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Energy Procedia 32 (2013) 183 189

International Conference on Sustainable Energy Engineering and Application


[ICSEEA 2012]

Effect of pretreatment process by using diluted acid to


characteristic of oil palms frond
Anis Kristiani*, Haznan Abimanyu, A. H Setiawan, Sudiyarmanto, Fauzan Aulia
Research Centre for Chemistry, Indonesian Institute of Sciences, Kawasan PUSPIPTEK Serpong, Tangerang 15314, Indonesia

Abstract
One of lignocellulosic biomass feedstock, oil palms frond is the raw material for a potential second-generation bioethanol production. Pretreatment process is an important process in series of process to produce bio-ethanol. This
research aims to study the effect of pretreatment process by using diluted acid to oil palms frond characterization as
raw materials in the hydrolysis reaction producing monomer sugars which will be fermented into ethanol. The raw
materials are characterized in term of specific surface area and surface morphology. Analysis results of the specific
surface area by BET (Brunauer Emmett Teller) method showed that after pretreatment by using diluted acid, their
specific surface area increasing from 2.23 m2/g to 5.57 m2/g, while the surface morphology of the images shown by
Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD) showed that there is changing the morphology
of surface followed by the increasing of amorphous part.

Authors.
by Elsevier Ltd. Open access under CC BY-NC-ND license.
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Keywords: Bioethanol; diluted acid; oil palms frond; pretreatment; spesific surface and surface morphology.

1. Introduction
Lignocellulosic biomass as a renewable energy resource has big potency for ethanol production
because it is less expensive than starch (corn) dan sucrose (mollase) producing ethanol in high yield and
abundance [1]. Lignocellulose is composed by cellulose, hemicellulose, lignin, extractive, and some

* Corresponding author. Tel.: +62-21-7560090; fax: +62-21-7560549.


E-mail address: anis.kristiani87@gmail.com.

1876-6102 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of the Research Centre for Electrical Power and Mechatronics, Indonesian Institute of Sciences.
doi:10.1016/j.egypro.2013.05.024

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Anis Kristiani et al. / Energy Procedia 32 (2013) 183 189

inorganic materials [2]. Cellulose or -1-4-glukan is polysaccharide linear polymer from glucose
composed by celobiose units [3,4]. Cellulose chain is wrapped by hydrogen bonding named elementer
and microfibril [5]. These fibrils are attached one to another by hemicellulose, amorphous polymer from
different sugar like other polymers, such as pectin and closed by lignin [3].
Microfibril is connected to macrofibril. This special and complicated structure caused cellulose being
resistant to biology and chemistry treatments. Cellulose is available in lignocellulose or purified into
paper or pure cellulose, such as cotton or blended by other materials [6].
Lignin is a complex molecule composed by fenilpropan units and connected to three dimentional
structure which is difficult to be biodegradabled. Lignin is hard to be degradabled both of chemically and
enzymatically. Soft wood contains more lignin than hard wood and mostly agriculture residue. Since
there is chemical bonding between lignin and hemicellulose in fermentation so it makes lignocellulose to
be resistant for chemical and biological degradation [7,8].
Ethanol production from lignocellulose biomass includes three main processes, which are
pretreatment, hydrolysis and fermentation. Pretreatment process by physical, chemical and biological is
one of the main processes in ethanol production process from lignocelluloses [9]. This pretreatment is
needed to produce macroscopic and microscopic biomass structure for fast and efficient hydrolysis to
fermentable sugar [10]. Pretreatment can effect bio-digestibility of waste for ethanol production and
increase enzyme accessibility into material [11]. Pretreatment process also aims to break lignin and
hemicellulose bonding and cystal structure to be simple sugar compound [12].
According to Nathan et.al [10] and Zheng et.al [23], pretreatment process by using diluted acid can
dissolve almost all hemicellulose and break lignin and cellulose bonding so it can increase digestibility of
enzyme/catalyst in hydrolysis process. Yang et.al use diluted sulfur acid in the chemical pretreatment
process and this chemical pretreatment process can dissolve almost all hemicellulose component (80-90
%), increase suspectibility of cellulose, but little break lignin component [22]. Pretreatment process by
using diluted acid can dissolve almost all hemicellulose, but not for lignin component [23].
The size of raw material will affect porosity so it will maximize contact between material and acid to
increase hemicellulose hydrolysis rate. Since the smaller size of raw materials size will produce a large
surface area, this will make the degradation process easier. Sun [12] has done pretreatment process for
bagasse by 80 mesh. In this research, we will use lignocellulose from oil palms frond about 30-40 mesh.
Acid pretreatment can operate in high temperature and low acid concentration or in low temperature
and high acid concentration. Sulfuric acid is commonly used, while other acids such as chloride acid and
nitric acid have been reported. The pretreatment of lignocellulose in high temperature can increase
enzymatic hydrolysis efficiently [13]. But, high acid concentration (30-70 %) makes the process to be
more corrosive and dangerous. Therefore, this process needs a special non metal construction or
expensive alloy [14-16].
Diluted acid hydrolysis perhaps is common method used in pretreatment method. It can be used well
in lignocellulose pretreatment for enzymatic hydrolysis, or as actual sugar hydrolysis method. These
processes and different aspects from diluted acid hydrolysis have been reviewed [13,17]. In a limit
temperature (140-190 C) and low acid concentration (0.1-1 % sulfuric acid), the pretreatment can reach
high reaction rate and increase cellulose hydrolysis significantly. Almost 100 % removing hemicellulose
is done by diluted acid pretreatment. Pretreatment is not effective to dissolve lignin but it can interfere
lignin and increase cellulose suspectibility for enzymatic hydrolysis [14,18].
Diluted acid pretreatment can take place in short resistence time (5 minutes) at temperature of 180 C
or relative long resistence time (30-90 minutes) at temperature of 120 C. Sun and Cheng [19] have done
pretreatment of rye straw and grass to produce ethanol by using enzymatic hydrolysis at 121 C with
different concentration of sulfuric acid (0.6; 0.9; 1.2 and 1.5%, w/w) and residence time (30; 60; and 90
minutes). Emmel et al. [20] have done pretreatment Eucalyptus grandis impregnated by 0.087 and 0.175

