121

75.22

50

0.0220

50.89

100

0.0171

61.83

150

0.0133

70.31

200

0.0893

79.24

IE, inhibition efficiency; GT, green tea

G. High Performance Liquid Chromatography


(HPLC) analysis
The HPLC system used consisted of two LC-10
AD VP pumps for high-pressure gradient elution
attached with a SPD-10Avp UV detector (Shimadzu,
Japan). The mobile phase composition comprises of
water: acetonitrile: methanol (83:6:11). The column
used was a monolithic Rp18 e 1004.6 mm (Merck
KGaA, Germany). Signals were monitored at 280
nm. Standard solutions and tea samples were filtered
through a 0.45 m acrylic polymer filter before being
injected into the HPLC unit. Quantification was done
using the external calibration method where peak
areas versus concentrations were plotted. Linear
least-square analysis on the straight line was used
for the quantification, while qualitative analysis
was based on comparison of the retention times
of standards. 20 L of the analytical samples were
injected.
III. RESULTS AND DISCUSSION

F. Scanning electron microscopy (SEM)

A. Weight loss measurement

Surface analysis was conducted on the MS surface


before and after the electrochemical measurements.
After the electrochemical measurements, the MS
specimens were removed, slowly rinsed with distilled
water and dried. The analysis was performed using
SEM LEO SUPRA 50VP instrument.

The % IE obtained for different concentrations


of green tea extract is depicted in Table 1.
The results show a positive correlation between
the concentration of green tea extract and the
inhibition efficiency for mild steel in 1 M HCl
solution. This trend may result from the fact that
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CORROSION INHIBITION OF MILD STEEL IN

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VOL. 35, NO. 1, APRIL 2012 : 11 - 24

the amount adsorbed and the coverage of inhibitor


molecules on the mild steel surface increased with the
increase of the green tea extract concentration, thus
the mild steel surface is efficiently blocked from the
hydrochloric acid. The maximum % IE was obtained
at maximum concentration of 200 mg L-1 for both
green tea extracts and was found to be 75.22 and
79.24 % for GT 1 and GT 2, respectively.

It is clear from the potentiodynamic experimental


results that the presence of tea extracts reduces the
corrosion current density, Icorr, which is an indication
of the decrease in the corrosion rate. The decrease
in Icorr values is due to the decrease of the aggressive
acid attack on the mild steel surface, attributed to the
adsorption of inhibitor molecule. Furthermore, the
additions of tea extract shift the corrosion potential
to the positive side, due to the decrease in the anodic
reaction. This indicated that the inhibitors were
adsorbed on the anodic sites of the mild steel surface,
which prevented the metal dissolution reaction and
thus controlling the corrosion process. However, the
Tafel constants c and a did not change significantly
with inhibitor concentrations, indicating that

B. Potentiodynamic polarisation measurements


The various corrosion parameters viz., corrosion
potential Ecorr, corrosion current density Icorr, cathodic
(c), anodic (a) Tafel slopes and (IE) were calculated
using the intersection of the anodic and cathodic Tafel
lines and are given in Table 2.

Polarisation results are depicted as Tafel plots in Figures 1a and b


0

(a)

Current Density Log I)

-1
-2
-3

-4
e

-5

a. blank 1 M HCI
b. 50 ppm
c. 100 ppm
d. 150 ppm
e. 200 ppm

-6
-7
-8
-800

-700

-600

-500

-400

-300

-200

Potential (mV) vs SCE

(b)

Current Density Log I)

-1
-2
-3
-4

a. blank 1 M HCI
b. 50 ppm
c. 100 ppm
d. 150 ppm
e. 200 ppm

-5
-6

a
b

-7
-800

-700

-600

-500

-400

-300

Potential (mV) vs SCE

Figure 1
Tafel plots of (a) GT 1, and (b) GT 2 extracts on mild steel in 1 M HCl

14

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VOL. 35, NO. 1, APRIL 2012 : 11 - 24

Table 2
Effect of green tea extracts for the corrosion of mild steel in 1.0 M HCl
(Polarization studies)

Inhibitor
-

GT 1

GT 2

Icorr

Concentration
Ecorr (mV)
(ppm)

a (mV/dec) - c (mV/dec)

(A/cm2)

% IE

-484

386

88.7

147.9

50

-477

158

87.3

152.5

59.07

100

-468

136

40.4

54.1

64.77

150

-461

94

32.5

34.8

75.65

200

-452

78

30.1

32.1

79.79

50

-482

132

86.8

155.9

65.80

100

-468

111

85.7

143.6

71.24

150

-455

77

78.3

132.1

80.05

200

-442

62

42.2

114.3

83.94

GT, green tea; IE, inhibition efficiency

120
(a)

60
40
20
a
0

50

100
150
Z real (, cm2)

e
200

250

200
(b)

-Z imaginary (, cm2)

The impedance parameters,


viz., charge transfer resistance
( R ct) , a n d c o n s t a n t p h a s e
element (CPE) were calculated
by analysing the impedance
plots using the equivalent circuit
(Figure 3) and the values are listed
in Table 3.

80

C. Electrochemical impedance
studies (EIS)
EIS analysis shows typical
Nyquist plots for GT 1 and GT
2 extracts which are given in
Figures 2a and b, respectively.

a - blank 1M HCI
b - 50 ppm
c - 100 ppm
d - 150 ppm
e - 200 ppm

100

-Z imaginary (, cm2)

the retardation of the reactions


(hydrogen evolution and metal
dissolution) was affected without
changing the mechanism. The %
IE was found to enhance when
the concentration of the green tea
extract was increased, resulting
in maximum of 79.79% for GT
1 and 83.94% for GT 2 extracts,
respectively. The results obtained
are in good agreement with those
obtained from the weight loss
measurements.

a - blank 1M HCI
b - 50 ppm
c - 100 ppm
d - 150 ppm
e - 200 ppm

160

120
80

40
a

0
0

100

200
Z real (, cm2)

300

400

Figure 2
Nyquist plots of (a) GT 1, and
(b) GT 2 extracts on mild steel in 1 M HCl

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The usefulness of these data permits


the analysis of the alternating current
(AC) impedance data, which are based
on the modelling a corrosion process by
an electrical circuit (Hussin & Kassim,
2010).
From Figures 2a and b, it was observed
that the Nyquist plots showed slightly
depressed semi-circular shapes with only
one time constant and the diameters of the
capacitive loop increased with increasing
inhibitor concentration. This indicates
the increasing coverage of the metal
surface and also signifies a charge transfer
process as the main controlling factor in
the corrosion process (Benabdellah et al.,
2007).

VOL. 35, NO. 1, APRIL 2012 : 11 - 24

Table 3
Effect of green tea extracts for the corrosion of mild
steel in 1.0 M HCl (Impedance studies)

Inhibitor
-

GT 1

GT 2

Rct
(.cm2)

CPE
(Fcm2)

% IE

41.4

48.7

50

87.6

28.7

52.74

100

127.8

25.3

67.60

150

177.1

22.1

76.79

200

250.6

18.1

83.47

50

110.2

33.4

62.70

100

291.1

28.7

85.88

150

351.1

21.1

88.21

200

409.4

18.1

89.96

GT, green tea; IE, inhibition efficiency; CPE,


constant phase element

Further, it is also observed from


Table 3 that the Rct values increased with
increasing concentrations of inhibitors.
This is because, the addition of inhibitor increases the
adsorption of phyto-constituents over the MS surface
and results in the formation of a protective layer which
may decrease the electron transfer between the metal
surface and the corrosive medium. The values of CPE
decrease with the increase in inhibitor concentrations
due to the addition of inhibitor that increases the
adsorption phenomena, which consequently may
decrease the electrical capacity and/or increase in
the thickness of the electrical double layer (Bentiss
et al., 2007). The % IE of impedance results, are in
good agreement with the polarisation and weight loss
studies that shows maximum of 83.47 and 89.96%
for GT 1 and GT 2 extracts, respectively for the
maximum concentration of 200 g mL-1.
D. Adsorption isotherm
To examine the adsorption behaviour of the
green tea extracts on the MS surface in 1 M HCl
medium, the adsorption isotherm was plotted. The
dependence of the fraction of the surface covered
() obtained by the ratio of E/100 as a function of
the logarithm of the concentration (log C) of tea
extracts was tested graphically by fitting it to several
adsorption isotherms. The experimental data from
all measurements was found to fit well with the
Langmuir adsorption isotherm and are depicted in
Figures 4a, b and c for weight loss study, polarization

16

Concentration
(ppm)

Rs

Cdl
Rct

Figure 3
Electrical equivalent circuit for AC
impedance measurement

and impedance studies respectively, which obeys


(Morad & El-Dean, 2006):

C 1
=
+ C and Gads = - RT ln Cwater Kads ... (4)
Kads
Where, C is the concentration of inhibitor, is
the surface coverage determined by E/100, Kads is
the adsorption equilibrium constant and Gads is the
standard Gibbs free energy, R is molar gas contant,
T is the temperature and Cwater is the concentration of
water in 1000 g L-1. The Gibbs free energy values
(Gads), linear regression coefficient and adsorption
desorption equilibrium constant (Kads) derived from
the Langmuir plot are depicted in Table 4.
The negative values of G ads revealed the
spontaneity of the adsorption process (Hosseini et al.,

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VOL. 35, NO. 1, APRIL 2012 : 11 - 24

Table 4
Adsorption isotherm parameters
Inhibitor

Goads (kJ/mol)

0.9994

13.47

-23.61

Potentiodynamic

0.9992

23.79

-25.18

EIS

0.9996

25.41

-25.44

0.9994

18.01

-24.51

Potentiodynamic

0.9998

26.61

-25.49

EIS

0.9998

35.79

-26.31

2003). Generally, Gads values


around 20 kJ mol1 or lower
are associated with electrostatic
interactions between the charged
centers of inhibitors and charged
metal surface (physisorption)
(Ashassi-Sorkhabi et al., 2005).
Values more negative than 40
kJ mol1 involve charge sharing
or transfer from the inhibitor
molecules to the metal surface to
form a coordinate type of bond
(chemisorption) (Bentiss et al.,
2002). The calculated -Gads
values for all the studies were
depicted in Table 4. The -Gads
values were found to be in the
range between -23 to -27 kJ mol-1
for both the green tea extracts,
which evidenced the typical
physisorption of inhibitors on
mild steel surface. The higher
Kads values obtained for GT 2,
suggesting that this inhibitor was
more strongly adsorbed onto the
MS surface compared to GT 1
(Kardas & Solmaz, 2006).
E. High Performance Liquid
Chromatography (HPLC)
analysis
The concentrations of the
catechin monomers and caffeine
in the green tea extracts were
determined by using the HPLC
technique. This method is by

