08/10/2014

Abstract:

Introduction:
Sago palm (Metroxylon sagu) is known for high starch content and found abundantly in
Malaysia (particularly in Johor Bharu and Sarawak). Since it is a staple food source around the globe, an
increase in the cultivation of sago starch production leads to higher quantities of sago biomass which
could lead to environmental pollution. The lignocellulosic biomass from sago waste could be used
extensively in the energy industries, chemical and pharmaceutical due to its biocompatibility,
biodegradable and abundant in nature (Lynd et al., 2005). Lately, the use of polymer in pharmaceutical
science has provided great achievement in the design and development of drug delivery systems. The
sodium carboxymethyl cellulose (CMC) has provided a great usage in pharmaceutical industries due to
its characteristics such as highly insoluble in acidic condition, absorbent and hydropholic resulting in
excellent swelling properties and therefore the bioconversion of cellulose biomass to CMC is vital.
Sodium carboxymethyl cellulose provides a great pharmaceutical excipient for its excellent drug
dissolution and disintegration quality. However, the use of sodium carboxylmetyl cellulose from
lignocellulosic biomass in the pharmaceutical industry should meet pharmaceutical standards that should
be free from heavy metal and impurities.
Essentially, common source of commercial cellulose is synthesized from purified cotton linters
obtained from Gossypium species (Ohwoavworhua et al., 2009). The usage of fiber from biomass
sources in pulp preparation have provided a great impact in industrial application due to an increasing
demand for market pulp globally that leads to a fall in wood availability causes a great deal on the
importance in this field. Moreover, agricultural residues such as sago waste are outstanding materials to
substitute wood because they are plentiful, widespread and easily accessible (Pushpamalar et al., 2006).
Hence, utilizing sago biomass not only prevents environmental pollution but also economically
profitable for agricultural industries.

In the present work, we investigate sago biomass, an agricultural waste, as a source for
pharmaceutical grade cellulose. The effects of pulping methods (sodium hydroxide and multistage
pulping) and varying bleaching time on yield and the cellulose obtained was characterized using
FESEM, infrared spectroscopy (FTIR), X-ray powder diffractometer (X-RPD), differential scanning
calorimetry (DSC) and compared with commercial grade cellulose. The cellulose was used to produce
carboxylmethylcellulose (CMC). The optimized product has a large degree of substitution (DS) of 0.9.
Fourier Transform Infrared spectra (FTIR) were used to characterize the product and starting sago
cellulose. Digital photographs of sago waste and sago cellulose showed the expected rough woody
structure while that of the CMC generated from the pulp showed a smooth surface morphology. XRD
results shows cmpleat conversion of sago cellulose from crystalilline form to amorphous form in the
final product.
We conclude that peroxyacid chemistry coupled with chlorite bleaching will produce an effective
way to extract cellulose from sago waste. The extracted pulp was carboxymethylated by one step
esterification processes in water-isopropanol medium under similar conditions. The degree of
substitution (DS) of CMC was identified as dependent on the method of extraction. The clarity,
crystallinity, viscosity of CMC also depends on the treatment method.

3.1 Materials & Methods

3.1.1

Sample preparation

To obtain a 0.10.25-mm particle size dry sago biomass was ground {Borella, 1998 #1} and
passed through 100-m sieve and washed with 2 % non-ionic detergent to remove water soluble organic
compounds and dirt, which was then dried at 60 C for 12 h until constant weight was observed. Dried
sago biomass mainly composed of lignocellulose material was then subjected to resins extraction using
Soxhlet apparatus. The dried washed lignocellulose material was then subjected to DE-waxing protocol
for 24 h in 2:1 Chloroform:ethanol, then for 24 h in 100% ethanol. The sample is then oven-dried (60
C) and their dry mass and yield of extractive-free wood is determined.
The sample was then divided into bags and heat sealed, two bags were designated for each five
chemical treatments (Figure 1). 20 g of sample was used for all the batches during chemical processing.
All the chemical processes are toxic and were carried in a fume hood.
3.1.1.1 holo-cellulose and cellulose preparations
Samples in Treatments 1 and 2 were holocellulose were extracted by following the acedified
Sodium chlorite extraction {Pushpamalar, 2006 #2a}. DE-waxed sago lignocellulose biomass is added
to 640 ml of pre heated distilled water (70 C) along with 4 ml of glacial acetic acid (CH3COOH) and 6
g of 80 % sodium chlorite. (NaClO2). The mixture was then filtered in a well-ventilated fume hood using
a cheesecloth sieve and washed with approximately 2.5 L of distilled water. The white residue (sago
pulp) obtained was then dried to constant weight at 60 oC in an oven and yield was determined. The
dried holocellulose was ground using a stainless steel blender, followed by sieving. Then Peroxyformic
acid treatment (treatment 1) was then carried out for cellulose extraction {Dapa, 2000 #3} 20 g of dried
holocellulose was treated with 20 % formic acid and 10 % hydrogen peroxide at 121 C for 20 min.
Further bleaching processes using peroxide bleaching technique was equipped. Extracted cellulose fibers
were re-suspended in 10% of hydrogen peroxide at pH 11 for 90 min at 80 C at a 10 % pulp
concentration. The pH was adjusted with 10 % of sodium hydroxide. The cellulose content is then
determined according to Tappi Test Method (T 203 om-88).
3.1.1.2 Crude cellulose preparation using Peroxyformic acid