Anis Kristiani et al. / Energy Procedia 32 (2013) 183 189

% (w/w) H2SO4 at 200210 C for 2 to 5 minutes. The best condition for recovering hemicellulose is at
210 C for 2 minutes, while the optimum pretreatment temperature is at 200 C.
The aim of pretreatment process is to change these properties for preparing materials of enzymatic
degradation. Because of lignocelullose is so complex, pretreatment process needed is not simple. The
best pretreatment method and condition depend on the type of lignocellulose. This research aims to study
the effect of pretreatment process by using diluted acid to the characteristic of oil palms frond as a raw
material in term of specific surface area and surface morphology.
2. Materials and experimental
2.1. Materials
Raw material of oil palms frond used in this research is oil palms frond from PT. Perkebunan
Nusantara VIII (PTPN VIII) in Malimping, Lebak-Banten. While, chemical used pretreatment process is
NaOH and H2SO4.
2.2. Instrumentation
Equipments used in this pretreatment process are milling-grinding machine, autoclave, glass
equipments, Sorptomatic 1800 CARLO ERBA Instruments, XRD Phillip PW 1710 and SEM JEOL.
2.3. Procedure
A simplified process diagram is shown in Fig.1. Raw material used is oil palms frond will be
pretreated physically by milling then chemically by using diluted acid, H2SO4. After neutralized by using
NaOH, solid sample will be analyzed its chemical component and physical properties.
2.3.1.

Milling (physical/mechanic pretreatment process)

Oil palms frond is cut into 2-3 cm then dried at 50oC for 24 hours and then milled by using millinggrinding machine and sifted to 30-40 mesh. Water content from oil palms frond resulted from milling
process is measured and characterized.
Raw material

Physical/Mechanic Pretreatment Process

Chemical Pretreatment Process

Solid Part

Liquid Part

Characterization
Fig. 1. Experimental process diagram

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Table 1. Chemical compound content of oil palms frond raw material
Characteristic

2.3.2.

Content (% w/w)

Lignin

29.50

Cellulose

40.01

Hemicellulose

30.78

Chemical pretreatment

In this research, we use pretreatment technology of oil palms frond by using diluted acid. Comparison
between solid with liquid (S/L) ratio of 1:15 (w/v) use sulfuric acid concentration, H2SO4 of 0.25 until 2
% (v/v). The sample was put into autoclave at 121 oC for 30, 60, and 90 minutes. A slurry mixture with
pH between 1 to 2 was neutralized to pH 7 by adding NaOH solution then the liquid and its solid was
separated.
2.3.3.

