Proceedings of the National Engineering Research Symposium (NERS 2020),Vol 1, pp. [13–20], 2020.

c National Engineering Research and Development Centre of Sri Lanka.

Processing of Sodium Carboxymethyl Cellulose from bagasse

T N Fernando1 , Y M M K Ranathunga2

Abstract

CarboxyMethylCellulose (CMC) is one of the derivatives of cellulose and linear, long chain,
water soluble, anionic polysaccharide. CMC is prepared by substitution of MonoChloroacetic
Acid (MCA) or its sodium salt (NaMCA) to hydroxyl groups in cellulose Anhydroglucose
units. The protocol of processing of CMC/NaCMC consists mainly of two steps. First step
is Mercerization with aqueous sodium hydroxide at room temperature and the second step is
Etherification with MCA/NaMCA for 3 12 hours at 600C. The present study focused on the
preparation of NaCMC for non-food applications using bagasse as a raw material to extract
cellulose from alkaline hydrogen peroxide pre-treatment and use of ball mill technique for
etherification. Fourier Transform Infrared (FTIR) spectroscopy was used for confirmation of
the developed product. Water soluble and color of developed products were observed. Degree
of substitute (Ds) and active matter content were measured using IS3520 methods. The
results of FTIR analysis confirmed that the developed product was NaCMC. The average
(Ds) values was 0.25 and active matter contents was 38%. Water solubility was 69.5 g/l
and processed products has off-white in color. The results indicated that NaCMC could be
processed using pre-treated bagasse from alkaline hydrogen peroxide pre-treatment without
mercerization and balls mill technique is eliminate the use of an external heat source required
for etherification to produce NaCMC. Further, developed NaCMC samples could be used to
process detergent grade NaCMC by exploiting such improvements of increasing Ds up to 0.4
and active mater content is 40%.

Keywords: Sodium carboxyl methyl cellulose, Bagasse, Ball mill

1. Introduction polysaccharide [1] (Figure 1a). CMC is pre-

pared by substitution of MonoChloroacetic
CarboxyMethylCellulose (CMC) is one of the Acid (MCA) or its sodium salt of sodium
major ingredients widely used in different MonoChloroacitic Acid (NaMCA) to hydroxyl
non-food industries. Non-food applications groups in cellulose Anhydroglucose (AGU)
of CMC includes its usage in formulations units (Figure 1a and 1b). The average num-
for cleaning products such as detergents and ber of carboxymethyl groups per one AGU
co-binders for paper making, formulation of group of cellulose is defined as the Degree of
oil drilling solvents and in some textile and substitution (Ds ).
cosmetic industries. CarboxyMethylCellulose
(CMC) is one of the derivative of cellulose The manufacturing process of NaCMC
and linear, long chain, water soluble, anionic (Chemical structure, Figure 1c) consists
mainly of two steps. The first step is Mer-
1 National Engineering Research and Development
cerization with aqueous sodium hydroxide
Centre, nilanthi@nerdc.lk
2 National Engineering Research and Development (NaOH). In this step, aqueous NaOH and cel-
Centre, malini1@nerdc.lk lulose are mixed for 1 hour at room tempera-