Treatment 3 crude cellulose is extracted from lignocellulose material using 90 % formic acid
with 4 % hydrogen peroxide the reaction was carried out at 80 C and pulp concentration was
maintained at 8 w/v. At the completion of 120 min, the crude cellulose was filtered and further washed
using 80% formic acid. Bleaching of crude cellulose was carried out using 5 % hydrogen peroxide at pH
11 for 90 min at 80 C. The pH was adjusted with 10% of sodium hydroxide.
3.1.1.3 Crude cellulose preparation using NaOH extraction.
Lignocellulose material was subjected to treatment 4 and 5 using 10 % H2O2 (100 ml) + 10 %
NaOH (100 ml). Digested at 121 C for 20 min. washed until clear filtrate was observed. Then ovendried (70 C) for treatment 4 acid digestion was performed using 20 % formic acid and 10 % hydrogen
peroxide was treated at 80 C for 3 hrs. Bleaching crude celluloses using Sodium chlorite (treatment 5).
20 g of crude cellulose was added to 640 ml of pre heated distilled water (70 C) along with 4 ml of
glacial acetic acid (CH3COOH) and 6 g of 80 % sodium chlorite. (NaClO2).

Holo cellulose used for further analysis

The yields of the methods were calculated from dry mass of the wood and the final cellulose.

3.1.2

Fourier transform infrared spectroscopy

The extracted pulp sample and formation of sodium carboxylmethylcellulose (Na CMC) polymer interactions was characterized by FTIR
spectroscopy using Varian 640-IR Fourier-Transform Infra-Red (FTIR) spectrophotometer. The scanning range was 400-4000 cm-1.

3.1.3

Bleached
Cellulose
(PEROXIDE BLEACHING)
Cellulose extraction
(acid
digestion)
Extracted cellulose fibers
re-suspended
of hydrogen
peroxide
at pHat11
at 60 oC. The pH was
20 %were
formic
acid and 10 in
% 10%
hydrogen
peroxide
was treated
80for
C90
formin
3 hrs.

Differential scanning calorimeter (DSC) investigations.

Melting and recrystallization behavior of the pulp samples could

be studied
using DSC.
DSC was (acidified
performed using
the DCS
220C calorimeter (Seiko
Bleached
Cellulose
extraction
Sodium
Chlorite)
DE-waxed
sago lignocellulose
is added
to 640
pre heated
C) along
4 mlrecords
of glacial
acid
(CH3COOH)
and 6
Instruments,
Japan). Pulpbiomass
samples are
examined
usingml
anof
empty
standarddistilled
aluminumwater
pan as(70
reference.
DSCwith
scanning
wereacetic
done at
a heating
and
cooling rate of 5 K/min.
Cellulose extraction (Peroxyformic acid treatment)

20 % formic acid and 10 % hydrogen peroxide was treated at 121 C for 20 min.

3.1.4

HPLC analysis.

