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Comparison of Cellulose Extraction from Sugarcane Bagasse Through Alkali

Article  in  Materials Research · October 2018

DOI: 10.1590/1980-5373-mr-2017-0750

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Materials Research. 2018; 21(6): e20170750
DOI: http://dx.doi.org/10.1590/1980-5373-MR-2017-0750

Comparison of Cellulose Extraction from Sugarcane Bagasse Through Alkali

Zimele Nkosivele Treasure Mzimelaa , Linda Zikhona Linganisoa, Neerish Revaprasadua,

Tshwafo Elias Motaunga*

a
Department of Chemistry, University of Zululand (KwaDlangezwa Campus), Private Bag X1001, 3886,
South Africa

Received: August 22, 2018; Revised: July 27, 2018; Accepted: September 28, 2018

This article investigated the cellulose obtained from sugarcane bagasse by five different extraction
mercerization methods. The comparison of the methods gives a clearer picture of that is more effective
and feasible for production of SCB cellulose. All the celluloses were characterised by X-Ray Diffraction
(XRD), Fourier Transform Infrared (FT-IR), Thermal Gravimetric Analysis (TGA), Scanning Electron
Microscope (SEM) and Optical Microscope (OM). All the methods led to white material resembling
pure cellulose due to removal of non-cellulosic constituents as can be seen by disappearance of aromatic
bands. The removal indicated a decrease in diameter and improved thermal stability in most methods.
The materials in general stand a better chance of competing as fillers for polymeric composites.
Keywords: Sugar cane bagasse, extraction methods, cellulose, crystallinity.

1. Introduction
removes most of the residual phenolic molecules like lignin
The extraction of cellulose from natural matrix in plants or polyphenols.
involves the removal of lignin, hemicelluloses and pectins. There are lot of different methods used to extract cellulose,
Over the past few years, a lot of methods have been suggested nonetheless the literature is virtually mute about a methodical
and used by different researchers to extract cellulose from comparison of properties from different methods and possible
different plants 1-17. The methods generally involve basic benefits for different applications. Five different methods of
or oxidative treatments that have the ability to discharge extraction of cellulose from the same sugar cane bagasse
cellulose. Alternatively, treatment with peracids has been were used in this study. Characterization techniques used
used to extract cellulose. This step is significant due to the for comparison included TGA, FTIR, XRD, OM, and SEM.
ability to change the thermal stability and crystallinity of a
cellulosic material. Other researchers used an acid-induced 2. Experimental
destructuring process, during which the heterogeneous acid
hydrolysis involves the diffusion of acid molecules into cellulose 2.1 Materials
fibres, followed by cleavage of glycosidic bonds. That was
followed by centrifugation, dialysis and ultrasonication 18. Sugarcane bagasse was obtained from a sugarcane mill
Most studies used six steps, which were the pre-treatment in Felixton near Empangeni, South Africa. Acetic acid was
of the fibres with sodium hydroxide, hydrogen peroxide, obtained from Laboratory Consumables and Chemical
sodium hydroxide and Na2B4O7.10H2O, HNO3 and HAc, Suppliers, sodium sulphite and sodium hydroxide were
ethanol, water and finally drying the product in an oven until obtained from Merk, sodium chlorite was obtained from
constant weight. Other researchers involved the treatment Sigma Aldrich, and sodium hypochlorite was obtained from
of fibres with sodium chlorite which facilitated the removal a local supermarket. All chemicals were used without further
of lignin, which was followed by NaOH and drying until purification, but were prepared to the desired concentrations.
constant weight 19. Although both methods resulted in cellulose
2.2. Extraction of cellulose from sugarcane
with significant quantities of hemicelluloses or lignin, the
first procedure was less environmentally aggressive, while
bagasse
the second involved less process time and led to fibres with
2.2.1. Method 1(M1)
more homogeneous diameter distribution.
Treatments consisting of alkali extraction and bleaching Sugarcane bagasse was boiled in water (4hrs). Soaked
have been the mostly used in the extraction of cellulose 20. in 4% sodium hydroxide (4hrs), followed by treating with
The alkali extraction treatment allows the removal of soluble 4 % sodium hypochlorite and 2% sodium hydroxide (4hrs)
polysaccharides, and the subsequent bleaching treatment at 100 ºC before washing with distilled water to pH neutral.
The final product was dried at room temperature for 2 days.