C/0 (g L-1)

Weight Loss

0.30
0.25
0.20
0.15
0.10
0.05
0.00

(a)

y = 0.8464x - 0.0787
R2 = 0.9994

GT 1
GT 2

0.00

0.05

y = 0.8968x - 0.0553
R2 = 0.9994

0.10
0.15
0.20
Concentration (g L-1) C

0.25

dl

C/0 (g L-1)

GT 2

Kads (L g -1)

Weight Loss

(b)

0.30
0.25
0.20
0.15
0.10
0.05
0.00

y = 1.0473x - 0.0253
R2 = 0.9992

GT 1

y = 1.0009x - 0.0218
R2 = 0.9998

GT 2

0.00

0.05

0.30

0.10
0.15
Concentration (g L-1)

0.20

0.20
0.15

0.25

(c)

y = 1.0260x - 0.0419
R2 = 0.9996

0.25

C/0 (g L-1)

GT 1

R2

Methods

GT 1
y = 1.0040x - 0.0209
R2 = 0.9998

0.10

GT 2

0.05
0.00
0.00

0.05

0.10

0.15

0.20

0.25

Concentration (g L-1)
Figure 4
Langmuir adsorption isotherm plots for GT 1 and GT 2 extracts
on the mild steel surface from (a) weight loss, (b) potentiodynamic and
(C) EIS measurement

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VOL. 35, NO. 1, APRIL 2012 : 11 - 24

far the most popular technique for analysing tea


catechins. Wang et al. (2000) reported on the use
of methanol/ water and acetonitrile/water as mobile
phase for the catechin analysis. The catechin
monomers and caffeine were separated in about 40

minutes. In contrast to all previous HPLC analysis that


uses particle-type stationary phase, the present study
uses a monolithic column. The use of highly porous
monolithic columns has resulted in many advantages
to the user (e.g., minimum back pressures, faster

Table 5
Determination of catechins and caffeine
in green tea samples by HPLC analysis

Table 6
Consumption of catechin monomers
after the corrosion process determined by
HPLC analysis

Concentration (mg g-1)

Analytes

GT 1
GC

GT 2
Inhibitor

Catechin
monomers

Inhibition
consumed (%)

3.29 0.43

4.89 0.78

12.07 0.55

16.22 0.19

2.21 0.24

2.47 0.52

EGC

8.830.24

Caffeine

33.24 0.38

36.51 0.72

ECG

11.590.32

EGCG

30.72 0.45

33.01 0.59

EGCG

13.260.29

EC

6.12 0.27

7.08 0.29

GCG

2.82 0.13

2.99 0.16

EC

4.250.21

ECG

7.23 0.17

9.21 0.16

EGC

10.310.19

CG

0.53 0.07

0.58 0.08

ECG

13.660.38

ECGC

16.150.27

EGC
C

GT 1

EC

GT 2

n = 3, GT, green tea; GC, gallo catechin; EGC,


epigallocatechin;C,catechin;EGCG,
epigallo catechin gallate; EC, epicatechin;
GCG,gallocatechingallate;ECG,
epicatechin gallate and CG, catechin gallate

3.250.11

n = 3, GT, green tea; EGC, epigallo catechin;


EGCG,epigallocatechingallate;EC,
epicatechin; ECG, epicatechin gallate

4
0.50

Volts

0.50

0.25

5
3

0.25
8

0.00

0.00
0

10

12

14

16

18

20

Time (minutes)

Figure 5
The separation of catechin and caffeine standards mixture (40 ppm) using of water:
acetonitrile: methanol (83: 6: 11) as mobile phase. Peak assignment :
(1) (-)-gallocatechin, (2) (-)-epigallo catechin (EGC), (3) (-)-Catechin (C), (4) (-)-caffeine, (5)
(-)-Epigallocatechin gallate (EGCG), (6) (-)-Epicatechin (EC), (7) (-)- gallocatechin gallate (GCG),
(8) (-)-Epicatechin gallate (ECG), and (9) (-)- catechin gallate (CG)

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Catechin

Epicatechin

Epigallocatechin

Gallocatechin

Catechin gallate

Gallocatechin gallate

Epicatechin gallate

Caffeine
Epigallocatechin gallate

Figure 6
Structures of catechin monomers and caffeine

separations, consumption of less mobile phases).


In the present study, the optimised isocratic system
comprising water: acetonitrile: methanol (83:6:11)
as mobile phase was used and satisfactory separation
of the catechins and caffeine was obtained using a
flow rate of 1.4 mL min-1 (Figure 5). All components
were separated in about 8 min. The separation was
comparatively faster than the previous reports
(Fernandez et al., 2000; Wang et al., 2000; Nishitani

& Sagesaka, 2004) that are based on conventional


particle-type stationary phase. Nine peaks were
observed for the tea extracts and their concentrations
are given in Table 5. Based on the retention times,
the peaks were identified as gallocatechin (GC),
epigallocatechin (EGC), catechin (C), caffeine,
epigallocatechin gallate (EGCG), epicatechin (EC),
gallocatechin gallate (GCG), epicatechin gallate
(ECG), catechin gallate (CG). The order of elution
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VOL. 35, NO. 1, APRIL 2012 : 11 - 24

was: GC > EGC > C > caffeine > EGCG > EC >
highest caffeine content, the HPLC results did not
GCG> ECG > and > CG (Figure 5).
show the consumption of caffeine alkaloid. This
contradicts to the earlier studies that reported caffeine
In order to determine the anticorrosion ingredients
as an effective metal corrosion inhibitor (Anthony et
of tea extracts quantitatively, HPLC analysis of
al., 2004). This disparity could be due to the fact that
test solutions was carried out before and after the
the presence of the catechin monomers (EC, EGC,
corrosion processes. The concentrations of catechin
ECG and EGCG) may have blocked the adsorption
consumed after the inhibition process from the
of caffeine molecule over the MS surface or due
weight loss measurements are given in Table 6. In all
to the different electrolyte used. The structures of
previous reports (Rahim et al., 2007), it was assumed
the various catechins and caffeine are shown in
that all monomers would act as inhibitors for steel
Figure 6.
corrosion and their inhibitive performance depended
on their concentrations. However, a key findings of
F. FT IR studies
this study was that only certain catechin monomers
The green tea extracts were studied by FTIR
gave significant contributions to the corrosion
spectroscopy
in order to identify the functional
inhibition.
groups.
Figure
7 shows the IR absorption spectrum
Among the eight catechin monomers
of the green tea extracts and the typical functional
present in the tea extract, only epicatechin (EC),
groups of catechin namely O-H, C=C (for aromatic
epigallocatechin (EGC), epicatechin gallate (ECG)
rings) and C-O that were evidenced at 3400-3100,
dan epigallocatechin gallate (EGCG) were found to
1600 and 1150 1010 cm-1, respectively (Maoela et
be consumed in the inhibition process as witnessed
al., 2009). These are the functional groups that were
from the reduction of peak areas in the HPLC
already identified as potent anticorrosion groups in
chromatogram. The order of increasing consumption
organic
corrosion inhibitors as reported by many
and thus adsorption is as follows EC < EGC < ECG <
researchers (Blustein et al., 2006).
EGCG. The peak areas for the other components were
virtually unchanged. Interestingly, none of the chiral
It was assumed that a catechin monomer
counterparts [(C), (GC), (GCG) and (CG)] were
which has more numbers of hetero functionality
found to participate in the inhibition process although
and electronic clouds could serve as a better
some of these monomers have shown inhibitive effect
corrosion inhibitor. According to this consideration,
Epigallocathecin gallate (EGCG) monomer was
when used individually (Rahim et al., 2007). This
assumed to contribute more during the corrosion
suggests that the inhibition is stereospesific and the
(R, R) conformation. (Figure
6) may have facilitated the
absorption of these molecules.
The higher catechin content
of the GT 2 extract showed
higher consumption of
the monomers, which is
consistent with the higher
inhibition efficiency of the
GT 2 extract as compared to
the GT 1 extract. The amount
of monomers consumed also
showed a positive correlation
with the time of immersion
when higher consumption
of monomers was recorded
for the weight loss method.
Figure 7
IR spectra of (a) GT 1, and (b) GT 2 extracts.
Surprisingly, although both
green tea extracts had the
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CORROSION INHIBITION OF MILD STEEL IN

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inhibition process since it has three


aromatic rings along with eight OH
groups while ECG contains seven
OH groups and EC, EGC having less
numbers of aromatic rings and OH
groups. Indeed, as mentioned earlier,
HPLC results showed that EGCG
monomer was consumed the most
during the inhibition process, suggesting
that the presence of hetero functional
groups (OH) and - electrons on
the benzene ring contributed to the
corrosion inhibition by EGCG.