Crude cellulose (acid digestion)

Cellulose samples (160 mg) from all the20different

methods
were
to HLPC
analysis
identifyatthe
presence
xylose,
% formic
acid and
10subjected
% hydrogen
peroxide
wastotreated
121
C for of
20 glucose,
min.
arabinose and lignin according to the National Renewable Energy Laboratory (NREL) procedure (Sluiter et al., 2008). The samples (160 mg) were
treated with 72% (w/w) H2SO4 1.5 mL at 30C for 1 h. The solutions were adjusted to 4% (w/w) H2SO4 with 42 mL of water and autoclaved at 121C
for 1 h. The hydrolysate was separated into the acid insoluble residue fraction and the filtrate fraction. The latter fraction was neutralized with barium
hydroxide (Ba(OH)28H2O), and then analyzed for sugar contents of the pretreated solid fraction with HPLC analysis used a Bio- Rad HPX-87H
organic acid column (Bio-Rad Laboratories Inc., Hercules, CA).The acid insoluble residue fraction was dried overnight at 105C and weighed.
DE-waxed sago lignocellulose biomass (20 g) is added to 10 % H2O

The sample was thereafter incinerated in the muffle furnace at 550C for 24 h to determine the ash content. The acid insoluble lignin content was
determined as the weight of the acid insoluble residue subtracted the ash content. The column temperature was fixed at 65C using 5 mM H2SO4 as
mobile phase at a flow rate of 0.6 ml/min and detected with an refractive index (RI) detector (Waters 2414) at 40C (Sluiter et al., 2012). All samples
were filtered through a 0.45-m filter prior to sample injection. All analytical determinations were performed in duplicate.

3.1.5 Determination of types of cellulose in the sample.

Extracted cellulose fibers were re-suspended in 10% of hydrogen

Crude Cellulose Extraction

(NaOH extraction)
(100 ml)+ 10 % NaOH (100 ml). Digested at 121 C for 20 min. washed until clear filtrate was observed. Th

their dry mass and yield of-cellulose determined.

T 203 cm-99 method was used to determine the cellulose content. In a 300-ml tall-form beaker, take 75.0 ml of 17.5 % NaOH (25 C). The 1.50
g of oven-dried pulp sample was added and stirred until complete dispersion was achieved. Add 25 ml of 17.5 % NaOH (25 C). The total reaction
medium was placed in a water bath at 25 C. After 30 min 100 ml of D.H20 was added and incubated for 30 min. Later the sample was filtered.
To determination Alpha-cellulose, to 25 ml of filtrate 10.0 ml of 0.5 N potassium dichromate solution was added fallowed by 50 ml of
Con.H2SO4. The reaction was incubated for 15 min and 50 ml D.H 20 is added. Ferroin indicator was added and titrated with 0.1N ferrous ammonium
sulfate to turn purple. Blank titration of the filtrate is done using 12.5 ml of 17.5 % NaOH and 12.5 ml of water.

To determination Beta- and gamma-cellulose, to 50 ml of filtrate add 50.0 ml of 3 N H 2SO4 placed it in a water bath at 70-90C for a few
minutes. Beta-cellulose coagulates, and centrifuged at 1000 g for 5 min. To the clear supernatant add 10.0 ml of 0.5 N K 2Cr2O7 and 90 ml Con. H2SO4
and titrated with 0.1 N ferrous ammonium sulfate to turn purple. Blank titration of the filtrate is done using 12.5 ml of 17.5 % NaOH, 25 ml of 3 N
H2SO4 and 12.5 mL of water.
7.5 % and 9.45 % sodium hydroxide solution in the test solution does not have any reaction on Alpha-cellulose is the pulp fraction. The soluble
fraction contains the Beta-cellulose that can be precipitated by changing the pH of the medium to acidic. The fraction that remains unreacted is the
gamma-cellulose.
Calculate the alpha-cellulose content in pulp:
Alpha-cellulose, % = [6.85 (V2 - V1) N x 20] /[100 - A x W]
Gamma cellulose, % =[6.85 (V4 - V3) x N x 20] / [25 x W]
Beta-cellulose, % = [100 x (alpha-cellulose % + gamma-cellulose %)]
Where,
V1 = titration of the pulp filtrate, mL
V2 = blank titration, ml
V3 = titration of the solution after precipitation of beta-cellulose, ml
V4 = blank titration, ml

n oven-dried (70 C)

N = exact normality of the ferrous ammonium sulfate solution

A = volume of the pulp filtrate used in the oxidation, ml

3.1.6

Degree

of

swelling

for

alkaline

cellulose.

Analyzing thermogravimetry of the sample saturated with water identified the degree of swelling in
water for cellulose samples. Pulp sample was treated with 10 % NaOH for about 1 hr and the sample
was then neutralized with dilute HCl. The sample was then filtered and water retained by the cellulose is
determined by TGA analysis. Temperature was increased from 40 to 130 C at a heating rate of 5
C/min, and was kept at 130 C for 30 min.

