Lignin recovery from alkaline hydrolysis and

glycerolysis of oil palm fiber

Cite as: AIP Conference Proceedings 1614, 433 (2014); https://doi.org/10.1063/1.4895236
Published Online: 17 February 2015

Nur Syakilla Hassan, and Khairiah Haji Badri

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AIP Conference Proceedings 1614, 433 (2014); https://doi.org/10.1063/1.4895236 1614, 433

© 2014 AIP Publishing LLC.

 Lignin Recovery from Alkaline Hydrolysis and Glycerolysis
of Oil Palm Fiber
a
Nur Syakilla Hassan and bKhairiah Haji Badri
a
School of Chemical Sciences and Food Technology, Faculty of Science and Technology
Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Malaysia
b
Polymer Research Center, Faculty of Science and Technology Universiti Kebangsaan Malaysia,
43600 UKM Bangi, Selangor Malaysia

Abstract. In the present work, two types of treatment namely alkaline hydrolysis and glycerolysis have been conducted
for lignin extraction from oil palm empty fruit bunch (EFB) fiber. Lignin has been retrieved from two sequential methods,
which was the klason lignin from residue and lignin from precipitation of the filtrate. Alkaline hydrolysis was performed
using 10% NaOH solution at room condition. This has extracted 13.0 % lignin. On the other hand, glycerolysis was
carried out using 70% glycerol catalyzed with 5% of 1 M NaOH at 60-70 °C. This has successfully extracted 16.0%
lignin. The SEM micrographs exhibited some physical changes on the surface where the impurities and waxes have been
removed, exposing the,lumen. Besides that, FTIR analysis was conducted on untreated EFB, treated EFB and extracted
lignin. Delignification of EFB fiber was confirmed based on the intensity reduction at 1245 cm-1 that showed lignin was
removed from the fiber. The presence of C=O, C=C and C=C aromatic peaks in the FTIR spectra of the dried filtrate gave
an evidence on the presence of lignin.

Keywords: EFB, lignocellulose, lignin, alkaline hydrolysis, glycerolysis, glycosidic bond

PACS: 80

INTRODUCTION
Lignocellulose is defined as fibrous material that forms the cell walls of the plants and has a complex internal
structure. It is comprised of a number of major components which is cellulose, hemicellulose and lignin with
complex structures [1-2]. The source of lignocellulosic is biomass such as empty fruit bunch, rice husk and kenaf.
Malaysia is one of the largest palm oil producers in the world. The oil palm industry generated various biomass
products such as oil palm trunks (OPT) and fronds (OPF), kernel shell, empty fruit bunch (EFB), pressed fruit fiber
(PFF) and palm oil mill effluent (POME) after palm oil processing [3]. Numerous approaches have been used to
isolate cellulose, hemicellulose and lignin from lignocellulose biomass by means of mechanical, physical, chemical
and biological methods. These components have been widely used in conversion to chemical feedstock such as
reducing sugars, furfural, and ethanol [4].
Lignin consists of phenolic monomers which are coniferyl alcohol, coumaryl alcohol and sinapyl alcohol [5].
FIGURE 1 showed the structure of these three monomers. Nowadays, lignin has been widely used for value-added
products which gave a lot of benefits towards the environment and the economy around the world. However, method
of extracting cellulose is more extensively discussed compared to lignin extraction. Isolating lignin from
lignocellulosic materials is considered difficult because of the undesirable structure changes through condensation
and oxidation reactions during segregation. The existing lignin isolation methods are divided into some parts. The
first part was based on the hydrolysis or solubilisation of cellulose and hemicelluloses by chemical reagents leaving
lignin as an insoluble material. Another part conducted are based on the dissolution or removal of lignin into the
filtrate and can be recovered by subsequent treatment [6]. Some bases such as hydrogen peroxide, calcium
hydroxide and sodium hydroxide can be used in alkaline extraction of lignin [5]. Sodium hydroxide (NaOH) is
commonly used in the alkaline pretreatment which help solubilize and extract lignin from the biomass by affecting
acetyl group in hemicellulose and linkages of lignin–carbohydrate ester. This treatment does not disturb the lignin
aromatic structure significantly [7-8].

The 2014 UKM FST Postgraduate Colloquium

AIP Conf. Proc. 1614, 433-438 (2014); doi: 10.1063/1.4895236
© 2014 AIP Publishing LLC 978-0-7354-1250-7/$30.00

433
 CH2OH CH2OH CH2OH

OMe MeO
OMe
OH OH OH

coumaryl alcohol coniferyl alcohol sinapyl alcohol

FIGURE 1. The structure of lignin monomers.