VOL. 35, NO. 1, APRIL 2012 : 11 - 24

Table 7
The composition of samples from the EDX analysis

Fe

Fresh mild steel

97.57

0.88

1.54

Mild steel without inhibitor

74.23

23.54

1.41

Mild steel with GT 1 extract

89.21

7.45

4.81

Mild steel with GT 2 extract

90.68

5.79

4.07

GT green tea

G. Scanning Electron MicroscopyEnergy Dispersive X-Ray


Spectroscopy (SEM-EDX)
studies
To monitor the morphological
changes on the MS surface during the
corrosion process, SEM EDX studies
were carried out. MS specimens were
screened after the potentiodynamic polarisation studies and the micrographs
are given in Figures 8a, b and c. From
Figure 8a.
It is clearly seen that the surface is
very rough and severely damaged in the
absence of inhibitors while in Figures
8b and 8c the surfaces are transformed
into smoother, more uniform deposits
upon addition of the green tea extract.
The distribution of rough surfaces were
significantly reduced. The composition
of the sample from the EDX analysis
showed the increase of carbon and
reduction of oxygen atoms due to the
reduction of corrosion products (Table
7), probably due to the adsorption of the
monomers of the green tea extract.
IV. CONCLUSIONS
The two commercial Indonesian
green tea extracts showed comparable
inhibition properties for the corrosion
of mild steel in 1 M HCl medium. The
% IE obtained via polarisation measurement is in good agreement with

Element (%)

Sample

Mag:1.5 KX 10um

Mag:1.5 KX 10um

Mag:1.5 KX 10um

Figure 8
SEM images of mild steel in 1M HCl medium
(a) absence of inhibitor (b) GT 1, and (c) GT 2 extracts

that obtained by using the weight loss and impedance methods. The
polarisation results also revealed that both inhibitors control the corrosion through mixed mode of inhibition. SEM - EDX studies show
the adsorption of catechin monomers which forms a protective layer
over the MS surface. Both the tea extracts were found to obey the
Langmuir adsorption isotherm and the thermodynamic parameters
prove the physical adsorption of the phytoconstituents. The HPLC

21

CORROSION INHIBITION OF MILD STEEL IN


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technique proved to be an indispensable tool for the


simultaneous determination of the active components
of the green tea extracts that are responsible for the
inhibition of MS corrosion.
V. RECOMMENDATION
The HPLC technique has proven to be an
essential tool for simultaneous determination of
catechin monomers that are responsible for the
corrosioninhibition of mild steel. This technique
can be used to explore different corrosion inhibition
mechanism for various corrosive media viz.,
H2SO4, basic electrolytes (e.g, NaOH) and neutral
electrolytes (e.g, NaCl) as well as for various
metals viz., Zn, Cu dan Al. The active constituents
from other natural products containing alkaloids,
flavonoids and polyphenols for corrosion inhibition
of metals can be similarly determined. In addition,
through the same technique, the antioxidant studies of
these plant extracts can be correlated to the corrosion
inhibition properties.
REFERENCES
1. Anthony, N., Malarvizhi, E., Maheshwari,
P., Rajendran, S., & Palaniswamy, N. (2004).
Corrosion inhibition by caffeine: Mn2+ system.
Indian journal of chemical technology, 11(3),
346-350.
2. Ashassi-Sorkhabi, H., Shaabani, B., &
Seifzadeh, D. (2005). Effect of some pyrimidinic
Shciff bases on the corrosion of mild steel in
hydrochloric acid solution. Electrochimica acta,
50(16-17), 3446-3452.
3. Benabdellah, M., Touzani, R., Aouniti, A.,
Dafali, A., El Kadiri, S., Hammouti, B., &
Benkaddour, M. (2007). Inhibitive action of
some bipyrazolic compounds on the corrosion of
steel in 1 M HCl:: Part I: Electrochemical study.
Materials Chemistry and Physics, 105(2-3), 373379.
4. Bentiss, F., Lebrini, M., Lagrene, M.,
Traisnel, M., Elfarouk, A., & Vezin, H. (2007).
The influence of some new 2, 5-disubstituted 1,
3, 4-thiadiazoles on the corrosion behaviour of
mild steel in 1 M HCl solution: AC impedance
study and theoretical approach. Electrochimica
acta, 52(24), 6865-6872.

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SCIENTIFIC CONTRIBUTIONS OIL & GAS


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5. Bentiss, F., Traisnel, M., Chaibi, N., Mernari,


B., Vezin, H., & Lagrene, M. (2002). 2, 5-Bis
(n-methoxyphenyl)-1, 3, 4-oxadiazoles used as
corrosion inhibitors in acidic media: correlation
between inhibition efficiency and chemical
structure. Corrosion Science, 44(10), 22712289.
6. Blustein, G., Romagnoli, R., Jan, J., Di Sarli,
A., & del Amo, B. (2006). Zinc basic benzoate
as eco-friendly steel corrosion inhibitor pigment
for anticorrosive epoxy-coatings. Colloids and
Surfaces A: Physicochemical and Engineering
Aspects, 290(1-3), 7-18.
7. Bothi Raja, P., & Sethuraman, M. (2009a).
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15. Fan, H. B., Fu, C. Y., Wang, H. L., Guo, X. P.,


& Zheng, J. S. (2002). Inhibition of corrosion of
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18. Hara, Y. (2006). 3 Prophylactic Functions of Tea
Catechins. Protective effects of tea on human
health, 16.
19. Hosseini, M., Ehteshamzadeh, M., & Shahrabi,
T. (2007). Protection of mild steel corrosion
with Schiff bases in 0.5 M H2SO4 solution.
Electrochimica acta, 52(11), 3680-3685.
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antagonism in mild steel corrosion inhibition
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oolong tea. Journal of agricultural and food


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40. Taniguchi, S., Kuroda, K., Doi, K. I., Inada, K.,


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695-700.

THE IMPROVEMENT OF MERCURY REMOVAL


IN NATURAL GAS BY ACTIVATED CARBON
IMPREGNATED WITH ZINC CHLORIDE
Lisna Rosmayati
Technological Assessor at LEMIGAS R & D Centre for Oil and Gas Technology
Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230 INDONESIA
Tromol Pos: 6022/KBYB-Jakarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150
First Registered on January 30th 2012; Received after Corection on March 14th 2012
Publication Approval on : April 30th 2012

ABSTRACT
Natural gas being produced from gas fields around Indonesia areas, along with a large number
of other harmful substances (CO2,H2S, RSH,COS etc) often contains mercury. Even in small amounts,
mercury and its compounds have an extremely harmful effect on human health. Mercury content
in the natural gas should be removed to avoid equipment damage in the gas processing plant or
the pipeline transmission system from mercury amalgamation and embrittlement of aluminium.
Mercury can be removed by using adsorption processes such as activated carbon that is impregnated
with chlor, iodine or sulfur. This research is dealing with the process of mercury removal from gas
based on principle of adsorption and of chemisorption of mercury by means of activated carbon
impregnated with ZnCl2. Time of impregnation is a significant variable that can effect adsorption
capacity. The experiment results showed that ZnCl2 impregnation time of 12 hours significantly
enhanced the adsorptive capacity for mercury vapour.
Keywords: mercury removal, activated carbon, impregnated zinc chloride
I. INTRODUCTION
Mercury is a trace element in the natural gas with
relatively low contents. Mercury is vaporized from
the natural gas and exists as elemental mercury (Hg0).
Mercury is emitted to the atmosphere as a hazard air
pollutant if without effective gas purification systems.
Generally, mercury can be removed from the natural
gas through activated carbons. In the natural gas
processing industry, activated carbon is frequently
employed for the removal of mercury to protect
aluminum heat exchangers as well as providing a safe
working environment at the plant. Mercury content in
the natural gas should be removed to avoid damaging
equipment in the gas processing plant or the pipeline
transmission system from mercury amalgamation
and embrittlement of aluminium. Mercury is then
removed by using adsorption processes such as
activated carbon that is impregnated with zinc
chloride (ZnCl2).
Elemental mercury (Hgo) is oxidised to form
mercuric oxide (HgO), mercuric chloride (HgCl2) and

mercurous chloride (Hg2Cl2). Only a small amount


of vapor-phase mercury is removed by particulate
control devices, e.g. electrostatic precipitators or
bag house and the rest are emitted to the atmosphere
as a hazard air pollutant if without effective gas
purification systems. Mercury may accumulate and
concentrate within living organism by food chain,
causing various diseases and disorders to animals
and humans. Generally, oxidized mercury can be
removed from the natural gas or flue gas through wet
scrubbing or dry sorbent injection.
Adsorption by activated carbons, particularly
those impregnated with sulfur (S), chloride (Cl) or
Iodine (I), is a technology that offers great potential
for the removal of Hgo from the natural gas. The main
scope of this paper is to investigate the removal of Hgo
from the natural gas by granular activated carbons
treated with zinc chloride (ZnCl2) impregnation. The
effects of ZnCl2 time impregnation at an adsorption
temperature and ZnCl2 solution concentration on
the mercury removal performance were studied.

25

THE IMPROVEMENT OF MERCURY REMOVAL

SCIENTIFIC CONTRIBUTIONS OIL & GAS

LISNA ROSMAYATI

VOL. 35, NO. 1, APRIL 2012 : 25 - 29

The treatment with ZnCl2 impregnation on activated


carbon have been effectively reducing the mercury
content in natural gas. Hypothesis of this research is
increasing time of ZnCl2 impregnation will improve
the mercury adsorption by activated carbons.

show the constituent of Cl-impregnated activated


carbons (see Table 1). The EDX analysis used ZAF
method quantitative analysis.

II. EXPERIMENTAL

The working principal of this mercury removal


equipment is to follow the natural gas containing
mercury vapor at known concentration through an
adsorbent. An amount of mercury will be adsorbed
and the remaining mercury in the natural gas will be
adsorbed by KMnO4 solution. After that the solution
is analyzed by Lumex mercury analyzer. The volume
of the flowing gas is measured by a wet test meter
equipment.
A schematic diagram of the experimental setup
used in mercury adsorption tests is shown in
Figure 1.

A. Sample Preparation
The test material in this research used was carbon
black or activated charcoal and the chemical used
were Zinc Chloride (ZnCl2) 5%, Chloride Acid (HCl)
0,5 N dan 5%, Iodium ( I2) 0,1 N, Sodium thiosulphat
(Na2S2O7) 0,1 N, Kalium dichromat (K2Cr2O7) 0,1
N, Indicator, Whatman paper No.40 and distillation
water.
Commercial granular activated carbons was
sieved to have 70 mesh size, prepared from coconut
shells charcoal by activation at 700oC in a tubular
stainles steel reactor. The obtained Activated carbons
were then by impregnated with 5% (w/v) ZnCl2
solution for 6, 12 and 24 hours. Impregnated activated
carbons were dried in an oven at 90oC, cooled down to
the room temperature and then stored in a desiccators
for future use.
B. Sample Characterization

C. Adsorption of Mercury Removal from


Natural Gas

Table 1
Adsorbent composition analyzed
by ZAF method
Element

Mass %

C K
O K
Al K
Si K
Cl K
Zn K
Total

81.99
5.87
1.32
0.23
4.94
5.65
100.00

The characteristics of adsorbent sample were


determined by Iodine number, BET (BrunauerEmmett-Teller) and Scanning Electron Microscope
(SEM). The Iodine Number is determined by
iodometric method. BET
analysis is a measurement
of surface area and pore
distribution by adsorption
and desorption of N 2 gas.
SEM-EDX is a scanning
Electron Microscopy to
determine the micro structure
of a material including texture,
morphology, composition
and christallography particle
surface. The morphology is
monitored by SEM analysis
were shape, size and particle
formation. EDX (Energy
Dispersive X-ray), is a material
characterization method using
x-ray emission. The Result
Figure 1
data of EDX analysis will
An experimental setup of mercury adsorption test

26

THE IMPROVEMENT OF MERCURY REMOVAL

SCIENTIFIC CONTRIBUTIONS OIL & GAS

LISNA ROSMAYATI

Measurement of standard mercury and mercury


sample in Outlet Adsorber
- The natural gas is flown through mercury cylinder
placed in a water bath at a temperature of 37oC.
- The gas from the outlet of the mercury cylinder is
put into a mercury solution ( KMnO4 + H2SO4) .
- The mercury concentration is in the solution
analyzed by Mercury Analyzer (Lumex 91),
measured in g/m3.