3.1.7

X-Ray Diffraction analysis (XRD)

The extracted cellulose was investigated using X-ray diffractometer (D8-Advance Bruker-AXS) to
understand the phase behaviour. The instrumental settings were set at 1.540oA wavelength (CuK
radiation), with a scan speed of 2o per second and a 2 range of 2-30 o. CIr, crystallinity index was
calculated for all the cellulose samples.
CIr = [(I002-Iam/I002)] 100
The highest peak intensity (I002) is the crystalline fractions and the low intensity peak (I am) is for
amorphous region. Scherrers equation was used to determine the crystallite size (Patterson 1939),
D = K / cos
where,

K is the constant 0.91

is Braggs angle

is the intensity of the full width at half of the maximum (FWHM) corresponding to a high
intensity peak.

3.1.8

ISO Brightness

ISO brightness measurements were performed using TAPPI Standard ISO-3688-1999. Pulp was dried
and three replicates were performed.

3.1.9

Characterization of sodium carboxymethyl

cellulose
3.1.9.1 Determination of degree of substitution.
The moisture content, degree of substitution (DS), and purity of NaCMC were determined by the ASTM
D1439-94 standard method (ASTM., 1994). The water holding capacity was detected by the method of
(Larrauri et al., 1996). The degree of substitution was calculated using equation (E1) as fallowing
(Pushpamalar et al., 2013).

A=

BCDE
F

Degreeof substitution=

(0.162) A
1(0.058 A) (E1)

Where:
DS
A
B
C
D
E
F
162
58

=
=
=
=
=
=
=
=
=

Degree of Substitution
Mili-equivalents of consumed acid per gram of specimen
Millimeters of added sodium hydroxide
Normal sodium hydroxide
Millimeters of consumed hydrochloric acid
Normal hydrochloric acid
Specimen gram used
Molecular weight of the anhydrous glucose unit
Net increment in the anhydrous glucose unit for every substituted carboxymethyl group

10

3.1.9.2

Determination of viscosity.
To determine the viscosity of Na-CMC solutions, 2% (w/w) sample is prepared in distilled water. The
viscosity is measured using Brookfield viscometer. The temperature is maintained constant at 30C.
Magnetic stirrer is used to stir the solution that assures all the material soluble (1 to 3 hr). When
complete solubility is attained the spindle is inserted immediately into the solution. Start the rotor for the
spindle and take the reading after about 3 min.

3.1.9.3 To determine the solubility

Weigh 1 g of the NaCMC residue and dissolve in 100 ml of distilled water, the mixture is vigorously
agitated under increasing temperature conditions for up to 80 C for about 30 min. the sample is then
centrifuged at 6000 g for about 30 min. The supernatant is then transferred on a petri dish and dried at
105 C for 24 hr. the solubility percentage is calculated by the weight difference after complete drying of
the sample(Lawrence and Rees, 2000).

3.2 Result

3.2.1

Fourier

transform

infrared

spectroscopy
In Figure 3.2, the structural characterizations of all pulp samples were evaluated and the typical
functional groups were identified. The presence of lignin, hemicellulose and cellulose were
acknowledged by the presence of the main characteristics. In general, the FTIR studies for the
chemically modified pulp showed that the most prominent peaks in the spectrum is from OH stretching
vibration in cellulose representative in the 3200-3600 cm-1 range. At the range of 2,887-2933cm-1, the
absorption band noticed is associated to the axial deformation of C-H group. This vibration is expected
from hemicellulose,
cellulose
and lignin in the pulps.
METHOD
1
METHOD
METHOD
METHOD
METHOD

3600

2
3
4
5

3200

2800

2400

1735

2000

1600

1248

1200

800

11

Figure 3.1: FTIR spectrum for cellulose sample using different methods.
According to Sain and Panthapulakkal, 2006 the peak centered at 1700-1736 cm -1 could related to the
acetyl and uronic groups of hemicellulose or the ester linkage of carboxylic group of ferulic and pcoumaric acids of lignin and/or hemicellulose. This could be seen in all methods except method 1. It was
also stated that 1705 cm-1 is from unconjugated ketone or carbonyl stretching, while a shoulder at 1638
cm-1 is attributed to carbonyl stretching with aromatic rings (Cite). Several intense peaks occurred in the
region range of 1651-1594cm-1 which could be from the stretching mode of aromatic skeleton vibrations.