Characterization

Solid samples are analyzed their lignin, cellulose and hemicellulose content by using TAPPI T 13m-45
and ASTM 1104-56 method, specific surface area by using BET, surface morphology by using SEM, and
crystalinity by using XRD methods.
3. Result and discussion
Lignocellulose biomass is composed by cellulose, hemicellulose and lignin connected each other
because of amorphous structure and 1,4- bonding in cellulose and also the existence of lignin between
cellulose chain [10]. Analysis result of oil palms frond is shown in Table 1. Table 1 showed that
cellulose content in oil palms frond raw material is higher than lignin and hemicelluloses [21]. Higher
cellulose content in the sample can produce higher glucose, however hemicellulose content can also
hydrolyze to xylose, while lignin can produce derivative compound of phenol. This research used a
chemical pretreatment process using diluted sulfuric acid. The use of dilute sulfuric acid is dissolving
most of the hemicellulose, increasing the susceptibility of cellulose, but breaking little of the lignin [22].
Figure 2 shows the influence of acid pretreatment to the composition of oil palms frond. As can be
seen from the figure, a smaller percentage of hemicelluloses were at pretreatment condition of 2 %
sulfuric acid at 30 minutes than at any other conditions. In fact, this condition accounted for 10 % of the
hemicelluloses. On the other hand, the process condition of less than 2 % sulfuric acid accounted for 30
% of the hemicelluloses. In addition, the percentage of lignin was more or less same at any conditions. It
is also show that percentage of cellulose changed with the hemicellulose content. It is caused by the
addition of acid concentration broke the microfibril bonding of lignin and hemicellulose bonded in
cellulose component so cellulose content will increase. Oil palms frond pretreated by using 2 % sulfuric
acid has the highest cellulose and the lower lignin will be characterized their physical properties to
observe the effect of pretreatment process.
Oil palms frond sample before and after pretreatment process are analyzed on their specific surface
area by using BET method. Oil palms frond material has two type of specific surface area, which is
external and internal. External specific surface area is related to particle size and shape; while internal
specific surface area is depend on capiler structure of celullosic fiber. Specifically, dry cellulosic fiber has
small size about 15 until 40 m, and so it has external specific surface area which can be considered,

Anis Kristiani et al. / Energy Procedia 32 (2013) 183 189

Fig. 2. Chemical content in oil palms frond after H2SO4 pretreatment at 121C for 30 minutes [21]
Table 2. Specific surface area of oil palms frond before and after H2SO4 pretreatment
Sample

Specific Surface Area (m2/g)

Raw material oil palms frond

2,2334

Pretreated oil palms frond

5,5670

about 0.6 to 1.6 m2/g. But, internal specific surface area of this dry celullosic fiber is smaller than external
specific surface area [24].
Table 2 showed that pretreatment of oil palms frond by using 2 % H2SO4 for 30 minutes increase
specific surface area of raw material. Specific surface area measured by this BET method is external
specific surface area. Higher specific surface area will make contact between raw material and solvent to
be effective so hydrolysis reaction will be more optimal. Figure 3 and 4 showed the SEM micrograph and
XRD profile of oil palms frond before and after 2% H2SO4 pretreatment. The goal of the pretreatment
process is to break down the lignin structure and disrupt the crystalline structure of cellulose, so that the
acids or enzymes can easily access and hydrolyze the cellulose [10].

Fig. 3. SEM micrograph and XRD profile of oil palms frond before H2SO4 pretreatment

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Fig. 4. SEM micrograph and XRD profile of oil palms frond after H2SO4 pretreatment