VOL. 35, NO. 1, APRIL 2012 : 25 - 29

BET Characterization
Table 2
BET (Brunauer-Emmett-Teller) result

Temperature
(oC)

Pore diametre
(nm)

Surface
Area (m2/g)

700

219,26

463,17

III. RESULTS AND DISCUSSION


B. Discussion
A. Experimental Result
SEM and EDX Characterization

Figure 2
SEM foto of the sample at T = 700OC,
12 h impregnation after activation

Figure 3
EDX result of the sample at T = 700OC,
12 h impregnation after activation

Adsorption results of Hg0 onto the untreated as


well as impregnated ZnCl2 activated carbons for
6, 8, 12 and 24-h testing time are shown in
Figure 4 and 5. It can be seen that Hg concentration at the outlet of adsorber having no
adsorbent is 27.633 g/m3 (Table 3). For the
untreated activated carbon, the amount of Hgo
adsorbed decreased progressively, indicating
a typical physisorption mechanism due to van
der Waals forces between the adsorbate and
the adsorbent. For the activated carbon with
impregnated of ZnCl2 solution, the amount
of Hgo adsorbed increased progressively,
because ZnCl2 properties can behavior as
chemical activator, increasing the adsorption
capacity of the activated carbon and ZnCl2
solution can create new pores and can form
C-Cl bonding whenever Cl group can attach
the mercury (Hg) by chemical bonding to be
HgCl or HgCl2
Optimum adsorption occurs for adsorbent
of 12 hours impregnation time and in vertical
position adsorber. Amount of mercury
adsorbed in the adsorbent was 96 %.
Impregnation with ZnCl2, particularly with
the solution concentration of 5%, increased
the Hg 0 adsorption amount significantly.
This optimum adsorption probably due to
the occurrence of chemisorption by forming
chemical bonds between the adsorbate and
the chlorides present on the adsorbent. It is
worth to note that the impregnation of ZnCl2
longer than 12 hours decreased the mercury
adsorption of the activated carbon samples.
This probably due to the blockage of internal
pores by incorporated ZnCl2 molecules.
27

THE IMPROVEMENT OF MERCURY REMOVAL

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LISNA ROSMAYATI

VOL. 35, NO. 1, APRIL 2012 : 25 - 29

Adsorption Result and Mercury Analysis


Table 3
Hg concentration measurement without adsorbent,
and adsorbent without ZnCl2

Experiment
number
1

Type of Sample

Measurement
Hg in KMnO4
solution
(g/m3)
27.633

Without adsorbent
Adsorbent without ZnCl2
Horizontal Adsorber

Adsorbent without ZnCl2

2.564

2.653

Vertical Adsorber Position

While generally, for pure physisorption


process, the adsorptive capacity of the
activated carbon increases with increasing
the specific surface area, in this research is
suggested the occurrence of chemisorption
of elemental mercury onto the Climpregnated samples. Hg0 adsorbed onto
the Cl-impregnated samples attributed to a
combined physisorption and chemisorption.
A typical physisorption mechanism due to
van de Waals forces between the adsorbate
and the adsorbent. The mechanism of
chemisorptions of elemental mercury onto
the Cl-impregnated activated carbons was
proposed as follows. During impregnation,
ZnCl2 was reduced by the carbon content in
activated carbons and some Cl-contained
complexes were formed:
ZnCl2 + CnHxOy Zn + [ Cl2-CnHxOy ]
These Cl-contained functional groups
accounted for the chemisorption of Hgo
through the following reactions below :
Hg0 + [Cl]- [HgCl]+ + 2e and
Hg0 + 2[Cl]- [HgCl2] + 2e
In the presence of extra Cl species, the
mercury atom even is tended to adopt
four-coordination numbers as:
[HgCl2] + 2[Cl]- [HgCl4] 2-

Figure 4
Mercury concentration at adsorber outlet horizontal position

The characterization test by SEMEDX instrument has detected Cl-contained


functional group on the activated carbon
adsorbent.
IV. CONCLUSIONS

Figure 5
Mercury concentration at adsorber outlet vertical position

28

1. ZnCl2 as chemical activator is very


important for increasing the adsorption
capacity activated carbon because it
can create new pores and can form C-Cl
bonding the Cl group can then catch the
mercury by chemical bonding to be
HgCl or HgCl2
2. Hg0 adsorbed onto the Cl-impregnated
adsorbent attributed to a combined
physisorption and chemisorption
3. Mercury adsorption by activated
carbons that impregnated ZnCl2 for 12
hours shows the best result.

THE IMPROVEMENT OF MERCURY REMOVAL


LISNA ROSMAYATI

4. As chemisorption of mercury by Cl-contained


functional groups, created by ZnCl2 impregnation, were probably due to the formation of various complexes.
5. The experiment test showed that indicating
the impregnated adsorbent was able to adsorp
mercury (Hg) as much as 27.629,94 g/m3.
6. The mechanism of chemisorptions of elemental
mercury onto the Cl-impregnated activated
carbons.
REFERENCES
1. AWWA.1974.Standard for Granular Carbon.
AWWA B604-74. Colorado.
2. ASTM D 4607-94. Standard Test Method for
Determination of Iodine Number of Activated
Carbon.
3. ASTM D 1510-03. Standard Test Method
for Determination of Carbon Black-Iodine
Adsorption Number

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 25 - 29

4. Radisav D.Vidic, Control of Mercury Emissions


in Flue gases by Activated Carbon Adsorption,
University of Pittsburgh, PA 15261.
5. Rong Yan; Yuen Ling Ng, Bench-Scale
Experimental Study on The Effect of Flue gas
Composition on Mercury Removal by Activated
carbon Adsorption. Energy & Fuels 2003, 17,
1528 1535.
6. HESSLER, J.W. 1951. Active Carbon, Chemical
Publishing Co Inc. Brooklyn.
7. Hancai Zeng, Feng Jin, Removal of elemental
mercury from coal combustion flue gas by
chloride-impregnated activated carbon. Science
Direct, Revised 13 May 2003.
8. K a u t u b h a M o h a n t y, P re p a r a t i o n a n d
Characterization of activated carbons from
Sterculia alata nutshell by chemical activation
with zinc chloride to remove phenol from
wastewater. Springer Science, Revised : July 5,
2006.
9. Giacomo Corvini, Julie Stiltner, Mercury
Removal from Natural Gas and Liquid Stream.
UOP LLC, 2002.

29

30

COMPARISION DEPOSIT FORMATION ON THE VALVE


DIESEL ENGINE CAUSED BY BIODIESEL AND
PETROLEUM DIESEL FUELS
Maymuchar1), and Ismoyo Suro Waskito2)

Researcher, Litkayasa, at LEMIGAS R & D Centre for Oil and Gas Technology
Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230 INDONESIA
Tromol Pos: 6022/KBYB-Jakarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150
First Registered on December 13rd 2011; Received after Corection on April 17th 2012
Publication Approval on : April 30th 2012

1)

2)

ABSTRACT
The research on the influence of the biodiesel to the formation of deposits on the intake and
exhaust valves diesel engine has been carried out by means analysis of merit rating. The fuels used
on this study are FAME (B-100), a mixture of 50% (v)of FAME in diesel fuel 48 (B-50), and diesel
fuel 48 (B-0). The objective of this research is to obtain data which represent the influence of the
biodiesel to the formation of deposits on the intake and exhaust valve diesel engine. The test used
a diesel engine driving 5 KVA generator which is operated for 100 hours with 1.000 Watt electrical
load. The results of the study show that the use of either FAME or biodiesel as alternative fuel in
the diesel engine generator 5 KVA has a positive effect on reducing the deposit on the intake and
exhaust valves.
Keywords: biodiesel, intake valve, exhaust valve, diesel engine
I. INTRODUCTION
The use of biodiesel as an alternative fuel for
diesel engines is a government policy which aim to
develop the application of biofuels. This program
has already stated in Presidential Decree No. 1 2006.
This program becomes a priority to decrease the
dependence on fossil fuels in the future.
The specification of Diesel Fuel 48 or 51
stated in the Directorate General of Oil and Gas
No. SK. 3675K/24/DJM/2006 dated March 17,
addition of FAME into diesel fuel up to 10% of
volume is allowed. This 10% addition of FAME
is still debatable, especially by the manufacturers
of vehicles and machinery. According to World
Association of the vehicle and engine manufacturers
(ACEA, Alliance, EMA, JAMA) in the World-Wide
Fuel Charter (WWFC) September 2006 still restricts
the content of FAME in diesel fuel to a maximum
of 5% by volume of Categories 1, 2 and 3, whereas
Category 4 is mentioned non-detectable. The
limitation of biodiesel is due to the negative side
at high concentration, i.e : unstable to oxidation,
the problem of viscosity at low temperatures,

hygroscopic properties, the compatibility of the


components of natural rubber seals and the formation
of deposits on parts of the engine including the intake
and exhaust valve.
Intake and exhaust valve are parts of the engine
mechanism that are located on cylinder head. The
function of these valve are to regulate fluid or gas
in and out the combustion chamber. Intake valve
regulates the fresh air needed for combustion coming
into the cylinder. This air intake process occurs due to
the piston movement from top to bottom dead center.
Whereas the exhaust valve is to let the combusted gas
flows from the combustion chamber. The mechanism
of exhaust gases of the combustion occurs in exhaust
stroke where the piston moves from the bottom dead
center to the top dead center. The more fluid can move
in and out of the engine the more efficient and power
the engine is. Therefore, the intake and exhaust valve
plays a significant role in an engines performance.
The objective of this research is to obtain data
which represent the influence of the biodiesel to the
formation of deposits on the intake and exhaust valve
diesel engine.
31

COMPARISION DEPOSIT FORMATION ON THE VALVE


MAYMUCHAR AND ISMOYO SURO WASKITO

II. RESEARCH PREPARATION AND


METHOD

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 31 - 37

The test engine shows on Figure 1.