The table represcents the peaks present in different samples:

3376

2970

2905

1731

1642

1421

1360

1248

1033

874

760

724

M
ethod 1
M
ethod 2
M
ethod 3
M
ethod 4
M
ethod 5

12

Key: -Present -Absent

Table 3.1: FTIR spectrum peaks for cellulose sample using different methods.
In Figure 3.1, the structural characterizations of all pulp samples were evaluated and the typical
functional groups were identified. The presence of lignin, hemicellulose and cellulose were
acknowledged by the presence of the main characteristics. In general, the FTIR studies for the
chemically modified pulp showed that the most prominent peaks in the spectrum is from OH stretching
vibration in cellulose representative in the 3200-3600 cm-1 range. At the range of 2,887-2933cm-1, the
absorption band noticed is associated to the axial deformation of C-H group. This vibration is expected
from hemicellulose, cellulose and lignin in the pulps.
According to Sain and Panthapulakkal, 2006 the peak centered at 1700-1736 cm -1 could related to the
acetyl and uronic groups of hemicellulose or the ester linkage of carboxylic group of ferulic and pcoumaric acids of lignin and/or hemicellulose. This could be seen in all methods except method 1. It was
also stated that 1705 cm-1 is from unconjugated ketone or carbonyl stretching, while a shoulder at 1638
cm-1 is attributed to carbonyl stretching with aromatic rings (Moore and Owen, 2001). Several intense
peaks occurred in the region range of 1651-1594cm-1 which could be from the stretching mode of
aromatic skeleton vibrations.
A very large difference was noticed in the fingerprint region (1800-800cm -1) and this could indicate a
group of IR absorbance of lignin that shows lignin is rich of methoxyl-O-CH3, C-O-C stretching and CC stretching (aromatic ring) containing compounds. According to Moore and Owen 2001, prominent
peaks appear at around 1245 cm-1 and 1532 cm-1 represents the most characteristics bands of lignin that
represents C-H and O-H bending frequencies. These bending frequencies were seen in all method except
in method 1. This indicates that the pulp obtained after H 2O2 hydrolysis in method 1 eliminates
hemicellulose and lignin from the biomass fibers during chemical extraction.
The band at a range of 1423 - 1433cm-1 indicates symmetric deformation of CH2 group of cellulose and
this were seen in all the methods conducted. The band at 1200 cm -1 is in connection with asymmetric
deformation of C-O-C of the cellulose, hemicellulose and lignin.

13

The band at about 1640 - 1651 cm-1 is assigned to the absorbed water however, the small peak occurred
at 1593cm-1 in method 2, may be due to water but it can be seen that the peak disappears in method 1.
This could be due to aromatic C=C stretch of aromatic ring in lignin as this particular peak vanishes in
other spectra of method 1, 4 due to the removal of lignin. The peak at about 1,059- 1051 cm-1 and 779809cm-1 was associated with the C-O stretching and C-H rock vibration of cellulose which appears in all
of the spectra.

3.2.2

Swelling of cellulose

Efficient conversion of cellulose to any chemically modified derivatives can only be achieved by
changing the crystalline structure of cellulose. this can be achieved chemically by forming swelled
structures of cellulose. this helps the reagents to penetrate the cellulose very easily and thus it becomes
easier to substitute the hydroxyl group of the anhydrous glucose unit. Treatment with concentrated
NaOH will increase the reactivity of cellulose to undergo chemical reaction when compared with
untreated cellulose. During the alkalisation processes small oligosaccharides are also derived from the
cellulose samples, which are not removed from the reaction medium. these will also undergo chemical
modification through out the processes and thus results in affecting the properties of the final product.

3.2.3

Diffraction analysis (XRD)

Cellulose molecules were arranged in a regular faction and linked by hydrogen bonds, which gives them
a crystal-like property. Cellulose exhibits monoclinic crystalline lattice. In native cellulose it is seen that
crystallite measure about 100-125 nm and several crystallites form a cellulose molecule. The
crystallinity of cellulosic fibers is affected by chemical and mechanical treatments. The amorphous
region is dissolved by diluted acid treatment and crystalline region is resistant to the treatment (Fengel
and Wegener, 1984).
The ratio of diffraction portion of the crystalline region (Ic) and total diffraction from the sample (Ic+b) is
a common method of measuring crystallinity. Where background (Ib) is substracted to obtain the value of
Ic.
C % = (Ic / Itotal) 100
where Itotal = Ic + Ib.

