International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333

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Extraction and Characterization of Lignin from Moroccan
Sugarcane Bagasse Using Response Surface Design
S. Aoul-hrouz a,*, Y. Essamellali a,b, M. Zahouily,a,b
a
Laboratory of Materials, Catalysis and Valorization of Natural Ressources (URAC 24), Faculty of Sciences and
Technical Mohammedia, Hassan II University of Casablanca, Morocco.
b
MAScIR Foundation, VARENA Center, Rabat Design, Madinat Al Irfane, 10100 Rabat, Morocco

Abstract— The central composite design was used to design an
experimental program to provide data to model the effects of
various factors on extraction lignin from Moroccan sugarcane
bagasse. The variables chosen were sodium hydroxide volume,
temperature, and reaction time. The mathematical relationship
of extraction yield on the three significant independent
variables can be approximated by a nonlinear polynomial
model. Predicted values were found to be in good agreement
with experimental values. This procedure provides several
advantages such as high yield, clean isolated lignin, and short
reaction time. This lignin was submitted to a comprehensive
structural characterization employing spectroscopic (UV, FTIR,
liquid state 13C NMR and MALDI ToF spectroscopy) and
different complementary analysis such as scanning electron
microscope (SEM), thermogravinometric analysis (TGA) and
derivative thermogravinometric (DTG). Results obtained
showed that this lignin is mainly composed of G and S units
and less free hydroxyls and highlights the absence of residual
sugars in lignin.
Keywords—Lignin; Bagasse; Moroccan sugarcane; Response
Optimization; Central Composite Design.
I. INTRODUCTION
Sugarcane bagasse, Saccharumofficinarum L., is one of the
largest residuals on agriculture in the world [1-3]. This fibrous
residue is obtained after crushing and extraction of juice from
the sugarcane. Sugarcane is an energy crop that is largely
grown on flat land in countries such as Brazil, China, India,
Thailand and Australia [4]. In Morocco, the production of sugar
cane performed in 2013 is of the order of 580000 tonnes against
510834 tonnes in 2012, an improvement of 13%. In general, 1
tonne of sugarcane generates 280 kg of bagasse; thus, with one
production of about 580000 tonnesof sugarcane, Moroccan
produced 162400 tonnes of bagasse during the year 2013 [5].
Normally sugarcane bagasse has been used as a fuel to generate
power of sugar mill. However, a huge quantity of the remaining
bagasse is not used and burnt in the fields, which can cause
environmental problems. Sugarcane bagasse is a rather
heterogeneous material, generally consisting of three main
components: 50% cellulose and 25% each of hemicelluloses
and lignin [6].
Because of its low ash content, bagasse offers numerous
advantages for usage in bioconversion processes using
microbial cultures. Also, in comparison to other agricultural
residues, bagasse can be considered as a rich solar energy
reservoir due to its high yields (about 80 tonnes per hectare in
comparison to about 1, 2 and 20 tonnes per hectare for wheat,
other grasses and trees, respectively) and annual regeneration
capacity [1].
Sugarcane bagasse wastes have been applied in the following
instances: i) cellulose, lignin, rind, comrind, pith enhance
reinforcement in materials manufactured based on different
methods applied; ii) Mixed with tapioca starch and glycerol to
produce composite materials; iii) mixed with gelatin, starch and
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agar to produce tableware packaging material ; iv) sugarcane
bagasse ash and sugar cane straw ash can partially replace
cement and act as pozzolanic additive in manufacturing of
concrete and ash block; v) Sugarcane bagasse ash mixed with
Arabic gum and water to produce ceramic and refractory
products ; and vi) Both sugar cane combined and their mixture
with hardwood are used with phenol formaldehyde resin and
wax to manufacture composite board.
Lignin is an amorphous, and consists in a complex phenolic
polymer composed of three phenylpropane monomeric building
units [7-10]. The type of monomeric units present in lignin
structure and their relative abundance depend on its botanic
origin. The major chemical functional groups present in lignin
structure include hydroxyl, methoxyl, carbonyl and carboxyl
moieties in various amounts depending on its botanic origin
[11]. Hydroxyl groups and free positions in the aromatic ring
are the most characteristic functions in lignin, which determine
its reactivity and constitute the reactive sites to be exploited in
macromolecular chemistry.