* e-mail: motaungte@live.com
2 Mzimela et al. Materials Research

2.2.2. Method 2(M2) 3. Results and Discussion

From the M1 1, 4 % of sodium hypochlorite was acidified 3.1. Optical microscope

with acetic acid to pH4.
Optical microscope images of all the methods are shown
2.2.3 Method 3(M3)
in Figure 1 (a-e). The fibres of M1 and 2 are agglomerated.
From the M1, 2 and 1% of NaOH was used in the second In M1 the fibres are more agglomerated and closely packed
and last step respectively, 0.7 % sodium chlorite acidified than in M2. M3, 4 and 5 show defibrillation and thinning of
with acetic acid to pH4 was used instead of 4 % sodium fibres, which signal the removal of non-cellulosic components
hypochlorite. in SCB. The thinning and defibrillation is further noted for
the M5.
2.2.4. Method 4(M4)
The M1 (Figure 1a) showed agglomeration compared
From the M3, the last step was eliminated. to M2. This is because sodium hypochlorite is highly basic
in nature and therefore could not effectively facilitate the
2.2.5. Method 5(M5)
digestion of the cell walls which is meant to make the treatment
From the M3, the additional step was added after sodium with alkali more effective. The introduction of acetic acid
chlorite step, in which sample was treated with 5% sodium in sodium hypochlorite in M2 (Figure 1b) increased the
sulphite at 100 ºC for three hours. defibrillation, but to a very small extent.
In M3, 4 and 5 (Figure 1 c-e), acidified sodium chlorite was
2.3 Analysis
used for the digestion of the cell walls of SCB. This proved
to be more effective than M1 and M2. Further defibrillation
2.3.1. Optical Microscopy (OM)
was noted for the M5 (Figure 1e) and can be attributed to
The optical microscope images of the samples were sodium sulphite used for dissolved lignin-chlorine complex
viewed using a LEICA MC 120 HD microscope. Dark and that forms during the digestion process.
bright field modes were used to capture the images at a
3.2. Scanning Electron Microscope (SEM)
magnification of 40 x/ 0.65.
Figure 2 showed SEM micrographs of raw sugarcane
2.3.2. Scanning Electron Microscope (SEM)
bagasse (a and b) ranging from 100 to 250 µm. There are
The SEM and EDX measurements of the as-deposited many non- fibrous materials, from waxes and pectin, which
thin films were performed on a Philips XL 30 FEG (at 10 kV) are scattered over the surface. The SEM micrographs of the
and DX4 detector (at 20 kV), respectively. The films were different methods used for the extraction of cellulose from
carbon-coated by using Edward’s E306A coating system, sugarcane bagasse are shown in Figures 3, 4 and 5. The
prior to the analyses. surfaces of all the cellulosic materials are cleaner and a bit
rougher in comparison to those of raw bagasse. Furthermore,
2.3.3 Fourier Transform infrared (FTIR)
individual fibres show a decrease in diameter from about
Infra-red spectra of the samples were recorded on a 3 to 10 µm, which signify the removal of hemicelluloses,
Bruker FT-IR Tensor 27 spectrophotometer equipped with a lignin, pectins and waxes.
standard ATR crystal cell detector. The spectra were recorded As the bagasse is treated with different chemicals,
at a wavenumber range of 500-4000 cm-1. the non-cellulosic components are removed to promote
defibrillation, which causes reduction in diameter. SEM
2.3.4. X-Ray Diffraction (XRD)
results are in correspondence with observations made from
The diffraction patterns of the cellulosic materials were the optical microscope analysis.
investigated at room temperature using an Advanced Bruker
3.3. Fourier Transform infrared (FTIR)
AX D8 diffractometer in the range 2θ = 10 - 90 º, equipped
with nickel-filtered Cu Kα radiation (λ = 1.542 Å) at 40 kV Figure 6 represents FT-IR spectra of extracted cellulosic
and 40 mA. The scan speed was 0.5 sec/step. materials. For all the samples, the FTIR spectra showed O-H
stretching broad band at 3500-3200 cm-1. The spectra also
2.3.5 Thermal Gravimetric Analysis (TGA)
showed C-H stretching vibration at around 2894 cm-1, which
Thermogravimetric analyses were carried out using a is also characteristic of cellulosic materials. Absorbance
Perkin Elmer Pyris 6 TGA equipped with a closed perforated peaks around 1649-1641 cm-1 resulted from O-H bending
pan at a heating rate of 10 ºC.min-1. Approximately 2 mg of adsorbed water. The peaks around 1054 cm-1 are due to
of each sample was heated from 30 - 600 ºC under N2 gas the C-O-C pyranose ring stretching vibration 10. Another
flow rate of 10 ml.min-1. important absorption band is at around 902 cm-1 which is
associated with the β-glycosidic linkages between glucose 6,9,13.
 Comparison of Cellulose Extraction from Sugarcane Bagasse Through Alkali 3

Figure 1. OM images of methods 1(a), 2(b), 3(c), 4(d), and 5(e)