14

Figure 3.2: XRD spectrum for cellulose sample using different

methods.
General Area Diffraction Detection System (GADDS), was equipped using D8 Discover X-ray
Diffraction System to calculate the percentage crystallinity (%) and amorphous region of the sample.
The peak and background area is maintained constant for all the samples. The powder X-ray diffraction
(PXRD) patterns for treated and untreated cellulose samples as shown in figure 3.2.
The sharp peak at 2 = 22.5 is more sharper for cellulose from method 1 than untreated and
cellulose from method 2-5. The percentage crystallinity was estimated to be 79.8 % for method 1 and
56.5%, 54.8%, 57.8%, and 60.6% for method 2-5. In all the samples the crystallinity index was seen to
be higher than un-treated sago fibers due to the partial removal of hemicellulose and lignin by various
chemical treatments. It is also clearly seen that high the crystallinity (%) higher the rigidity of cellulose
fibers thus expected to have higher tensile strength and change in mechanical property of the cellulose
fibers.
3.2.4

TGA
The TGA curves cellulose, hemicellulose and lignin are shown in Figure 3.4 for all samples of method
1-5. There were several obvious differences were found among these samples. It was found that
humidity was removed around 100C and hemicellulose for sample method 2 started its decomposition
easily, with the weight loss mainly happened between 200-300C. The maximum weight loss rate (0.20
wt.%/C) took place at 268C. As for sample method 1,3,4,5, no hemicellulose decomposition was
noticed. This indicates that this particular method has significantly removed the presence of
hemicellulose in the sample. At a higher temperature range of 315-400C, cellulose was seen to

15

decompose with the maximum weight loss rate (0.8 wt. %/C) attained at 355C, providing mainly
volatile products.
The decomposition process of lignin covered larger temperature range, between 250 and 600C.When
temperature was higher than 400C, almost all cellulose was pyrolyzed with a very low solid residue
(0.1wt%/C) left. Lignin was the most difficult one to decompose. Its decomposition happened slowly
under the whole temperature range from ambient to 900C, but at a very low mass loss rate (<0.14 wt
%/C). The solid residue left from lignin (45.7 wt.%) was the highest. The differences in the inherent
structures and chemical nature of the three components possibly account for the different behaviors
observed. Hemicellulose is consisted of various saccharides (xylose, mannose, glucose, galactose, etc.),
it appears a random, amorphous structure, rich of branches, which are very easy to remove from the
main stem and to degrade to volatiles evolving out (CO, CO2, and some hydrocarbon, etc.) at low
temperatures.

120

METHOD 1
METHOD 2
METHOD3
METHOD 4
METHOD 5

100
80
60
40

WEIGHT (%)
20
0
200

400

600

800

600

TEMPERATURE (C)

16

Figure 3.3: TGA analysis for cellulose sample using different methods.
3.2.5

FESEM
The FESEM of extracted cellulose samples clearly shows compact fibril packed in the composite. When
comparing method 1 to method 2-5, it is clearly seen that method 1 samples exhibits isolated fibrils
separated, which explains complete removal of cementing wax, hemicelluloses, and lignin.
Distinguishing fibrils separation is not seen is not clearly visible in other methods. This could because of
irregular deposition of hemicellulose, lignin, wax and other inorganic components like Na, Mg, K, Ca,
S, Al, Si. This is also supported by EDX spectrum (Data not shown).

3.2.6

Degree of substitution, purity and molar mass distribution

17

The primary venture in the carboxymethylation is the formation of alkali cellulose, which
modies its crystalline structure and expands its availability to chemicals by swelling. Cellulose could
be swollen in concentrated NaOH yet not broken up. Be that as it may, smaller oligosaccharides and
other low molar mass segments are extracted from cellulose by soluble alkaline treatment. Since they are
not expelled from the reaction media, these salt extractives will be additionally etheried, yielding low
molar mass subsidiaries that may influence the properties of the cellulose subsidiary (Meltzer 1976).
Table demonstrates the solubility of our cellulose pulps in 20% NaOH.
Cellulose sample

Swelling degree (g Swelling degree after

Solubility in 20%

H 2O/100 g of dried being alka- linized (g

NaOH (%)

matter)

3.2:

H 2O/100 g of dried

matter)
METHOD 1
83.9
88.78
METHOD 2
81.5
84.3
METHOD 3
77.2
74.2
METHOD 4
78.5
80.2
METHOD 5
75.3
78.1
Swelling and solubility ratio of cellulose in NaOH and water.