Lignin has been studied for two general uses; the first is
production of small molecule chemicals by decomposition or
refinery process. Catalytic methods used to convert lignin
include various types of reduction, oxidation, and catalytic
cracking process [12-14]. Because lignin is an aromatic
macromolecule derived from plants, this is an ideal strategy to
substitute petroleum-based feedstock by those based on
renewable resources. However, additional research is needed to
overcome serious practical issues associated with the huge
energy costs and necessary purification process to produce
small molecule chemicals from this complex natural material.
The second approach to the general use of lignin is as a starting
material of a diversity of commercial polymer products [15,
16]. The incorporation of lignin into polymeric materials
directly or after chemical modification, is recognized as one of
the most viable approaches to accomplish its valorization and
properly exploit its unique intrinsic properties [17, 18].
However, the physicochemical properties of lignin, and
therefore its suitability for specific polymer applications, are
largely dependent on the plant species and the isolation
processes [19]. The applications of material from lignin that
have been identified include packaging films, food coatings,
cationic biopolymers, hydrogels and biomedical uses. Recently,
lignin extracted from herbaceous plants are currently receiving
increasing attention as proven by the recent industrial and pilot
scale production of nonwood lignin by Green Value SA and
CIMV, respectively [20, 21]. The reasons justifying this recent
interest stand in the annual renewability of herbaceous plants,
their high tonnage per year, the increased conversion of
cellulosic substrate into biofuel when lignin is first extracted
from the lignocellulosic feedstock, and the improved
economics of cellulosic processes when developing value-
added lignin co products. However, the physicochemical
properties of lignin, and therefore its suitability for specific
polymer applications, are largely dependent on the plant species
and the isolation processes [19]. The resulting increased
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 International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333
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heterogeneity and complexity of herbaceous lignin compared to
wood lignin and the much more limited knowledge of their
chemistry requires that additional efforts be dedicated to their
characterization [22-24].
Therefore, in the present study, the extraction of lignin present
in the Moroccan sugarcane bagasse was optimized using the
central composite experimental design, by studying three
factors: the amount of sodium hydroxide, temperature, and
reaction time, aiming at extracting lignin in a highly efficient
way. The structure of the extracted lignin was characterized
with Fourier transform infrared spectroscopy (FTIR), 13C
nuclear magnetic resonance (13C NMR), UV-visible
spectroscopy, thermogravimetric analysis (TGA) and derivative
thermogravinometric (DTG).
II. EXPERIMENTAL
A. Raw naterials
Sugarcane bagasse was obtained from a local supplier
(COSUMAR is a Moroccan group, a subsidiary of the National
Investment Company, specializing in the extraction, refining
and packaging of sugar in different forms. It is the only
Moroccan sugar bowl operator).
B. Extraction process
The method of separation of lignin is an alkali treatment which
consists to hydrolyze bagasse (5%) by hot water 60°C for a
period of 120 minutes in order to remove hemicelluloses. The
residue obtained is treated with sodium hydroxide (NaOH
15%). Then, the black liquor is recovered acidified with 5N
sulfuric acid H2SO4 to pH between 2 and 3. The precipitate
formed is washed, air dried, and then crushed in a mortar to
obtain a uniform powder.
C. Method of experimentally design
The central composite design (CCD) is an experimental design
used to achieve maximal information about a process from a
minimal number of experiments [25]. For k independent
variables was employed to design the experiments in which the
variance of the predicted response, Ŷ, at some points of
independent variables, X, is only a function of the distance
from the point to the design center. In CCD, the central
composite face centered (CCFC) experimental design was used
in this study to determine the optimal conditions and study the
effect of three variables. Sodium hydroxide weight (X 1),
temperature (X2) and reaction time (X3) are investigated as
independent variables and extraction yield as response. After
selection of independent variables and their ranges,
experiments were established based on a CCFC design with
three factors at three levels coded as -1, 0 and +1. The coded
and uncoded independent variables used in this study are listed
in table 1.
Table 1: Experimental ranges of the independent variables used
in the central composite face centered design for the lignin
extraction yield (Y%)
Factors Codes Levels
-1 0 +1
Volume of NaOH (ml) X1 15 25 35
Temperature (°C) X2 25 62.5 100
Reaction time (min) X3 30 75 120
In this study, a total of 16 experiments [consisting of 8 factorial
points, six star points and four replicates at the center points (in
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order to allow the estimation of pure error)] were carried out
and the total number of experiments were calculated from the
following equation 1 [26] :
N =2n + 2n + nc (1)
Where: N is the total number of experiments required; n is the
number of factors; and c is the number of center points.
In this study, the response was lignin extraction yield (Y%).