Alkaline hydrolysis requires lower temperature and pressure but the reaction time can be long compared to other
methods [6]. Other lignin extracting method is through precipitation of black liquor by mineral acid. Mineral acid
was added to the filtrate until pH 2 was achieved. Then, the precipitate was filtered and dried. This method requires
25% NaOH solution concentration with reaction temperature of 100-170 ºC. High concentration of mineral acid was
used, which was up to 50% [9-10]. The variety of functional groups presented in lignin allows a wide range of
applications such as as activated carbon, dispersants, surfactant, vanillin and others [11]. In this paper, NaOH
treatment was performed in a mild condition. The treatment was performed at room temperature with low pressure.
Furthermore, glycerolysis was also conducted using glycerol in the presence of catalyst. These methods broke the
glycosidic bond between lignocellulose components thus remove lignin from EFB in form of filtrate [12-13]. Lignin
in EFB fiber is composed of guaiacyl propane units (G) that have one methoxy group and syringyl propane unit (S)
that have two methoxy groups [14]. These two were the possible lignin unit to be retrieved from the EFB. This paper
aims to determine the total recovery of lignin using two sequential methods from the filter cake and filtrate with
mild conditions.

MATERIALS AND METHOD

Materials
The EFB fiber was obtained from Sri Ulu Langat Palm Oil Mill Sdn Bhd, Selangor, Malaysia. The fiber was
ground and sieved using a sieve shaker to obtain a size of 250 to 315μm. Sodium hydroxide pellet (~99% purity)
and glacial acetic acid (CH3COOH, 99.8 wt %) were purchased from Merck (M) Sdn Bhd, Selangor, Malaysia.
Glycerol (anhydrous, 99% purity) was manufactured by R & M Ltd. Steinheim, Germany. Sulphuric acid (H2SO4,
95-98 wt %) was purchased from Systerm Sdn Bhd, Selangor, Malaysia.

Methods
The EFB fiber undergone two types of treatment namely alkaline treatment and glycerolysis. For the alkaline
treatment, the EFB fiber was treated with NaOH. The EFB fiber was soaked in 10% NaOH solution at a ratio of 1:20
for 48h at room condition. The mixture was filtered and rinsed with diluted CH3COOH and distilled water until it
reached pH 7. The filter cake was dried at 105°C for 24 h according to ASTM D2016-65 standard method of drying
(Methods of test for moisture content of wood). The filtrate from the treatment was kept in the oven at 60-70 °C
until complete dryness. The solid remained after drying process was kept in a screw-cap jar for further analysis.
Glycerolysis was conducted according to the method reported by Ibrahim et al. [13]. The mixture of EFB and 70%
(w/w) aqueous glycerol at a ratio of 1:20 was refluxed with purged nitrogen gas at 60-70 °C under constant stirring
at 600 rpm. The reaction was catalyzed using 5% (w/v) 1 M NaOH. After 3 h, the mixture was filtered; the filter
cake was dried in the oven and kept for further analysis.
Filter cake from both treatments was analysed for klason lignin (TAPPiT222 cm-98) and compared to the
untreated EFB fiber. The surface morphology of the untreated and treated EFB was examined using a scanning
electron microscope (SEM) model Evo MA10 at 500× magnifications. The FT-IR spectrum of each sample was
obtained using a spectrophotometer model Perkin Elmer Spectrum 400 FT-IR at wave numbers of 4000 to 650 cm-1.

434
The FTIR spectroscopy analysis was conducted using the ATR-FTIR technique. Filtrate obtained from the filtration
of the treated mixture was dried in the oven until the volume was reduced to half. It was then centrifuged and the
solid part was taken and filtered, rinsed with water several times, and dried in the oven.

RESULTS AND DISCUSSION

FIGURE 2 shows the FTIR spectrum of the untreated EFB (UT-EFB), NaOH-treated EFB (N-EFB) and
glycerolysed EFB (Gly-EFB). All spectrums have broad and intense peak at 3328 cm-1, 3335cm -1 and 3340cm-1.
These peaks were assigned to the O-H stretching vibration from cellulose of the fiber. These peaks were slightly
shifted after treatments that might be associated to hydrogen bonding between different functional groups as shown
in FIGURE 1 [15].

FIGURE 2. ATR- FTIR spectrum of UT-EFB, N-EFB and Gly-EFB.

An absorption peak at 2900 cm-1 in the spectrum of treated EFB indicated the present of C-H stretching. Besides,
a band observed at 1728 cm-1 in the spectrum of UT-EFB was due to C=O stretching but this peak was disappeared
upon treatments. The band observed at 1650-1590 cm-1 in UT-EFB and treated EFB were assigned to C=C aromatic
vibration exhibited the present of lignin. The syringyl propane unit (S) at 1375 cm -1 and guaiacyl propane units (G)
at 1245 cm-1 were detected. However, intensity of this peak decreased after treatment. This was contributed to small
portion of lignin that has been partially released into the filtrate [16]. An absorption band at 897 cm−1 was assigned
to C–O–C stretching at the β–(1, 4)–glycosidic linkage in cellulose [14]. The FTIR spectra of N-EFB and Gly-EFB
did not show any significant different from one to another. Both spectra showed disappearance of peak at 1700 cm-1
due to removal of hemicellulose [16].
The fiber surface morphologies of UT-EFB, N-EFB, Gly-EFB were analysed from SEM micrographs and the
results were showed in FIGURE 3. UT-EFB exhibited smooth surface with wart as shown in FIGURE 3 (a). This
condition might be caused by the presence of impurities and wax layer. FIGURE 3 (b) and FIGURE 2 (c) shows the
changes of surface morphology on the EFB upon treatment with NaOH aqueous solution and aqueous glycerol
respectively. UT-EFB structure was distorted after treatment compare to the structure before treatment which
appeared as rigid and highly ordered fibrils. Detachment of the fibrils to form microfibrils occurred during