A. Test Fuel
There are 3 kinds of fuel used in this research
that is diesel fuel with cetane number 48, Fatty Acid
Methyl Ester (FAME) or biodiesel, and diesel fuel
and biodiesel blend.
1. Diesel Fuel 48 grade
One of the fuels used is diesel fuel 48 which has
a minimum cetane number 48. This fuel is used as
a reference fuel for comparison to other fuels. The
fuel is later referred to as B-0.

Figure 1
Diesel engine generator 5 KVA

2. Fame
Palm-based biodiesel is often called FAME has
a chemical formula:
O
II
R C O CH3
FAME is the result of trigliseride process of palm
oil with methanol (CH3OH) via transesterification
process using a catalyst of sodium hydroxide
(NaOH). The fuel is later referred to as B-100.
3. Biodiesel
Biodiesel is a mixture of petroleum diesel fuel 48
with biodiesel FAME. The blending concentrations
are respectively 50% and then called as B-50.
B. Test Engine
Diesel engine generator with a 5 KVA capacity
as a test engine that is widely used in community
as a power supply for small houses. The main
specification of the diesel engine used are listed in
Table 1.
Table 1
Test engine specification

32

Type

: 4 stroke, 1 cylinder, Horizontal

Type Injection

: Direct Injection

Displacement

: 583 cc

Power (Cont.)

: 9,2 HP / 2400 rpm

Power (Max)

: 10,5 HP / 2400 rpm

Figure 2
Parts of valve observed

The research was conducted in two phases of test;


fuel characteristics test and applied test. The fuel used
by the test parameters tested characteristics cetane
number, distillation, viscosity, density and lubricity
in accordance with the specifications and standard test
methods. The applied test is carried out by using a
diesel engine driving generator. The 5KVA generator
diesel engine is run by fuel B-0, B-50 and B-100.
Each of the fuel was used to operate the engine test
for 100 hours with 1.000 Watt electric load. After 100

COMPARISION DEPOSIT FORMATION ON THE VALVE

SCIENTIFIC CONTRIBUTIONS OIL & GAS

MAYMUCHAR AND ISMOYO SURO WASKITO

VOL. 35, NO. 1, APRIL 2012 : 31 - 37

hours of operation, the engine was overhauled and the


deposits on valve was assessed and weighed.
Intake and exhaust valve for each test of each fuel
must be in new condition. Replacing parts were also
done to the parts which affect the performance of the
engine such as fuel filters, oil filters, etc.
The Evaluation is done by comparing the results
of assessment of intake and exhaust valve engine
with fuel B-100, B-50 with B-0. Valve condition
assessment was done in two ways that is merit
analysis by using standard CEC (The Coordinating

European Council) and weighing the deposit. The


observed parts of the valve are head/topside valve
and tulips/ underside valve (Figure 2).
III. RESULT AND DISCUSSION
A. Characteristic Fuel
The laboratory test results show the main
characteristics of the sample B-0 used as reference
fuel and B-50 which meets the requirements of test
specifications set by the government according to
Director General of Oil and Gas Decree No.3675.K/24/

Table 2
Characteristic B-0 and B-50 test result

Result
No

Characteristic

Unit
B50

B-0
1

Ki
i viscosity
i
i @ 40C
Kinematic

Density @ 40C,

Cetane number

Flash point

Cooper corrosion

Carbon residu

Acid number

Diesel fuel 48
specification

Test
method

mm /s

4
4
4,4

4
9
4,9

2050
2,0-5,0

D445

849

867

815-870

D1298

48,6

50,2

Min48

D613

kg/m
CN
C

67

96,5

Min60

D93

No.ASTM

No.1

No.1

Max No 1

D130

% massa

0,01

0.09

Max 0,1

D4530

mg-KOH/g
mg KOH/g

0 09
0,09

02
0.2

Max 0
0,6
6

D664

Sulphur content

% m/m

0,15

0.09

Max 0,35

D1266

Lubricity, scare diameter

micron

286

205

D6079

10

Calorific value

Mj/Kg

4377

39.9

D240

Table 3
Characteristic B-100 test result

No

Characteristic

Unit

B-100

Biodiesel
specification

Test method

Kinematic viscosity @40C

mm2/s

6,0

2,3-6,0

D445

Density @40C,

884

850 - 890

D1298

Cetane number

kg/m3
CN

51,4

min 51

D613

Flash point

134

min 100

D93

Cooper corrosion

No.ASTM

No.1

max No. 3

D130

Carbon residu

% massa

0,028

max 0,05

D4530

Acid number

mg-KOH/g

0,32

max 0,8

D664

Sulphur content

% m/m

0,01

Max 0,01

D1266

Lubricity, scare diameter

micron

196

D6079

10

Calorific value

Mj/Kg

38.3

D240

33

COMPARISION DEPOSIT FORMATION ON THE VALVE

SCIENTIFIC CONTRIBUTIONS OIL & GAS

MAYMUCHAR AND ISMOYO SURO WASKITO

DJM/2006 decree dated March 17, 2006 for diesel


fuel 48. The result is showed in Table 2.
From the results of laboratory tests the main
characteristics of the sample B-100, which is used
as biodiesel fuel meets the requirements of test
specifications set by the government according to the
Indonesian National Standard as outlined in the SNI
04-7182-2006. The result is shown in Table 3.
B. Rating Top Head and Tulip Intake Valve
Rating deposit at the top of intake valve has been
done for fuel B-0, B-50, and B-100. The results of
deposit rating top head intake valve for B-0, B-50
and B-100 is shown in Table 5.

VOL. 35, NO. 1, APRIL 2012 : 31 - 37

From the results of merit rating deposits at the


top head intake valve, the value of merit rating for
B-0, B-50 and B-100 is the same, 8.643 respectively.
Table 5
Merit rating and effect deposit
top head intake valve

Merit Rating
B-0

B-50

B-100

8,643

8,643

8,643

B50:B0

B-100:B0

0,00%

0,00%

Effect

Figure 3
Deposit on top head intake valve for B-0, B-50 and B-100
After 100 hour Operation

Figure 4
Deposit on tulip intake valve B-0, B-50 and B-100
After 100 hour operation

34

COMPARISION DEPOSIT FORMATION ON THE VALVE

SCIENTIFIC CONTRIBUTIONS OIL & GAS

MAYMUCHAR AND ISMOYO SURO WASKITO

There are no differences shown in the formation


of deposits on intake valve top head in biodiesel
addition. Physically the deposit on the top head
intake valve for fuel B-0, B-50 and B-100 is shown
in Figure 3.
The results of the intake valve tulips deposit
rating to B-0, B-50 and B-100 is shown in Table
6. From the results merit rating tulips intake valve
deposits, the value of merit rating to B-0, B-50 and
B-100 are 8.643, 9.643 and 9.708, respectively.
Value shows the addition of biodiesel tends to reduce
deposit formation in the intake valve tulips. The
value of merit rating tulips intake valve B-50 to B-0
is 10,37% and B-100 to B-0 rises 12.32%.
Physically deposits on the tulips intake valve to
fuel B-0, B-50 and B-100 after 100 hours of operation
is shown in Figure 4.
Weight measurements showed that the intake
valve deposits on the B-0 is heavier than the B-50
and B100 (see Table 7). Although the results of the
rating on the top head have the same value but the
tulip rating results B-0 are relatively poor.
C. Rating Top Head and Tulip Exhaust Valve
The results merit rating top head exhaust valve
deposits the value of merit rating to B-0, B-50 and
B-100 respectively 8.342, 8.643, and 8.643 (see Table
8). The value shows that the addition of biodiesel
tends to reduce deposit formation in the top head
exhaust valve. The effect value of merit rating top
head exhaust valve B-50 to B-0 rose 3.60%, and
B-100 to B-0 rose 3.60%. Physically deposit on top
head exhaust valve to fuel B-0, B-50 and B-100 after
100 hours of operation is shown in Figure 5.

VOL. 35, NO. 1, APRIL 2012 : 31 - 37

Table 6
Merit rating and effect deposit
Tulip intake valve

Merit Rating
B-0

B-50

B-100

8,643

9,643

9,708

B50:B0

B-100:B0

10,37%

12,32%

Effect

Table 7
Weight Measurement of Intake Valve

Inlet Valve Weight (gr)


Fuel

Effect

0 hour

100 hours

B
B-0
0

470.005
470 005

471.655
471 655

0.1650
0 1650

B-50

470.400

470.944

0.0544

B-100

475.976

476.568

0.0592

Table 8
Merit rating and effect deposit
Top head exhaust valve

Merit Rating
B-0

B-50

B-100

8 342
8,342

8,643
8 643

8,643
8 643

B50:B0

B-100:B0

3,60%

3,60%

Effect

Figure 5
Deposit on top head exhaust valve B-0, B-50 and B-100
After 100 hour operation

35

COMPARISION DEPOSIT FORMATION ON THE VALVE

SCIENTIFIC CONTRIBUTIONS OIL & GAS

MAYMUCHAR AND ISMOYO SURO WASKITO

Rating deposits in the exhaust valve tulip has been


done for the fuel B-0, B-50, B-100 and the result is
shown in Table 9. From the results merit rating tulips
exhaust valve deposits, the value of merit rating to
B-0, B-50 and B-100 are respectively 4.812, 5.237,
and 6.827. The value shows that the addition of
biodiesel tends to reduce deposit formation in the
exhaust valve tulips. The value of merit rating tulips
exhaust valve for the B-50: B-0 rose 8.84%, and
B-100: B-0 rose 41.87%. Physically the deposits on
the tulips exhaust valve to fuel B-0, B-50 and B-100
after 100 hours of operation is shown in Figure 6.
The results of weighing the deposit that occurs
at the outlet valve is shown in Table 10.