Each response was used to develop an empirical model that
correlated the response to the quantitative experimental
variables or factors for lignin extraction, using a second-degree
polynomial equation as given by equation 2:
Ŷ = β0 + β1X1 + β2X2 + β3X3 + β12X1X2 + β13X1X3 +β23X2X3 +
β11X12 + β22X22 + β33X32 (2)
Where β0 the constant coefficient, βi the linear coefficients, βij
the cross-product coefficients and βii is the quadratic
coefficients. The software JMP.7 was use d for the experimental
design, data analysis, model building, and graph plotting.
III. RESULTS AND DISCUSSION
A. Experimental Design
Preliminary experiments were carried out to screen the
appropriate parameters and to determine the experimental
domain. From these experiments, the effects of three variables
sodium hydroxide weight (X1), temperature (X2) and reaction
time (X3) are investigated on lignin extraction yield as
response. The experimental design matrix and the
corresponding experimental parameters and response value
were shown in table 2.
The sign and value of the quantitative effect represent tendency
and magnitude of the term’s influence on the response,
respectively. A negative sign in front of the terms indicates the
antagonistic effect; whereas the positive sign shows the
synergistic effect. The quality of the model developed was
evaluated based on the correlation coefficient value. The R
value for equation 3 was 0.9855. The R value obtained was
relatively high, indicating that there was a good agreement
between the experimental and the predicted values from the
model. The R2 value for equation 3 was 0.9714. This indicated
that 97% of the total variation in the extraction yield was
attributed to the experimental variables studied. From the
statistical results obtained, it was shown that the above model
was adequate to predict the extraction yield within the range of
variables studied.
The final empirical model in term of coded factors after
excluding the insignificant terms for extraction yield (Y %) is
shown in equation 3 :
Y% = 0.27 (± 0.004) + 0.03 (± 0.003) X1+ 0.04 (± 0.003)
X2 - 0.006 (± 0.003) X3 - 0.03 (± 0.003) X2X3 + 0.03
(± 0.005) X2 - 0.09 (± 0.005) X32 (3)
The measured responses can be plotted based on the responses
calculated by the model. For this, it is necessary to plot the
adequacy of the model. The plot of experimental and predicted
values of extraction yield (Fig. 1) from multiple linear
regressions showed a good fitting function.
Table 2: Central composite face centered experimental design
matrix of factors (X) and the response (Y) of lignin extraction
yield (%).
Observed yield
Run order X1 X2 X3
(%)
1 -1 -1 -1 14.49
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2 1 -1 -1 15.16 Table 3: Summary of ANOVA results of lignin extraction yield
3 -1 1 -1 27.92 (Y%)
4 1 1 -1 34.87
Coefficie Sun of Mean P-value
5 -1 -1 1 14.45 Term F-value
nt squares square *
6 1 -1 1 24.81
0.0000
7 -1 1 1 19.73 -
8 1 1 1 27.70 8
0.0113 <0.001
9 0 0 0 27.82 0.0000 -
6 *
0.27508 3 33.486
10 0 0 0 28.11 0.0220 0.0012
β0 0.03371 0.0000 3
11 1 0 0 31.91 6 *
β1 0.046965 3 64.997
12 -1 0 0 24.16 0.0004 0.0002
13 0 1 0 33.78 β2 -0.00641 0.0000 8
1 *
14 0 -1 0 28.12 β3 - 3 1.2108
0.0078 0.3143
β23 0.031219 0.0000 22.975
15 0 0 1 17.10 0 0.0030
β22 0.037450 4 8
16 0 0 -1 17.76 0.0037 *
β33 9 0.0001 10.896
0 0.0164
Residu - 3 3
0.0251 *
e 0.097724 0.0001 74.192
8 0.0001
Total - 3 3
0.0020 *
- 0.0003 -
4 -
4 -
0.0725 -
0.0008
4
2
* P-value < 0.05: significant
Figure 3: Shows the interaction between temperature (X2) and
reaction time (X3) at constant value of the sodium hydroxide
Figure 1: The predicted vs observed plot for lignin extraction volume X1 = 0 (Fig. 3a), and the interaction between sodium
yield (Y%) hydroxide volume (X1) and reaction time (X3) at constant value
of température X2 = 0 (Fig. 3b).