435
hydrolysis. The alkaline treatment was designed to clean the surface layer as well as to debond the linkages of the
outer surface with the internal composition and exposed the components in EFB [17]. Surface impurities have been
removed completely with NaOH hydrolysis as shown in FIGURE 3 (b). The NaOH has successfully tarnished the
fiber surface and the lumen that it resulted in a rough surface with craters. On the other hand, glycerolysis of EFB
(FIGURE 3 (c)) though resulted in clear lumens, detection of some impurities suspected coming from the glycerol
was clearly shown. Both chemical treatments reduced the fiber size (in the scope of diameter) due to removal of
outer fiber layer during defibrilation.

(a) (b)

(c)

FIGURE 3. SEM micrographs of (a) UT-EFB, (b) N-EFB and (c) Gly-EFB.

It has been reported that oil palm empty fruit bunch fiber (EFB) contains 45% cellulose, 32.8% hemicellulose
and 20.5% lignin [18]. Lignin comprised of insoluble and soluble lignins. The insoluble lignin or also known as
klason-lignin is the filter cake from the hydrolysis [19]. Soluble lignin can be either acid or alkali soluble lignin
depending on type of solvent used during the process. The amount of insoluble lignin in UT-EFB, N-EFB and Gly-
EFB after klason-lignin determination was as shown in TABLE (1). The content of the klason-lignin of UT-EFB, N-
EFB and Gly-EFB was determined at 17.0%, 9.0% and 12.5% respectively.

TABLE (1). The total amount of lignin.

Sampels Klason lignin % Soluble lignin %
UT-EFB 17.0 -
N- EFB 9.0 4.0
Gly-EFB 12.5 3.5

Total klason lignin in the N-EFB and Gly-EFB was lower than in UT-EFB. NaOH hydrolysis and glycerolysis
has formed cleavage to the ether bond in the lignin structure releasing lignin into the filtrate [20]. However, the total
klason lignin content in N-EFB was lower than in Gly-EFB. Alkaline treatment with NaOH removed more lignin
fraction from the biomass because of the solubilisation of lignin in alkaline solution [21]. NaOH degrade the lignin
into smaller units by cleaving phenylpropane unit linkages thus create free phenolic hydroxyl groups. The presence

436
of these hydroxyl groups making the lignin more soluble in solution [22]. Physical observation detected that the
klason lignin obtained from the NaOH treatment and glycerolysis was darker compared to klason lignin of the UT-
EFB. Natural lignin is a colorless or pale yellow but the color changed to brown or dark brown when it reacts with
acid or base [11]. Soluble lignin was the lignin derived from the filtrate after treatment. The presence of lignin was
identified by the presence of functional groups which can be seen through FTIR spectrum as shown in FIGURE 4.

FIGURE 4. ATR-FTIR spectra of the soluble lignin extracted from N-EFB and Gly-EFB.

The precipitate obtained after drying has been analyzed by FTIR and the spectrum was as shown in FIGURE 4.
Both spectra of N-EFB and Gly-EFB have peaks at 3372 and 3332 cm-1 indicating the alcoholic and phenolic OH-
groups related to hydrogen bond [23]. Absent of C-H stretching peak was clearly shown in the spectrum for N-EFB.
However, the presence of a shoulder at 1708 cm-1 indicated the absorption peak of C=O. Both absorption peaks at
1616 and 1633 cm-1 represented the C=C stretching vibration belonged to the aromatic ring in lignin [24].
Absorption bands for lignin at 1513 and 1515 cm-1 indicated aromatic skeletal vibrations which showed the
characteristic peaks of lignin [25]. Both G and S lignin units were detected in the spectrum of Gly-EFB at 1316 and
1236 cm-1 respectively. This confirmed the presence of lignin in the precipitate obtained from the filtrate.

CONCLUSION
Alkaline hydrolysis by NaOH and glycerolysis have not only managed to remove the impurities on the surface of
EFB but also played major role in delignification. Based on the FTIR spectrum, lignin has been recovered from the
filtrate from both treatments after drying process. Glycerolysis has successfully recovered lignin up to 16% total of
klason lignin and lignin in filtrate.

437
 ACKNOWLEDGEMENTS
The authors would like to thank Polymer Research Center and School of Chemical Sciences and Food
Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia for providing the working area,
Ministry of Higher Education (MOHE) for the Exploratory Research Grant Scheme (ERGS) with code no.
ERGS/1/2013/STG01/UKM/02/2 and Centre for Research Instrumentation Management (CRIM), Universiti
Kebangsaan Malaysia for the instrument provided for sample analysis throughout the study.

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