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 Figure 1: (a) Chemical structure of Cellulose [2] (b) Mechanism of substitution
(c) Chemical structure of NaCMC [3]
ture to facilitate the penetration of NaOH to
the structure of cellulose and hydroxyl groups
make available for the second step of Ether-
ification reaction by breaking the hydrogen
bonds [4]. The second step is Etherifying
with MCA/NaMCA. In the Etherification pro-
cess, alkali cellulose from Mercerization is re-
acted simultaneously with MCA/NaMCA for
3 12 hours at 600C to form CMC/NaCMC. Ad-
ditionally, two by-products of sodium glyco-
late and sodium chloride are produced [5].
Accordingly, cellulose is one of main raw ma-
terial is required for the processing of NaCMC.
Cotton is the naturally available cellulose and
it’s not abundantly available in Sri Lanka.
However, some agro plant wastes such as corn
husks, corn leaves, baggase, sugarcane leaves
and gunnia grass are reach of cellulose and
abundantly available material in Sri Lanka [6].
Baggase is selected to process NaCMC due
to low chlorophyll and cell pigments in plant
14
cells. Also this is a suitable for preparing of
pure NaCMC with recommended colour.
Pre-treatment methods are necessary to re-
move or alter the lignin. Researchers have
shown that alkaline hydrogen peroxide appli-
cation at atmospheric pressure and room tem-
perature is an effective pre-treatment method
for solubilizing lignin and improving digestibil-
ity than alkaline and mild pre-treatments [6].
In industry, CMC/NaCMC is prepared by var-
ious methods, which include fluidized bed
technique, sheet carboxymethylation, rotating
drum technique, solvent-less method using a
double screw press and paddle reactor etc. [3].
The present study focused on processing
NaCMC for industrial applications using cel-
lulose extracted from bagasse applying alka-
line hydrogen peroxide pre-treatment and in-
troduce ball mill techniques for etherification.
Several studies have used rotating drum tech- value as 1 for the developed NaCMC.
nique for processing of NaCMC [7, 2]. Fur-
thermore, the mentioned details in [7] is in- Calculation of weight of NaMCA
sufficient to compare with results indicated by Cellulose+NaOH +NaMCA ⇒ [NaCMC]+HO−CH2COONa+
[2]. However, the report published by [2] has NaCl (1)
allowed generation of heat from the impact of 1mol 1mol (Ds=1)
ceramic balls on the walls of a rotating drum
for an etherification process without further
use of an external heat source. (Molecular weight of cellulose, NaOH and
NaMCA are 162 kg mol −1 , 40 kg mol −1 and
2. Methodology 116.5 kg mol −1 respectively).
2.1 Materials A prepared alkaline cellulose sample has cel-
lulose and NaOH. 1 kg of cellulose was mea-
Industrial grade Sodium hydroxide (NaOH),
sured by subtracting of NaOH weight ob-
Hydrogen peroxide (H2 O2 ) and Sodium
tained from titration test.
MonoChloroacetic Acid (NaMCA) were pur-
chased from Glorchem Enterprise in Sri Lanka. Mole quantity of cellulose sample
Required cellulose for the experiment was ex-
tracted from bagasse, which was discarded = 1kg/162kgmol −1
from Pallawatta Sugar Industry in Sri Lanka. = 0.006173mol
A Ball mill is placed at the Industrial Institute
of Technology in Sri Lanka was used for the According to the balanced equation, one mole
processing and it has rpm 350. of NaMCA is reacted with one mole of cellu-
lose.
2.2 Extraction of cellulose
The required weight of NaMCA with Ds 1 was
The cellulose sample from bagasse was ex- obtained according to the balanced equation,
tracted using alkaline peroxide pre-treatment
= 116.5 × 0.006173 × 1
as details mentioned in the report of [6].
= 719.15g ' 720g
2.3 Determination of weight of NaOH in al-
kaline cellulose sample
2.5 Processing of NaCMC
The weight of NaOH in pre-treated alka-
line cellulose sample was measured following 1 kg of cellulose extracted from bagasse, 720g
the titration method. Half gram (0.5g) of of NaMCA, a certain amount of water and
three alkaline cellulose samples were added ceramic balls were added to the ball mill as
separately into containers (25 ml) in inside shown in Figure 2 and it was allowed to rotate
the centrifuge. Prepared samples were cen- for 31/2 hours. The inside temperature was
trifuged 1 h under 3500 rpm speed. Cen- measured at the end of the process using a
trifuge samples were titrated adding phe- digital thermo sensor. Finally, the developed
0
nolphthalein as an indicator and 1mol/L HCL. product was dried at 60 C until a constant
According to the volume of HCl required for weight was obtained and pulverized.
the neutralization, the weight of NaOH in al-
2.6 Characterization of developed products
kaline cellulose sample was determined.
2.6.1 Fourier Transform Infrared Spec-
2.4 Determination of weights of raw mate-
rials require for the experiment troscopy (FTIR)

Weights of raw materials required for the Developed NaCMC samples and the recom-
processing were calculated by considering Ds mended NaCMC sample available in export
markets were analyzed in Fourier Transform

15
Infrared spectroscopy (FTIR). Comparison of of 152g of NaOH.
wavenumbers of graphs, which were obtained
from FTIR spectra and products indicated by 3.2 FTIR Analysis for native bagasse and ex-
tracted alkaline cellulose
[8] was used to confirm that the developed
product is NaCMC. The results of the FTIR spectrum bands of
raw bagasse and alkaline cellulose prepared
from bagasse are shown in Figure 4 and 5
respectively. The report of the [10] men-
tioned that the peak centred at 1730 cm−1
is attributed to the C=O stretching vibra-
tion of the acetyl and uronic ester group from
pectin, hemicellulose or the carboxylic group
of ferulic and p-coumaric acids of lignin. Fur-
ther, [11] reported that the absorption peak
Figure 2: Used ball mill for the processing at 1622 cm−1 and faintly at 1509 cm−1 are
assigned to aromatic C=C in the plane sym-
2.6.2 Degree of Substitute (Ds), Active metrical stretching vibration of the aromatic
matter content, water solubility and
color ring present in lignin. Further, the peak at
1250 cm−1 present is associated with the C-O
IS3520, methods [9] were used for determina- out of plane stretching vibration of the aryl
tion of Ds and active matter content of devel- group in lignin [12]. Additionally, [12] indi-
oped product. Water soluble (l/g) was mea- cated that all these peaks are disappearing in
sured by mixing 1g of the developed product the spectra of Na-cellulose obtained after pre-
in 100 ml of tap water. The color of the sam- treatments. Also, the peak of 1644 cm-1 is
ple was visually observed. the spectra of Na-cellulose. Thus, wavenum-
bers for the alkaline cellulose has mentioned
3. Results and Discussion in the report of [3] is shown in figure 6 and
those are inclined with the findings of present
3.1 Result of chlorination method
study.
Figure 3 shows that the extracted cellulose 3.3 Characteristics of developed product
from bagasse and it has light yellow in color.
3.3.1 FTIR