The ANOVA required to test the significance and adequacy of
the model is listed in Table 3. From this ANOVA, the model F-
value of 22.9259 implied that the model was significant. Values
of "probability > F" (is worth 0.0006) less than 0.05. In this
case, the linear terms (X1, X2 and X3), the squared terms (X22
and X32) and the interaction term (X2X3) were significant model
terms. The relationship between the response and experimental
variables can be illustrated graphically by plotting the response
values from the levels of variables simultaneously. The
topography of the response surfaces in three dimensions can
also be illustrated by lines isoresponse outline, which shows Fig. 1. Response surface plot of lignin extraction yield (y) as
curves of constant response of a twovariables. These plots were function of temperature (X2) and reaction time (X3) at X1=25
useful for studying the effects of changes in the factors studied ml (Fig. 3a), and as function of sodium hydroxyde volume (X 1)
in the field and, therefore, to determine the optimal and reaction time (X3) at X2 = 62.5 °C (Fig. 3b).
experimental conditions. Fig. 2 shows the interaction between
sodium hydroxide volume (X1) and temperature (X2) at The investigation of the theoretical model representing the
constant value of the reaction time X3 = +1 (Fig. 2a) and X3 = - polynomial regression of the extraction efficiency of lignin
1 (Fig. 2b). showed that if X1 = 25 ml, X2 = 97 °C and X3 = 75 min; the
value predict from the results using response surface model is
35%. The experimental checking in this point, i.e. under the
optimum reaction conditions such as: sodium hydroxide
volume = 30 ml, temperature = 25 °C and reaction time = 67
min with high lignin extraction yield 27%, confirms this result.
Lignin offer potential for several applications in the field of
biomaterials [20, 21]. They can, for instance, be used as green
components in thermoplastics or as reagents in polyurethanes,
polyesters, phenolic and epoxy resins. However, each
application requires that the lignin have specific structural
characteristics and levels of purity.
Figure 2: Response surface plot for the lignin extraction yield
(Y) as function of sodium hydroxyde volume (X1) and The chemical composition of sugarcane bagasse in the as
temperature (X2) at a fixed reaction time of X3 = 120 min (Fig. received condition along with that reported in the literature is
2a) and 30 min (Fig. 2b). shown in Table 4. The analyses were performed and the
reported values are expressed in relation to the dry weight of
raw bagasse. It can be seen that the lignin content (27 %)
obtained in the present study is comparable than that reported
by others for these type of fibers from Brazil and China [27,
28]. The other constituents are somewhat comparable giving
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the total mass balance of 99.5%. Density values of sugarcane
bagasse and extracted lignin were found to be 1.25 and 1.75
kg.m-3 respectively. High-density value in extracted lignin can
be explained by the elimination of cellulose and hemicellulose.
Table 4: Comparison of chemical composition sugarcane
bagasse of Moroccan with Brazil and China.
B. Charaterization of extracted lignin
a. Lignin acetylation
Lignin acetylation was carried out according to the published
method [29], this lignin sample (≈ 200 mg) was acetylated with
2-4 ml of acetic anhydride/pyridine (1:1, v/v) at room
temperature overnight in a 100-ml flask. Ethanol (50 ml) was
added and, after 30 min, the solvents were removed using
rotary evaporation. Repeated addition and removal (rotary
evaporation) of ethanol (five times) resulted in the removal of
acetic acid and pyridine from the sample. The precipitated
lignin acetate was collected after centrifugation and dried under
high vacuum for 24 h (> 75% recovery yield).
b. Chemical structure by FTIR analysis
The Temperature Programmed Reduction (TPR) of AlP and
SiP calcined at 400°C does not present any hydrogen
consumption indicating that AlP and SiP are irreducible in the
range of temperature studied. On the other hand, the TPR
spectra of MoAlP and MoSiP shown in Fig. 5, revealed that, at
temperatures higher to 500°C, three reduction peaks. The
consumption of hydrogen of the MoAlP and MoSiP are
summarized in Table 4.