The effect of the pretreatment is to change their morphology and crystalinity. As can be seen from the
SEM micrograph at 100 micrometer scale, it is clear the change of their morphology before and after
pretreatment process. The peaks at 2 = 15 is the amorphous peak and the peak of 2 = 23o is the crystal
peak. From the figures, it may be calculated that the ratio between amorphous peak and crystal peak
before pretreatment more than their ratio after pretreatment process. On this basis, it may be concluded
that the pretreatment process could increase the amorphous part and consequently decrease the crystal
part of oil palms frond morphology. The amorphous part will make cellulose more accessible to the
enzyme that converts the carbohydrate polymers into fermentable sugars.
4. Conclusion
Pretreatment process of oil palms frond by using diluted acid, H2SO4 2 % at 121 0C for 30 minutes
increase the specific surface area, from 2.23 to 5.57 m2/g, and changing the morphology surface, which is
probably decreasing crystalinity of cellulose molecule.
References
[1] McKendry P. Energy production from biomass (part 1): overview of biomass. Bioresource Technol 2002:83;37-46.
[2] Sjstrm E. Wood chemistry: fundamentals and applications. San Diego: Academic Press; 1993.
[3] Delmer DP, Amor Y. Cellulose biosynthesis. Plant Cell 1995;7:987-1000.
[4] Morohoshi, N. Chemical characterization of wood and its components, In Wood and cellulosic chemistry. New York: Marcel
Dekker Inc; 1991.
[5] Ha MA, Apperley DC, Evans BW, Huxham IM, Jardine WG, Vietor RJ, Reis D, Vian B, Jarvis MC. Fine structure in
cellulose microfibrils: NMR evidence from onion and quince. Plant J 1998:16;183-190.
[6] Talebnia F, Bafrani MP, Lundin M, Taherzadeh MJ. Optimization study of citrus wastes saccharification by diluted acid
hydrolysis. Bioresources 2008:3;108-122.
[7] Taherzadeh MJ. Ethanol from lignocellulose: physiological effects of inhibitors and fermentation strategies. Ph.D thesis in
Biotechnology. Chemical Reaction Engineering. Chalmers University of Technology; 1999.
[8] Palmqvist E. Hahn-Hgerdal B. Fermentation of lignocellulosic hydrolysates. II: Inhibitors and mechanisms of inhibition.
Bioresource Technol 2000;74:25-33.
[9] Taherzadeh MJ. Karimi K. Pretreatment of Lignocellulosic Wastes to Improve Ethanol and Biogas Production: A Review.
Int J Mol Sci 2008:9;1621-1651.

Anis Kristiani et al. / Energy Procedia 32 (2013) 183 189

[10] Nathan M. et al. Features of promising technologies for pretreatment of lignocellulosic biomass. J Bioresource Technology
2005:96;673686.
[11] Taherzadeh MJ, Keikhosro K. Pretreatment of Lignocellulosic Waste to Improve Bioethanol and Biogas Production. Int J
Mol Sci 2008:9;1621-1651.
[12] Sun Y, Cheng J. Hydrolysis of lignocellulosic materials for ethanol production: a review. J Bioresource Technology
2000:83;1-11.
[13] Taherzadeh MJ, Karimi K. Acid-based hydrolysis processes for ethanol from lignocellulosic materials: A review. Bio
Resources 2007:2;472-499.
[14] Wyman CE. Handbook on bioethanol: production and utilization. Washington DC: Taylor & Francis; 1996.
[15] Sun XF, Xu F, Sun RC, Wang YX, Fowler P, Baird MS. Characteristics of degraded lignins obtained from steam exploded
wheat straw. Polym Degrad Stabil 2004:86;245-256.
[16] Jones J, Semrau K. Wood hydrolysis for ethanol production previous experience and the economics of selected processes.
Biomass 1984:5;109-135.
[17] Taherzadeh MJ, Karimi K. Enzymatic-based hydrolysis processes for ethanol from lignocellulosic materials: A review. Bio
Resources 2007:2;707-738.
[18] Yang B, Wyman CE. 2004. Effect of xylan and lignin removal by batch and flowthrough pretreatment on the enzymatic
digestibility of corn stover cellulose. Biotechnol Bioeng 2004:86;88-95.
[19] Sun Y, Cheng JJ. Diluted acid pretreatment of rye straw and bermudagrass for ethanol production. Bioresource Technol
2005:96;1599-606.
[20] Emmel A, Mathias AL, Wypych F, Ramos LP. Fractionation of Eucalyptus grandis chips by diluted acid- catalysed steam
explosion. Bioresource Technol 2003:86;105-115.
[21] Sudiyarmanto A, Kristiani F, Aulia, Setiawan AH. Studi Optimasi Proses Pretreatment Pelepah Kelapa Sawit Cara Asam
Encer untuk Pembuatan Bioetanol. Prosiding Seminar Nasional Jaringan Kerja sama Kimia Indonesia 3 November 2011.
Yogyakarta, Indonesia.
[22] Yang B, Wyman CE. Pretreatment: the key to unlocking low-cost cellulosic ethanol. Biofuels Bioprod Bioref 2008:2;26-40.
[23] Zheng Y, Pan Z, Zhang R. Overview of biomass pretreatment for cellulosic ethanol production. Int J Agric & Biol Eng
2009:2(3);51-68.
[24] Fan LT, Lee Y, Beardmore DH. Mechanism of the enzymatic hydrolysis of cellulose: Effects of major structural features of
cellulose on enzymatic hydrolysis. Biotechnol Bioeng 1980:22;177-199.

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