The FTIR spectral bands corresponding to

the recommended NaCMC sample available
in the export market and developed NaCMC
are shown in Figure 7 and 8 respectively. Fur-
ther, relevant spectral bands of these three
graphs and spectral bands reported by [8] for
NaCMC is shown in Table 1. [8] reported
that the presence of strong absorption bands
at around 1600–1640 cm−1 and 1400–1450
Figure 3: Alkaline cellulose prepared from bagasse
cm−1 were observed due to symmetric and
asymmetric vibrations of the ionized -COO-
group and its salts. This indicated that car-
The result of the chlorination method indi-
boxyl groups were substituted onto the cellu-
cated that cellulose sample extracted from
lose backbone when carboxymethylation reac-
bagasse consists 88.2% of cellulose. The re-
tion occurred and NaCMC was prepared.
sults of titration indicated that l kg of alka-
line cellulose prepared from bagasse consists

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 Figure 4: FTIR analysis of native bagasse

Figure 5: FTIR analysis of alkaline cellulose prepared from bagasse

Figure 6: FTIR result of Alkaline cellulose [3]

17
 Figure 7: NaCMC sample available in export market [2]

Figure 8: Developed NaCMC using bagasse

Comparison of similar bands of developed
NaCMC indicates in Figure 8 and Table 1
confirmed that the developed product was
NaCMC.
3.3.2 Color
Figure 9 shows that the visual observations
of prepared NaCMC from bagasse. Nor-
mally, the purified CMC is a white to cream
color [13]. The developed sample of the
present study had off white and its good for
processing of commercialized product. At
the end of the reaction process of ball mill,
86.98% weight of NaCMC was obtained after
pulverising and drying of the end product.
The average Ds values is < 0.4 in a devel-
oped NaCMC sample. [14] mentioned that
the theoretical maximum of the Ds value for
CMC/NaCMC is 3. However, the range for
commercially available CMC/NaCMC grade is
generally in the range 0.4 to 1.5.
In this batch, chemicals were used for pro-
cessing of NaCMC with Ds of 1. However,
comparison with the expected Ds value of de-
veloped product show a lower Ds value, which
may be low temperature rise during the etheri-
fication from the impact of balls to wall of ball
mill. At the end of the etherification process,
the average temperature inside the ball mill
was 380C.

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 Table 1: Comparisons of FTIR results with developed NaCMC

Type of bond Wave numbers [8] NaCMC sample Developed NaCMC

available in ex- from bagasse
port market
stretching vibrations of −OH 3000–3700 cm−1 3359.54 cm−1 3362.64 cm−1
C − H stretching vibrations 2850–2950 cm−1 2921.07 cm−1 2967.11 cm−1
C − O −C 1040 cm−1 1053.48 cm−1 1059.77 cm−1
Symmetric vibrations of ionized −COO 1600–1640 cm − 1 1587.16 cm−1 1596.33 cm−1
asymmetric vibrations of ionized −COO 1400–1450 cm−1 1413.88 cm−1 1409.10 cm−1

Table 2: Percentage of Alkalinity in prepared alkaline cellulose, water solubility, Ds value and Active matter
content of the prepared NaCMC

Sample Name Alkalinity % Water solubility g/l Ds Active matter content

Bagasse 15.2 69.5 0.25 38%

Fernando et al. [2] showed that the temper- Acknowledgements

ature rose to 740C during the etherification
using a ceramic balls added rotating drum for
the processing of NaCMC. Therefore, using
a ball mill that available in industries could
be increased, rising of temperature in inside
the ball mill during the etherification. The
technique of the present study is good for pro-
cessing of detergent grade NaCMC by increas-
ing Ds up to 0.4 and active matter content is
40%.
I wish to express my sincere gratitude to Mr.
N Gunathilaka and Mr.JCM Bandara at CAL
Export (PVT) LTD in Sri Lanka for their valu-
able support to arrange some laboratory facil-
ities at their company.
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4. Conclusions
The present study concludes that the alkaline
cellulose obtained from pre-treated fibers of
bagasse could be used directly for etherifica-
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