The specter FT-IR of lignin isolated from sugarcane bagasse is
presented in Fig. 4. The absorption peak at ≈ 3426 cm-1
belonged to the stretching of O-H groups, inclusive of R-OH
and Ar-OH. Peaks appear at 2916 cm-1 may be attributed to the
C-H stretching in the lignin molecules. Aromatic skeletal
vibration bands (1597, 1512, and 1490 cm-1), ring breathing
bands (1365 and 1329 cm-1), and aromatic C-H deformation
bands can be seen for the lignin isolated from Moroccan
sugarcane. In particular, all bands characteristic of G units are
found markedly stronger (1512, 1256, and 1060 cm-1),
indicative of a predominance of G units in this lignin. At 1033
cm-1, the band mainly accounts for the C–H in-plane
deformation in syringyl unit. The presence of syringyl (S) and
guaiacyl (G) bands with absence of the band of hydroxyl
phenyl propane (H) at 1166 cm-1 in the spectra for lignin,
indicate that the lignin extracted from Moroccan sugar cane
bagasse is more similar to wood lignin than annual plant lignin,
which is normally HGS lignin [30]. Furthermore, the
absorption band observed at ≈1490 cm-1 confirms that lignin
polymer does not change significantly during the soda
extraction procedure [31]. After acylation, lignin becomes
soluble in many organic solvents such as dichloromethane,
acetone, THF, 1, 4-dioxane, DMSO. The spectrum of the
acetylated lignin clearly shows the complete disappearance of
the hydroxyl functions at 3490 cm-1 and the appearance of the
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C = O ester carbonyl band to 1751 cm-1. The two strong bands
at 1230 cm-1 and 1074 cm-1 correspond to C-O bonds aromatic
and aliphatic esters.
c. 13C NMR spectrometry
13C NMR spectrometry has frequently been used in lignin
structural studies at qualitative and quantitative levels. 13C
NMR spectra of bagasse lignin and lignin acetate were
illustrated in Fig. 5. In order to illustrate the distinct
attributions, the corresponding assignments identified for the
lignin are listed in Figure 6 according to the previous literatures
[32, 33].
Figure 4: FT-IR absorption spectra of (a) lignin isolated from
Moroccan sugarcane bagasse and (b) lignin acetate sugarcane
The near absence of typical polysaccharide signals between 90
and 100 ppm in the 13C NMR spectrum of lignin confirms the
absence content of associated polysaccharides in lignin. In
aliphatic region below 102 ppm, signals at 75.99, 74.47, 73.14
and 63.66 ppm are attributed to β-O-4’ linkage, which is shown
the most abundant linkage in lignin fractions. After acylation,
the signals centered at 169, 130 and 102 ppm are attributed to
the aromatic acetyl, C1 in syringyl β-O-4 and CH3 in acetyl
group, respectively. This observation is in agreement with the
results found with the FT-IR spectra, confirming the absence of
bands characteristic of the cellulose.
d. Scanning electron micrgraph (SEM)
The morphology of the solids surface was observed in scanning
electron micrograph (SEM) images of extracted lignin in
comparison with Moroccan sugarcane bagasse (Fig. 6). It
clearly appears that some modifications have taken place after
alkali treatment. Fig. 6a shows that the fibers of bagasse were
covered by lignin and hemicellulose thereby forming a complex
three-dimensional structure. The analysis of the obtained
picture from lignin (Fig. 6b) shows clearly a homogeneous
microstructure made up of layers of various sizes and forms.
This confirmed the removal of major parts of cellulose and
hemicellulose after alkaline treatment.
e. Thermal stability
Thermal stability of the bagasse and pure lignin derived from
bagasse (after removal of cellulose and hemicelluloses) were
investigated by the thermogravinometric method.
Thermogravinometric analysis (TGA) and first derivative
thermogravinometric (DTG) curves are presented in Fig. 7.
TGA curves reveal the weight loss of substances in relation to
the temperature of thermal degradation, while the first
derivative of that curve (DTG) shows the corresponding rate of
weight loss. The maximum rate of degradation of bagasse was
observed at around 320 °C (Fig. 7a) while that the rate of
degradation of the lignin derived from bagasse becoming
maximum at around 280°C (Fig. 7b). The thermal
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decomposition of lignin results from complex reactions, which
explains the various hypotheses found in literature [34]. The
results (Figure 7a) of the thermogravimetric analysis showed
that the first weight loss step occurs at ≈ 40 to 150 °C due to the
moisture of the sample and evaporation of absorbed water,
subsequently the second stage occurred at around 250 to 300 °C
could be ascribed to the degradation of carbohydrate
components of the lignin. Carbon monoxide, carbon dioxide
and methane are also formed [35]. Decomposition of aromatic
rings occurs around 400 °C [36]. Continuous heating leads to
saturation of aromatic rings rupture of lignin C-C bonds, CO2,
CO and gives structural rearrangements [37].
f. UV-visible spectroscopy and MALDI-ToF
UV-visible absorption measurements of lignin isolated from
bagasse was carried out using sodium hydroxide (1%) aqueous
solution. This solution dissolves the lignin. Spectra of lignin
and raw bagass are shown in Fig. 8. Lignin shows absorption
maxima at 280 nm [38].