Table

3.1
15.2
8.1
9.2
7.2

Table 3.3: Cellulose composition using standard methods.

18

CELLULOSE

STANDARD

COMPOSITI
Lignin (%)
Organic

METHO

METHO

METHO

METHO

METHO

METHOD
D1
TAPPI T 15 os- 0.56
ASTM
D- 1.23
80

D2
5.2
1.34

D3
4.58
1.27

D4
10.26
1.15

D5
3.6
1.34

extractives (%)
-Cellulose (%)
ISO brightness
Intrinsic

110784
TAPPI
93.6
ISO3688-1999 94.6076
ISO
5351- 1400

70.4
90.1
525600

90.8
86.85
600850

92.6
88.77
550610

87.8
80.03
700

viscosity
Crystallinity
Residual

11998
X-ray
HPLC

1650
0.63
10.38

0.59
5.17

0.64
7.09

0.63
6.53

0.45
8.80

pentosan
Total yield %

HPLC

5.38

10.17

7.09

3.53

8.80

19

3.3 Conclusion

20

The experimentally analysis f o r t h e d i f f e r e n t m e t h o d s o f c e l l u l o s e e x t r a c t i o n

f r o m s a g o w a s t e is reported. It is evident that method 1 two-step extraction processes (Sodium
chlorite and performic acid) so for the b e s t

protocol

investigated to study produce

pharmaceutical grade cellulose. The obtained XRD data, suggests that the crystallinity of the
cellulose sample from method 1 is higher that all the other methods this suggests that the
cellulose obtained is highly pure with no or less contaminations . It was found from the TGA
results that method 2 contained considerable amount of hemicellulose that was not removed
and method 4 had presence of lignin in a detectable concentration. All the other methods either
did not have or it is under the detection limit. The samples were subjected to standard method to
determine the lignin% it was found that method 1 was the lowest among them and method 4 was the
highest with correlates to the TGA results. There was presence of lignin in all the other methods that
might affect the cellulose quality causes the production of byproducts during chemical conversion to
form cellulose derivatives. Owing to cellulose swelling ability to form alkaline cellulose, it is evident
that cellulose obtained from method 1 showed more swelling rate. Moreover the solubility in 20%
NaOH was also less which states there is less presence of non-celluloid material and method one can
undergo better conversion to produce carboxymethyl cellulose. Which is supported by the FTIR
spectrum obtained for all the cellulose samples. It was found that the brightness of cellulose from
method 1 was higher than all the other method.
When analyzing the carboxymethyl cellulose derived from cellulose from all the five methods 1-5 it is
observed that the reaction rate is higher when converting cellulose form method 1 and least with
method 2. This is because of the presence of other substances that prevent the reaction from taking
place. The solubility of the carboxymethyl cellulose is found to be 100% with cellulose from method
1.
It was found that the viscosity also differed between the samples produced and sample produced
from cellulose using method 1 had exhibited the higher viscosity. The investigated systems were
related to the solubility, clarity, crystallinity and degradation temperature of the relevant samples.
Solubility decreases with increasing number of contaminants in the cellulose and in the case of
samples prepared using method 1 showed the highest viscosity. The degradation temperature data
demonstrate that, there is a slight reduction when compared to the cellulose sample. Based on the

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EDX and XRD, it can be concluded that the cellulose in all the method showed
crystallinity and carboxymethyl cellulose showed to be amorphous. When comparing
the different methods it as concluded that there was complete conversion of crystalline cellulose to
amorphous carboxymethyl cellulose was observed. Which was not seen in other four methods (2-4).
There was also no presence of any heavy metals in all the samples except method 2. Since method 1 is
also considered to be an ecofriendly extraction method. Owing to its oxidizing and disinfecting action,
it is used in the chemical, medical and food industries. Performic acid is an organic compound with
the formula CH2O3. It is an unstable colorless liquid, which can be produced by mixing formic acid
with hydrogen peroxide. Owing to its oxidizing and disinfecting action, it is used in the chemical,
medical and food industries. hydrogen peroxide. Owing to its oxidizing and disinfecting action, it is
used in the chemical, medical and food industries. Sodium chlorite, which is used to generate chlorine
dioxide used for bleaching and stripping textiles, pulp, and paper. It is also used for disinfection of
municipal water treatment plants after conversion to chlorine dioxide.

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