IV. CONCLUSIONS
After assessing parts of the intake and exhaust
valve in 100-hour-engine operation to see the impact
of using biodiesel on the formation of deposits on
engine valves 5 KVA Diesel generator, it can be
summed up as follows:
- The rating of the valves above shows that the
use of biodiesel as a fuel substitution for diesel
fuel on the generator 5 KVA diesel engine has a
positive effect on reduction of deposit formation
on valves, especially the tulips.
- Biodiesel does not make a difference in the
formation of deposits on the top head intake valve,

VOL. 35, NO. 1, APRIL 2012 : 31 - 37

the value of merit rating to B-0, B-50 and B-100


is the same that is 8.643.
- The addition of biodiesel tends to reduce the

formation of deposits on the intake valve


tulips, the effect of tulips rating B-50: B-0
and B-100: B-0 are 10,37% and 12.32%
respectively.
Table 9
Merit rating and effect deposit
Tulip exhaust valve
Merit Rating
B-0

B-50

B-100

4,812

5,237

6,827

B50:B0

B-100:B0

8,84%

41,87%

Effect

Table 10
Weight Measurement of Exhaust Valve

Exhaust Valve Weight (gr)


Fuel

0 hour

Effect

B-0

409.651

418.251

0.8600

B-50

403.401

406.325

0.2924

B-100

403.098

405.389

0.2291

Figure 6
Deposit on tulip exhaust valve B-0, B-50 and B-100
After 100 hour operation

36

100 hours

COMPARISION DEPOSIT FORMATION ON THE VALVE


MAYMUCHAR AND ISMOYO SURO WASKITO

- The addition of biodiesel tends to reduce the


formation of deposits on the top head exhaust
valve, the effect of tulips rating B-50: B-0 and
B-100: B-0 are 3.60%.
- The effect of addition of biodiesel 50% to diesel
fuel tends to reduce the formation of deposits in
the tulip exhaust valves 8.84%, but using 100%
biofuel will reduce deposit on the exhaust valve
41.87%.
REFERENCES
1. ACEA, Alliance, EMA, JAMA, 2002, WorldWide Fuel Charter, December 2002
2. Ayhan D, Biodiesel; A Realistic Fuel Alternative
for Diesel Engines, Springer Verlag London
Limited, 2008

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 31 - 37

3. Badan Standardisasi Nasional, 2006, Standar


Nasional Indonesia Biodiesel, SNI 04-7182-2006,
Jakarta
4. Chevron Oronite, 1998, Diesel Fuels Technical
Review, Chevron Product Company, USA
5. Dirjen Migas, 1999, Spesifikasi Bahan Bakar
Jenis Minyak Solar, SK No. 3675.K/24/DJM/2006
tanggal 17 Maret 2006, Jakarta
6. Knothe, G, Krahl J, Gerpen JV, The Biodiesel
Handbook, AOCS Press, Champaign, Illinois,
USA 2005
7. Keith Owen, Trevor Coley, 1995, Automotive
Fuels Reference Book, Society of Automotive
Engineers,Inc., USA
8. UOP, 1998, Diesel Fuel Specifications and
Demand for the 21st Century, UOP LLC, Des
Plaines, Illinois, USA.

37

38

DILUTE ACID PRETREATMENT AND ENZYMATIC


HYDROLYSIS OF LIGNOCELLULOSIC BIOMASS
FOR BUTANOL PRODUCTION AS BIOFUEL
Devitra Saka Rani 1) and Cut Nanda Sari1)
1)

Researcher at LEMIGAS R & D Centre for Oil and Gas Technology

Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230 INDONESIA
Tromol Pos: 6022/KBYB-Jakarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150
First Registered on March 19th 2012; Received after Corection on April 19th 2012
Publication Approval on : April 30th 2012

ABSTRACT
Biobutanol is one of the promising biofuel for substituting gasoline. Biobutanol produced
from biomass fermentation using solventogenic clostridia which are able to convert a wide range
of carbon sources to fuels such as butanol. Therefore, lignocellosic biomass has great potential
as fermentation substrate for biobutanol production. Lignocellosic biomass should be hydrolized
before fermentation by a pretreatment process and enzymatic hydrolysis. The various lignocellulosic
biomass pretreatment will influence in butanol production depending on fermentable sugars
content. The objective of this research is to get potential lignocellulosic biomass using dilute acid
pretreatment and enzymatic hydrolysis process for biobutanol production. Eight types of biomass
from sugarcane bagasse, rice straw, rice husk, empty fruit bunch (EFB) of palm oil, corn cob,
pulp waste, traditional market organic waste, and microalgae were used in this experiment. After
hydrolysis, the high result of total fermentable sugars in corn cobs, bagasse, rice straw, and rice
husk, shows good opportunity of these biomass to be used as fermentation feedstocks for biobutanol
production. In addition, pulp waste, organic waste, and microalgae are prospective as raw material
but require more appropriate treatment either for to break down the cellulose/hemicellulose or
to enhance reducing sugar content. Fine milling and delignification have no significant effect
on cellulosic biomass conversion into fermentable sugars. Therefore, the production cost can be
reduced. In order to enhance the sugar content and reduce the formation of inhibitor product, it
is necessary to examine dilute acid pretreatment variations and appropriate operating conditions
of enzymatic hydrolysis process.
Keywords: biofuel, biobutanol, lignocellulosic biomass, dilute acid pretreatment, enzymatic
hydrolysis
I. INTRODUCTION
Biofuels development for fossil fuels replacement
has increased in recent years. One of the promising
biofuel for substituting gasoline is biobutanol, a four
carbon alcohol produced by biomass fermentation
using anaerobic bacteria. Compared to ethanol,
butanol has many superior properties as an alternative
fuel. Butanol contains more energy, less hygroscopic,
and easily mix with gasoline in any proportion.
Furthermore the air-fuel ratio of butanol in engine
combustion chamber is close to gasoline. Butanol
can be used directly or blended with gasoline without

any vehicle retrofit. In addition, butanol is also can be


supplied through the existing gasoline pipes without
any problems1.
The most abundant sources of renewable
biomass is lignocellulosic biomass obtained from
energy crops, wood and agricultural residues2. Using
biomass to produce energy can possibly solve the
problems that world faces because of excessive use of
fossil fuels, and may significantly reduce greenhouse
gas emissions, pollution and waste management
problems1. Indonesia has great natural resources and
biomass to produce biofuels. Agricultural residues,

39

DILUTE ACID PRETREATMENT AND ENZYMATIC


DEVITRA SAKA RANI AND CUT NANDA SARI

domestik organic waste and other non-edible are


easily found in a large amount. According to Ministry
of Energy and Mineral Resources Republic of
Indonesia, the potency of Indonesian biomass for
energy is 49.81 GW, while installed capacity is only
about 1618 MW. It might be caused by a lack of
biotechnology research for industrial-scale biofuels
production.
Anaerobic bacteria such as solventogenic
clostridia are able to convert a wide range of
carbohydrates to biofuels and chemicals such as
biobutanol. Therefore, the use of lignocellosic
biomass as a substrate is good approach for
biobutanol fermentation3. Butanol fermentation by
different strains using various biomass substrates has
been reported in recent years. These inovations may
help reduce fermentation substrate costs4. Biobutanol
fermentation technology has changed rapidly in
the last few years and a commercial scale process
based on biomass materials is nearly achieved. The
use of lignocellulosic substrates in combination
with developed technology is expected to make the
production of biobutanol economically viable3.
Since microorganisms do not have enzymes to
digest cellulose, it is essential to treat lignocellosic
materials before fermentation in order to break
it down into simple sugar 1. The production of
fermentable sugars from lignocellulosic biomass
after initial mechanical process is usually carried out
in two steps: a pretreatment process, and enzymatic
cellulose hydrolysis 5. Pretreatment is a crucial
process step and it has been recognized as one of
the most expensive processing steps in cellulosic
biomass to fermentable sugars conversion. The
pretreatment process needed to liberate the cellulose
from the lignin seal and its crystalline structure thus
makes cellulose more accessible to the enzymes that
convert the carbohydrate polymers into fermentable
sugars6. One of the most effective pretreatment
methods for lignocellulosic biomass is dilute acid
pretreatment 5. Dilute acid hydrolysis has been
extensively reviewed and is considered to be one
of the treatment methods with greater potential for
wide-scale application. For a given material, the best
conditions for hemicelluloses removal and recovery
in the hydrolysate do not always translate into the
best enzymatic digestibility. Enzymatic hydrolysis
is reaction using specific cellulase enzymes that
brakes cellulose into glucose molecules1. Obstacles
40

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 39 - 48

in the pretreatment and hydrolysis processes include


the insufficient conversion of cellulose to glucose,
high lignin content which is recalcitrant fraction,
high use of chemicals and/or energy, considerable
waste production, and formation of by-products that
inhibit fermentation 5. This research examine most of
all Indonesian potential biomass such as sugarcane
bagasse, rice straw, rice husk, empty fruit bunch of
palm oil, corn cob, pulp waste, traditional market
organic waste, and microalgae. The objective of this
research is to get potential lignocellulosic biomass
using combination of dilute acid pretreatment
and enzymatic hydrolysis process for biobutanol
production.
II. MATERIALS AND METHODS
A. Biomass Preparation
Eight prepared biomass from sugarcane bagasse,
rice straw, rice husk, empty fruit bunch (EFB) of palm
oil, corn cob, pulp waste, traditional market organic
waste, and microalgae are used in this experiment.
The sugarcane bagasse is obtained from sugar mill,
whereas EFB and pulp waste are collected from palm
oil mill and pulp industry respectively. Two types of
pulp waste, i.e TR (rough) and TF (fine) are used in
this experiment. The biomass used in this study are
shown in Figure 1. All of the biomass used are based
on % dry solid except for organic waste which is
based on its % wet solid, because the structure and
composition of carbohydrates may be degraded in
the drying process and consequently affect reducing
sugar yield7.
B. Dilute Acid Pretreatment and Enzymatic
Hydrolysis
Dilute acid pretreatment was conducted using
0.5 - 4% sulphuric acid with 1.5-12.5% w/v biomass.
The process was carried out in an autoclave either at
121C for 60 min or at 130C for 30 min. The mixture
was then cooled to room temperature and followed
by neutralization with NaOH 10 M. The hydrolysate
was finally separated from the solid fraction. The
hydrolisate was then examined for reducing sugar
content, while the solid fraction was subjected to
hydrolysis process. The dilute acid pretreatment
condition for each biomass is described in Table 1.
In order to recognize the effect of lignin removal
on reducing sugar enhancement, the delignification

DILUTE ACID PRETREATMENT AND ENZYMATIC

SCIENTIFIC CONTRIBUTIONS OIL & GAS

DEVITRA SAKA RANI AND CUT NANDA SARI

VOL. 35, NO. 1, APRIL 2012 : 39 - 48

Figure 1
Eight cellulosic biomass after mechanical preparation

Table 1
Dilute acid pretreatment condition for each biomass

Dilute acid pretreatment condition


No.