Figure 5: 13C NMR spectra of the (a) lignin isolated from Moroccan sugarcane bagasse and (b) acetylated lignin

Figure 6: SEM images of (a) raw bagasse and (b) lignin isolated from bagasse.
MALDI-ToF is a soft ionization technique to obtain polymers
fragments of high molecular weight (m/z). The MALDI-ToF
spectrum were performed to analyze the obtained lignin and
have an information about it structure (Fig. 9). For analysis
the lignin, the samples were derivatized by acetylation. The
lignin acetate sample must be previously dissolved in an
organic solvent and then crystallized in a matrix. From a wide
range of available matrices is in the 2, 5-dihydroxybenzoic we
observed the most fragments derived from the lignin acetate.
The analysis was performed in positive mode. A sample of
lignin acetate was solubilized in MALDI-ToF analysis in
positive mode of the non-acetylated lignin suggested that the
structure of lignin was too fragile to get mass fragments
greater than m/z = 900 [39]. In our conditions, we observed on
the MALDI-TOF spectrum of acetylated lignin fragments
with mass (m/z) equal to 1325 (Fig. 9). Its abundance is low.
The improvement of the solubility of the lignin by acylation
yielded a mass fragment (m/z) of greater than 900 [40]. This
observation agrees with the results of the FTIR spectra, which
indicate that the lignin extracted from Moroccan sugar cane
bagasse is more similar to wood lignin than annual plant
lignin.

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Figure 7: TGA and DTG curves of raw bagasse and lignin
(recorded in air atmosphere).
Figure 8: UV-Vis absorption spectra of raw bagasse and
lignin. (a) Lignin powder, (b) Sugarcane bagasse wastes and
(c) lignin in sodium hydroxide (1%) aqueous solution
Figure 9: MALDI-ToF spectrum of lignin acetate derived
from Moroccan sugarcane bagasse
Based on the results of the FTIR analysis, 13C NMR and
MALDI-TOF we proposed certain chemical structures of
polymer fragments from the Moroccan lignin bagasse
(Fig.10).
Figure 10: Chemicals structures of the Moroccan lignin
bagasse polymeric fragments.
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CONCLUSION
Central composite face-centered design was successfully
employed to optimize the extraction process of lignin from
Moroccan sugarcane bagasse. The results showed that three
variables; extraction temperature, sodium hydroxyde volume
and reaction time have significant effect on lignin extraction
yield. The model established for this purpose explains up to
97% of the variance and thus adequately predicted the lignin
extraction yield within the range of variables studied. On the
optimum extraction condition, obtained from the results using
response surface methodology, the lignin extraction yiel was
35%. FT-IR spectroscopy, 13C NMR spectrometry and
MALDI-ToF spectroscopy characterization of the lignin
confirm that all the cellulose and hemicelluloses were
eliminated during the separation process and reveals that
lignin is mainly composed of G and S units and less free
hydroxyls and highlights the absence of residual sugars in
lignin. Furthermore, the lignin was analyzed by different
complementary analysis such as scanning electron
microscope, UV-visible spectroscopy, thermogravinometric
analysis (TGA) and derivative thermogravinometric (DTG).
References
[1] A. Pandey, C.R. Soccol, P. Nigam, V.T. Soccol, 2000.
Biotechnological potential of agro-industrial residues. I:
sugarcane bagasse. Bioresource Technology, 74, 69-80.
[2] D.R. Mulinari, H.J.C. Voorwald, M. Cioffi, M. Silva,
T.G.D. Cruz, C. Saron, 2009. Sugarcane bagasse
cellulose/HDPE composites obtained by extrusion.
Composites Science and Technology, 69, 214-9.
[3] J.M. Hernández-Salas, M.S. Villa-Ramírez, N.J.S. Veloz-
Rendó, K.N. Rivera-Hernández, R.A. González-César,
M.A. Plascencia-Espinosa, 2009. Comparative hydrolysis
and fermentation of sugarcane and agave bagasse.
Bioresource Technology, 100, 1238-1245.
[4] K. Hofsetz, M. A. Silva, 2012. Brazilian sugarcane
bagasse: Energy and non-energy consumption. Biomass
and Bioenergy, 46, 564-573.
[5] Cosumar Group is a leading upstream sugar aggregator
and contributes to the development of sugar sector with a
total dedicated areas of 90 000 ha over 5 regions from
Morocco: Doukkala, Gharb, Loukkos, Tadla, Moulouya.