Figure 2. SEM micrographs of raw sugarcane bagasse

Figure 3. SEM micrographs of cellulose extracted from sugarcane bagasse through method 1 (c, d), method 2 (e, f)
4 Mzimela et al. Materials Research

Figure 4. SEM micrographs of cellulose extracted from sugarcane bagasse through method 3(g, h) andmethod
4 (i, j)

Figure 5. SEM micrographs of cellulose extracted from sugarcane bagasse through method 5

Figure 6. FTIR spectra of the methods used for the extraction of cellulose from sugarcane bagasse
 Comparison of Cellulose Extraction from Sugarcane Bagasse Through Alkali 5

The M1 revealed low O-H stretching band compared to Table 1. Crystallinity index and Crystallite size values of the methods.
the rest, except M3 which showed the lowest. Furthermore, it 2θ (Main Crystallinity Crystallite size
Method
revealed the aromatic peak at 1597 cm-1, whereas other were reflection) index (%) (nm)
reflected almost at 1640 cm-1. The O-H stretching band for M1 23.08 68 5.2 ± 2.1
M2 is more intense than all and not showing a peak at 1250 M2 22.98 70 5.0 ± 1.5
cm-1 compared to the rest. As for M3, most of the aromatic M3 22.63 67 3.9 ± 0.4
peaks (e.g. 1197 cm-1) have almost disappeared. The M4 M4 23.32 72 3.8 ± 1.2
and M5 followed the same trend as M3, even though their
M5 22.63 73 4.0 ± 2.2
peaks are slightly intense than M3 including O-H stretching.

3.4. X-Ray Diffraction

inconsistency in crystalline sizes versus crystallinity index
All the diffractograms at high reflection of the five particularly under different treatments of cellulosic material
methods are displayed in Figure 7. Crystallinity index (CI) is known in literature and that account for our observations 22.
values were calculated from the Segal empirical method 22. Nonetheless in this study an unsafe inference could be drawn
The CI values calculated from the height of the 002 peak that the increase in crystallinity index of cellulosic material
(I002) and the height of the minimum (Imin) between the 002 is indirectly proportional to crystallite size.
peak and the 001 peaks. The crystallite sizes were calculated
3.5. Thermal Gravimetric Analysis
using Scherrer equation 22.Very well-defined peaks at around
2θ = 12.5 º (for 110 planes) and 2θ = 22.5 º (for 200 planes), Figure 8 represented TG and DTG curves of cellulose
which are representative of a typical cellulose structure. extracted from the different methods. All curves appeared to
However, M1 and M2 revealed impurities which seemed to follow similar degradation mechanism with three degradation
have a little or/and no relation with the structure of cellulose. steps. The second step shouldered the third, except M1
Surprisingly they have almost the same crystallite size. The which indicated a resolution of the second and third steps
same is apparent for a reflection at approximately 61º for at approximately 250 and 300 ºC. In addition M1 indicated
M4 and M5. These indicated either formation or presence of poorest thermal stability with highest char content, while
cellulose derivatives from the chlorite salts 5,7,18. Furthermore, M5 and M3 revealed higher thermal stability trailed by M4
crystallinity index values of M4 and M5 dominated the rest and M2 respectively. This results seem to contradict SEM
followed by M2, M3 and M1 (See Table 1). which suggested a better surface area for M1, but FTIR and
The use of NaOH after the chlorite salts for M1, M2 M3 XRD suggested formation cellulose derivatives. It is known
promoted formation of cellulose derivatives which rendered in literature that lignin is catalytic to thermal degradation
the decreased crystallite index value. This is in line with of celluloses 13,16, but in this case the derivatives seemed to
literature which indicated that formation of some cellulose dominate because all samples indicated presence of lignin
derivatives is known to decrease initial crystallinity 5,7,18,19,21. from FTIR. By the way another factor may be the lignin
In fact, the difference in crystallinity of M1, M2 and M3 content or the nature of cellulose derivative which could
could be safely attributed to potential of the chlorite salts. explain higher thermal stabilities of the other methods.
For example, the M2 suggested that the use of 0.7% acidic
sodium chlorite over acidic sodium hypochlorite in M3 was 4. Conclusions
adverse to obtain high crystallinity but resolute to maintain
the cellulose structure. Coincidentally M3,M4 and M5 Cellulose has been successfully extracted from sugarcane
appeared to have almost similar crystalline sizes which are bagasse through five different methods. The use of acidified
less than M1 and M2 within experimental uncertainties. The sodium chlorite proved to be very effective in the digestion of

Figure 7. XRD diffractograms of the five methods used for the extraction of cellulose from sugarcane Bagasse
6 Mzimela et al. Materials Research

Figure 8. TG and DTG curves of the five methods used for the extraction of cellulose from sugarcane bagasse

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