H2SO4

Temp.

Time

(%)

(C)

(min)

10

0.5

130

30

8.6

121

60

1.5

130

30

Biomass
Dry Solid (%)

1.
2.
3.
4.

Bagasse

8
9

Rice straw
Microalage

10

11

5.

Rice husk
Organic waste

6.

Corn cob

7.
8.

EFB palm oil


Pulp waste

12

15

121

60

30*

130

30

10

121

60

12.5

121

60

10

130

30

*Wet solid

test was performed using pretreatment solid fraction


from 3 biomass, i.e bagasse, rice husk, and rice straw.
The delignification process was conducted before

enzymatic hydrolysis, using 1.5% NaOH at 100C


for 60 minutes8, then neutralized with H2SO4 and
washed with destillate water.

41

DILUTE ACID PRETREATMENT AND ENZYMATIC

SCIENTIFIC CONTRIBUTIONS OIL & GAS

DEVITRA SAKA RANI AND CUT NANDA SARI

VOL. 35, NO. 1, APRIL 2012 : 39 - 48

The solid fraction obtained from the previous


process was then hydrolyzed using an enzyme mixture
of Cellulase (Sigma, Cat. No. C1184) and Xylanase
(Sigma, Cat. No. X2753). Each enzyme powder was
dissolved 1 g/L in citrate buffer solution. Hydrolysis
process was carried out in 500 ml Erlenmeyer flask
containing 250 ml of enzyme solution in citrate
buffer, incubated in a shaker incubator at 50C and
pH 4.8, with 120 rpm, for 72 hours. Finally, the flask
was sterilized to denatured enzymes. Hydrolysate
from the enzymatic hydrolysis process was sampled
for reducing sugar analysis.

exhibits that the highest cellulose content found in


pulp waste TF, followed by pulp waste TR, bagasse,
and rice husk, respectively. The highest hemicellulose
content found in organic waste, followed by corn
cobs, and microalgae, respectively. The highest
lignin content found in the EFB palm oil, followed
by bagasse and organic waste respectively. EFB
Palm oil which has highest lignin content is not
appropriate for conventional butanol fermentation
because of high energy consume for pretreatment
and hydrolysis. According to Harmsen et al. 5
biomass with high lignin is suitable for heat and

C. Analysis
The carbohydrate and reducing
sugar were determined quantitatively
using gravimetric method and NelsonSomogyi method, respectively.
Carbohydrate analysis was conducted
in Centro Agro-Based Industry, Bogor
and Center for Food and Nutrition
Studies, Gadjah Mada University,
Yogyakarta.
III. RESULTS AND DISCUSSION
A. Carbohydrate composition
The average content of cellulose,
hemicelluloses, and lignin from each
biomass are presented in Table 2.
Analysis of biomass composition

Figure 2
Comparison of carbohydrate composition from each biomass

Table 2
Composition of various cellulosic biomass

Carbohydrate composition (%)


No.

42

Biomass
Cellulose

Hemicelullose

Lignin

1.

Rice straw

29.94

23.93

9.21

2.

Rice husk

33.85

24.06

8.56

3.

Bagasse

43.49

23.5

16.15

4.

Corn cob

23.29

37.64

9.64

5.

Microalgae

21.72

30.79

9.23

6.

Pulp waste TF

74.78

9.8

3.87

7.

Pulp waste TR

58.21

1.06

8.12

8.

EFB palm oil

25.24

7.45

27.92

9.

Organic waste

22.08

58.91

15.23

DILUTE ACID PRETREATMENT AND ENZYMATIC

SCIENTIFIC CONTRIBUTIONS OIL & GAS

DEVITRA SAKA RANI AND CUT NANDA SARI

VOL. 35, NO. 1, APRIL 2012 : 39 - 48

Table 3
Reducing sugar content after dilute acid pretreatment

No.

Biomass

% Dry Solid

% Reducing sugar

Reducing sugar
Biomass weight

1.

Organic waste

4.8

1.91

39.79

2.

Corn cob

10

2.93

29.30

3.

Bagasse

10

1.93

19.30

4.

Rice straw

8.6

1.54

17.91

5.

Rice husk

15

2.02

13.47

6.

Microalgae

1.5

0.18

12.00

7
7.

EFB palm oil

12 5
12.5

1 19
1.19

9 52
9.52

8.

Pulp waste TR

10

0.59

5.90

9.

Pulp waste TF

10

0.42

4.20

electricity production. Carbohydrate composition of


lignocellulosic biomass vary greatly, depending on
the type of plant, cultivation condition and the age
of plant12. Carvalho showed that there was different
cellulose content between two types of bagasse which
used in his research13.
Base on the comparison of carbohydrate
compositions (Figure 2), the highest fermentable
carbohydrate from the total amount of cellulose and
hemicellulose, is found in pulp waste TF, followed by
organic waste and bagasse. The highest of cellulose
and hemicellulose content in the biomass is expected
to be superior in terms of highest butanol production
yield.

Figure 3
Rice husk pre- (left) and post- (right)
dilute acid pretreatment

B. Dilute Acid Pretreatment


The conversion process of carbohydrate into sugar
has been commenced on dilute acid pretreatment,
as indicated by the color changes of the solution
(Figure 3).
The highest sugar content after pretreatment
process is found in corn cob, followed by rice husk,
bagasse, and organic waste, respectively. When
compared between the percentages of reducing
sugar per dry weight biomass, the organic waste
give the highest result with 39.79% followed by
corn cob and bagasse. Reducing sugar content of
each biomass after pretreatment with dilute acid is
shown in Table 3.

A comparison between the percentages of reducing


sugar per weight biomass with hemicellulose content
of each biomass is shown in Figure 4. It exhibit that
the greater the hemicelluloses, the greater the sugar
content obtained from the pretreatment process. The
high difference between hemicelluloses and reducing
sugar content on microalgae, pulp waste TF, and rice
straw shows that optimal condition of dilute acid
pretreatment process for these biomass has not been
achieved.
The cellulose and hemicellulose are more easy
to break down in small particles. However the
examination of particle size effect on sugar content

43

DILUTE ACID PRETREATMENT AND ENZYMATIC


DEVITRA SAKA RANI AND CUT NANDA SARI

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 39 - 48

Figure 4
Comparison of hemicellulose and reducing sugar content after pretreatment

after hydrolysis process indicate


that reducing the size of biomass
is not followed by increasing sugar
content. The increase of sugar
content after milled only found in
corn cobs (Figure 5). This means
that only certain biomass undergoes
increasing in sugar content when its
particle size reduced. As a result,
the elimination of fine milling
process can reduce production
costs. According to Carvalho
13
, several types of high energy
consuming grinding against some
types of biomass, but it works
much better with other biomass.
However, grinding is an energy
intensive process which is one of
the most important limitations in
the application of industry-wide
scale.

Figure 5
Effect of particle size on reducing sugar content after
dilute acid pretreatment

C. Enzymatic Hydrolysis
The highest percentage of reducing sugar content
after enzymatic hydrolysis is found in corn cobs,

44

followed by rice husk, bagasse, and rice straw,


respectively (Table 4). However, when compared
with the biomass weight, microalgae has the highest
value (78.74%) followed by corn cob (37.33%). It

DILUTE ACID PRETREATMENT AND ENZYMATIC

SCIENTIFIC CONTRIBUTIONS OIL & GAS

DEVITRA SAKA RANI AND CUT NANDA SARI

VOL. 35, NO. 1, APRIL 2012 : 39 - 48

is assumed that the hydrolysis of carbohydrates in


mikroalgae is complete. But the use of this biomass
is not efficient if using low weight dry biomass.
The microalgae biomass require more appropriate
pretreatment to increase reducing sugar content.
The highest content of cellulose in the pulp
waste does not generate the highest reducing sugar.
This may be caused by the crystalline structure of
cellulose which can inhibit the enzyme to access the
biomass particles. Polymer solubility of cellulose
intimately associated with the attainment of degrees
of hydrolysis5. Therefore, cellulose hydrolysis from
pulp waste requires more specific study in order to
achieved high fermentable sugars.
Reducing sugar content obtained via enzymatic
hydrolysis process can be improved. The application
of enzyme in the form of powder requires a
preliminary test in order to determine the accurate
activity of cellulase16. The measurement cellulase
activity will determine enzymes activity that can
be used as efficiently as possible considering the
expensive price of an enzyme. Anwar et al.17 stated
that the greater the ratio of enzyme to the substrate,
the greater the concentration of glucose is produced.
However, the efficiency of the enzyme becomes
smaller17. The incomplete enzymatic hydrolysis
may be caused by a number of factors including the
presence of inhibitor for the enzymes. Furthermore
knowledge about the physiology and genetics to

make the enzymatic hydrolysis process becomes


economically viable is required18. The results from
Qureshi et al.19 using strain C. beijerinckii showed
that the use of enzymes for hydrolysis in butanol
fermentation was not significantly different. It means
that both glucose and xylose are utilized efficiently
by the culture. Thus it is possible that low sugar
content from biomass in this study can reach higher
biobutanol production.
In the delignification test from bagasse, rice husk,
and rice straw, the increasing reducing sugar content
after enzymatic hydrolysis only found in rice straw.
Whereas delignification in bagasse and rice husk
decrease reducing sugar content (Figure 6). The
delignification process does not affect the reducing
sugar content in bagasse which contain more lignin
than rice straw and rice husk. This phenomenon
was described by Ishizawa et al.14 which found that
nearly complete removal of lignin after dilute acid
pretreatment have reduced access and conversion of
cellulose. Rollin et al.15 stated that increasing cellulose accessibility was a more important pretreatment
consideration than delignification for effectively
releasing sugars from recalcitrant lignocellulose at
high yield.
The total of reducing sugar content from
hydrolyzates of dilute acid pretreatment and
enzymatic hydrolysis shows high sugar yield
from corn cobs, rice husk, bagasse, and rice straw,

Table 4
Reducing sugar content after enzymatic hydrolysis

No.