80,000 farmers who work on producing sugar beet and
sugar cane that represents 10 million wordk days a year.
w.ww.cosumar.co.ma.
[6] D. Fengel, G. Wegener, 1989. Wood: Chemistry,
ultrastructure, reactions. New York: Walter de Gruyter.
[7] M. Ayyachamy, F.E. Cliffe, J.M. Coyne, J. Collier, M.G.
Tuohy, 2013. Lignin: untapped biopolymers in biomass
conversion technologies. Biomass Conversion and
Biorefinery, 3, 255-269.
[8] S. Sarkar, B. Adhikari, 2001. Synthesis and
characterization of lignin-HTPB copolyurethane.
European Polymer Journal, 37 (7), 1391-1401.
[9] R.W. Thring, P. Ni, S.M. Aharoni, 2004. Molecular
weight effects of the soft segment on the ultimate
properties of lignin-based. International Journal of
Polymeric Materials, 53, 507-524.
[10] C.A. Cateto, M.F. Barreiro, A.E. Rodrigues, 2008.
Monitoring of lignin-based polyurethane synthesis by
FTIR-ATR. Industrial Crops and Products, 27 (2), 168-
174.
[11] K.V. Sarkanen, H.L. Hergert, 1971. Classification and
distribution, in: K.V. Sarkanen, C.H. Ludwig (Eds.),
190
 International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333
www.ijtrd.com
Lignins: Occurrence, Formation, Structure and
Reactions, Wiley, New York, pp. 43-94.
[12] J. Zakzeski, P. C. A. Bruijnincx, A. L. Jongerius, B. M.
Weckhuysen, 2010. Chemical commodities from
biomass. Chemical Reviews, 110, 3552-3599.
[13] C. Crestini, A. Pastorini, P. J. Tagliatesta, 2004.
Metalloporphyrins immobilized on motmorillonite as
biomimetic catalysts in the oxidation of lignin model
compounds. Journal of Molecular Catalysis A: Chemical,
208, 195-202.
[14] W. A. Herrmann, T. Weskamp, J. P. Zoller, R. W.
Fischer, 2000. Methyltrioxorhenium: oxidative cleavage
of CC-double bonds and its application in a highly
efficient synthesis of vanillin from biological waste.
Journal of Molecular Catalysis A: Chemical, 153, 49-52.
[15] Y.L. Chung, J.V. Olsson, R.J. Li, C.W. Frank, R.M.
Waymouth, S.L. Billington, E.S. Sattely, 2013. A
renewable lignin-lactide copolymer and application in
biobased composites. ACS Sustainable Chemistry &
Engineering, 1, 1231-1238.
[16] E. Ten, W. Vermerris, 2015. Review: Recent
developments in polymers derived from industrial lignin.
Journal of Applied Polymer Science, 132, 42069- 42069.
DOI: 10.1002/APP.42069.
[17] C.A. Cateto, M. F. Barreiro, A. E. Rodrigues, M. N.
Belgacem 2011, Kinetic study of the formation of lignin-
based polyurethanes in bulk. Reactive & Functional
Polymers, 71, 863-869.
[18] S. Xiao, J. Feng, J. Zhu, X. Wang, C. Yi, S. Su, 2013.
Preparation and characterization of lignin-layered double
hydroxide/styrene-butadiene rubber composites. Journal
of Applied Polymer Science, 130, 1308-1312.
[19] A. Gandini, M.N. Belgacem, 2008. Lignin as components
of macromolecular materials. In: Belgacem, M.N.,
Gandini, A. (Eds.), Monomers, Polymers and Composites
from Renewable Resources. Elsevier, Amsterdam, pp.
243–271.
[20] J. Lora, 2008. Industrial commercial lignins: sources,
properties and applications. In: Belgacem, M.N.,
Gandini, A. (Eds.), Monomers, Polymers and Composites
from Renewable Resources. Elsevier, Amsterdam, pp.
225–241.
[21] M. Delmas, 2008. Vegetal refining and agrichemistry.
Chemical Engineering and Technology, 31, 792-797.
[22] S. Sahoo, M.Ö. Seydibeyoglu, A.K. Mohanty, M. Misra,
2011. Characterization of industrial lignins for their
utilization in future value added applications. Biomass &
Bioenergy, 35, 4230-4237.
[23] G.H. Delmas, B. Benjelloun-Mlayah, Y. Le Bigot, M.