Biomass

% DS

% Reducing sugar %

Reducing sugar
Biomass weight

1.

Corn cob

12.5

4.67

37.33

2.

Rice husk

18.75

3.97

21.17

3.

Bagasse

12.5

3.59

28.74

4.

Rice straw

12.5

3.28

26.27

5.

EFB Palm oil

12.5

2.95

23.56

6.

Pulp waste TR

12.5

2.47

19.76

7
7.

Organic waste

12 5
12.5

2 47
2.47

19 72
19.72

8.

Pulp waste TF

9.

Microalgae

12.5

1.99

15.93

1.875

1.48

78.74

45

DILUTE ACID PRETREATMENT AND ENZYMATIC

SCIENTIFIC CONTRIBUTIONS OIL & GAS

DEVITRA SAKA RANI AND CUT NANDA SARI

VOL. 35, NO. 1, APRIL 2012 : 39 - 48

Table 5
Total reducing sugar content from pretreatment and hydrolysis

% Reduction Sugar from


No.

Biomass
Pretreatment

Hydrolysis

Total

Corn cob

2.93

4.67

7.60

Rice husk

2.02

3.97

5.99

Bagasse

1.93

3.59

5.52

Rice straw

1.54

3.28

4.82

Organic waste

1.91

2.47

4.38

EFB palm oil

1.19

2.95

4.14

Pulp waste TR

0.59

2.47

3.06

Pulp waste TF

0.42

1.99

2.41

Microalgae

0.18

1.48

1.66

Figure 6
Effect of delignification on reducing sugar content after hydrolysis

respectively. The results of the total hydrolyzate of


the dilute acid pretreatment and enzymatic hydrolysis
are presented in Table 5.
IV. CONCLUSIONS
The current study demonstrates that some of
biomass such as corn cobs, bagasse, rice straw

46

and rice husk are good material for biobutanol


production. Pulp waste and microalgae have a
good chance. However, they still require more
appropriate treatment to break down the cellulose/
hemicellulose. Fine milling and delignification have
no significant effect in cellulosic biomass conversion
into fermentable sugars, therefore it can reduce

DILUTE ACID PRETREATMENT AND ENZYMATIC


DEVITRA SAKA RANI AND CUT NANDA SARI

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 39 - 48

production costs. In order to enhance the sugar


content and reduce the formation of inhibitor product,
it is necessary to examine the dilute acid pretreatment
variations based on acid concentration, temperature,
and retention time, and to search suitable operating
conditions of enzymatic hydrolysis.

for Lignocellulosic Biomass, Wageningen UR


Food & Biobased Research: Wageningen.
8. Qureshi, N., B.C. Saha, M.A. Cotta, 2007.
Butanol Production from Wheat Straw
Hydrolysate using Clostridium beijerinckii.
Bioprocess Biosyst Eng. 30: 419427.

V. ACKNOWLEDGEMENT

9. Ishizawa, C.I., T. Jeoh, W.S. Adney, M.E.


Himmel, D.K. Johnson, M.F. Davis, 2009.
Can delignification decrease cellulose
digestibility in acid pretreated corn stover?
Cellulose, 16:677686.
10. Lopz-Contreras, 2000. Utilisation of
Saccharides in Extruded Domestic Organic
Waste by Clostridium acetobutylicum ATCC
824 for Production of Acetone, Butanol
and Ethanol. Applied Microbiology and
Biotechnology, Vol. 54, No. 2: 162-167.

This work was supported by the government under


Program Pembinaan Usaha Pertambangan Migas
(Program No. 020.11.04.1913.02.25).
REFERENCES
1. Aleksic, S. 2009. Butanol Production From
Biomass, Thesis, Chemical Engineering,
Youngstown State University, US.

2. Adney, B. and J. Baker. 1996. Measurement


of Cellulase Activities. LAP-006 NREL
Analytical Procedure, National Renewable
Energy Laboratory, Colorado.
3. Anwar, N. A. Widjaya, S. Winardi. 2008.
Study of Enzymatic Hydrolysis of Rice
for Hydrogen Production Using Mixed
Cellulases. http://digilib.its.ac.id/public/
ITS-Research-11652-195209161980031002Paper3.pdf.
4. Carvalho, R.N.L., 2009. Dilute Acid and
Enzymatic Hydrolysis of Sugarcane Bagasse
for Biogas Production, Dissertation, Instituto
Superior Tecnico, Lisboa.
5. Ezeji, T.C., N. Qureshi, and H.P. Blaschek.
2007. Bioproduction of Butanol from Biomass:
from Genes to Bioreactors, Current Opinion in
Biotechnology, 18:220227.
6. Gmez-Sandra, M.R. Andrade Rafael R,
Santander Carlos G, Costa Aline C, Maciel
Filho Rubens, 2010. Pretreatment of Sugarcane
Bagasse with Phosphoric and Sulfuric Diluted
Acid for Fermentable Sugars Production by
Enzymatic Hydrolysis, In: E. Bardone and
A. Viglia (eds). 321 Chemical Engineering
Transactions, Vol. 20.
7. Harmsen, P., W. Huijgen, L. Bermudez,
and R. Bakker, 2010. Literature Review of
Physical and Chemical Pretreatment Processes

11. Mosier, N., C. Wyman, B. Dale, R. Elander,


Y. Y. Lee, M. Holtzapple, and M. R. Ladisch,
2005. Features of Promising Technologies for
Pretreatment of Lignocellulosic Biomass, Bioresource Technology 96(6): 673-686.
12. Harun, R. and M.K. Danquah. 2011. Influence
of Acid Pre-treatment on Microalgal Biomass for
Bioethanol Production. Process Biochemistry,
46: 304309.
13. Qureshi, N., T.C. Ezeji, J. Ebener, B.S. Dien,
M.A. Cotta, H.P. Blaschek, 2008. Butanol
Production by Clostridium beijerinckii. Part
I: Use of Acid and Enzyme Hydrolyzed Corn
Fiber. Bioresource Technology, 99: 5915
5922.

14. Rollin, J.A., Z. Zhu, N. Sathitsuksanoh, Y.H.


Percival Zhang, 2011. Increasing Cellulose
Accessibility Is More Important Than
Removing Lignin: A Comparison of Cellulose
Solvent-Based Lignocellulose Fractionation
and Soaking in Aqueous Ammonia.
Biotechnology and Bioengineering, 108 (1):
22- 30.
15. Snchez, O.J., C.A. Cardona (2008). Trends in
biotechnological production of fuel ethanol from
dif-ferent feedstocks, Bioresource Technololgy
99: 5270-5295.
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DEVITRA SAKA RANI AND CUT NANDA SARI

18. Shang-Tian, Y. 2007. Bioprocessing-

from Biotechnology to Biorefinery. in:


Bioprocessing for Value-added Products from
Renewable Resources: New Technology and
Apllications. Y. Shang-Tian (ed.). Elsevier,
Amsterdam.
19. Tashiro, Y. and K. Sonomoto. 2010. Advances
in Butanol Production by Clostridia, in: Current Research and Education Topics in Applied
Microbiology and Microbial Biotechnology, A.

48

SCIENTIFIC CONTRIBUTIONS OIL & GAS


VOL. 35, NO. 1, APRIL 2012 : 39 - 48

Mendez-Vilaz, (ed.), Formatex, Vol 2. p: 13831394.


16. Selig, M., N. Weiss, and Y. Ji. 2008. Enzymatic
Saccharification of Lignocellulosic Biomass,
Laboratory Analytical Procedure (LAP), Issue
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17. Saha, B.C., L.B. Iten, M.A. Cotta, Y. V. Wu,
2005. Dilute Acid Pretreatment, Enzymatic
Saccharification, and Fermentation of Rice Hulls
to Ethanol. Biotechnol. Prog. 21: 816-822.

SUBJECT INDEX
A

Activated carbon 25, 26, 27, 28, 29


HPLC 11, 12, 13, 17, 18, 19, 20, 21, 22, 23,
B

24

Biodiesel 31, 32, 34, 35, 36, 37


Biofuel 39, 40
Biobutanol 39, 40, 45, 46
C
Corrosion inhibition 11, 12, 19, 20, 21, 22,
23
D
Diesel engine 31, 32, 36, 37
Dilute acid pretreatment 39, 40, 43, 45, 46,
47
E

I
Impregnated zinc chloride 25
Intake valve 31, 34, 35m 36
L
Lignocellulosic biomass 39, 40, 43, 47
M
Mild steel 11, 12, 13, 14, 17, 21, 22, 23
Mercury removal 25, 26, 29

EIS 11, 12, 15

Exhaust valve 31, 33, 35, 36, 37

Potentiodynamic 11, 12, 13, 14, 15, 20

Enzymatic hydrolysis 39, 40, 41, 42, 43, 44,


45, 46, 47, 48

Smoke collector 1, 3, 9

Gas sensor 1, 3, 9

Green tea 11, 12, 13, 14, 15, 16, 17, 18, 19,
20, 21, 23

Thermal precipitator 1, 2, 3, 9

49

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Davis, Gordon B., 1976, Management Information System, Conceptual Foundation Structur and Development, Mc Graw Hill.
Newman W.H. and E. Kirby Warren, 1977, The Process of Management, Concept, Behavior, and Pratice, Prentice-Hall of India
Private Ltd., New Delhi, hlm. 213.
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More than three authors


Bennet J.D., Bridge D. Mcc, Camcron N.R., Djunuddin A, Ghazali S.A, Jeffery D.H., Kartawa W., Keats W., Rock N.M.S., and
Thompson S.J., 1981, The Geology of the Langsa Quadrangle, Sumatra, GRDC, Bandung.
or:
Bannet J.D., et al., 1981, The Geology of the Langsa Quadrangle, Sumatra, GRDC, Bandung.

b. Journal
-

A.S. Nasution and E. Jasjfi. 1996, Production of Gasoline and Impact of More Stringent Specification on Catalyst Performance, 4th
ASCOPE Refining Workshop, Thailand, November.

Weissmann J Dr.; 1972, Fuel for Internal Combustion Engines and Furnace, Report, In-house Research, May, LEMIGAS, Jakarta.

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