Delmas, 2011. Functionality of w heat straw lignin
extracted in organic acid media. Journal of Applied
Polymer Science, 121, 491-501.
[24] J.C.D. Rio, J. Rencoret, A. Gutiérrez, L. Nieto, J.
Jiménez-Barbero, A.T. Martínez, 2011. Structural
characterization of guaiacyl-rich lignins in flax
(Linumusitatissimum) fibers and shives. Journal of
Agricultural and Food Chemistry, 59, 11088-11099.
[25] B. Yang, X. Liu, Y. Gao, 2009. Extraction optimization
of bioactive compound scrocin geniposide and total
phenolic compounds from Gardenia Garde
niajasminoides Ellis fruits with response surface
methodology. Innovative Food Science and Emerging
Technologies, 10, 610-615.
[26] R. Azargohar, A.K. Dalai, 2005. Production of activated
carbonfrom Luscar char: experimental and modeling
IJTRD | Jan-Feb 2017
Available Online@www.ijtrd.com
studies. Microporous and Mesoporous Materials, 85,
219-225.
[27] M-X. He, J-L. Wang, H. Qin, Z-X. Shui, Q-L. Zhu, B.
Wu, F-R. Tan, K. Pan, Q-C Hu, L-C. Dai, W-G Wang,
X-V. Tang, G. Q. Hu, 2014. Carbohydrate Polymers,
111, 645-654.
[28] R.J. Brugnago, K. G. Satyanarayana, F. Wypych, L. P.
Ramos, 2011. The effect of steam explosion on the
production of sugarcane bagasse/polyester composites.
Composites: Part A, 42, 364-370.
[29] K. Lundquist, 1992. Proton (1H) NMR spectroscopy. In
Methods in Lignin Chemistry; Lin, S.Y.; Dence, C.W.,
Eds.; Springer-Verlag: Heidelberg, Germany, pp: 242-
247.
[30] X.B. Zhao, L. Dai, D. Liu, 2009. Characterization and
comparison of acetosolv and milox lignin isolated from
crofton weed stem. Journal of Applied Polymer Science,
114, 1295-1302.
[31] H. Nadji, P.N. Diouf, A. Benaboura, Y. Bedard, B. Riedl,
T. Stevanovic, 2009. Comparative study of lignins
isolated from alfa grass (Stipa tenacissima L.).
Bioresource Technology, 100, 3585-3592.
[32] X.Q. Pan, D. Lachenal, V. Neirinck, D. Robert, 1994.
Structure and reactivity of spruce mechanical pulp
lignins: 13C NMR spectral studies of isolated lignins.
Journal of Wood Chemistry and Technology, 14, 483-
506.
[33] M.F. Peter, J.R. Arthur, J.E. Jiang, 1996. Chemical
structure of residual lignin from kraft pulp. Journal of
Wood Chemistry and Technology, 16, 347-365.
[34] J.J.M. Orfao, F.J.A. Antunes, J.L. Figueiredo, 1999.
Pyrolysis kinetics of lignocellulosic materials-three
independent reactions model. Fuel, 78, 349-58.
[35] D. Meier, O. Faix, 1999. State of the art of applied fast
pyrolysis of lignocellulosic materials a review.
Bioresource Technology, 68, 71-77.
[36] R.S. Rohella, N. Sahoo, S.C. Paul, S. Choudhury, V.
Chakravortty, 1996. Thermal studies on isolated and
purified lignin. Thermochimica Acta, 287, 131-138.
[37] M. Garcia-Perez, A. Chaala, J. Yang, C. Roy, 2001. Co-
pyrolysis of sugarcane bagasse with petroleum residue.
Part I: thermogravimetric analysis. Fuel, 80, 1245-1248.
[38] W. Hoareau, W. G. Trindade, B. Siegmund, A. Castellan,
E. Frollini, 2004. Polymer Degradation and Stability, 86,
567-576.
[39] JO. Metzger, C. Bicke, O. Faix, W. Fuszynski, R.
Angermann, M. Karas, K. Struptat, 1992. Matrix-assisted
laser desorption mass spectrometry of lignins.
Angewandte Chemie International Edition, 31, 762-764
[40] J.H. Banoub, M. Delmas, 2003. Structural elucidation of
the wheat straw lignin polymer by atmospheric pressure
chemical ionization tandem mass spectrometry and
matrix-assisted laser desorption/ionization time-of-flight
mass spectrometry. Journal of Mass Spectrometry, 38,
900-903.
191