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Isolation of cellulose from non-conventional
source and its chemical modification
Sindhu R#
, Surendra Singh Bisht*
, Manjula Sarode#
# Dept of Chemical Engineering, RVCE, Bangalore, Karnataka, India
*
Chemistry of Forest Products Division, IWST, Bangalore, Karnataka, India
E mail: rsindhu79@yahoo.com
Abstract- In present study cellulose was isolated from Prosopis juliflora, one of the obnoxious wild plants
followed by its chemical modification into Cellulose acetate. The conditions optimized for isolation of cellulose
were concentration of aqueous NaOH, concentration of sodium chlorite, process time and temperature with
distilled water as solvent medium .Further reaction temperature for acetylation reaction were optimized. Best
results obtained for isolation of cellulose were 50% sodium chlorite with 20% sodium hydroxide at 90°C for
120 min. Optimized conditions for acetylation of cellulose was found to be at 100 °C for 18hr examined.
Cellulose and cellulose acetate were characterized by Fourier transform infrared spectroscopy.
Keywords- Cellulose, Cellulose acetate, Prosopis juliflora, Fourier transform infrared spectroscopy
I. INTRODUCTION:
Natural polymers have various advantages over synthetic polymers. Furthermore, utilizing biopolymers from
weed species will reduce its negative impacts on environment and also eradication cost. This study aims at
isolation cellulose from weed plant and its chemical modification. Plant biomass consists of cellulose,
hemicellulose, lignin, pectin and protein. Most of the plant biomass consists of about 33 % of cellulose as the
major component of the rigid cell walls. Cellulose is a linear and high molecular weight polymer as well as
natural, renewable and biodegradable material. However, due to its high crystallinity and strong inter- and intra-
molecular hydrogen bond, cellulose neither melts nor dissolves in the most common organic solvents, therefore,
reduces its applicability. In order to increase the cellulose applicability, an alternative pathway is to convert the
cellulose to its derivatives such as cellulose acetate through chemical reaction. Cellulose acetate is important for
its soluble property in organic solvents where several applications are utilized in frame coatings in manufacture
of eye glasses, membranes for waste water treatment .
II. MATERIALS AND METHODS
A. Selection and processing of plant weed
Prosopis juliflora was selected based on its availability in local regions and abundance, through extensive
literature survey. Raw material collected was chopped and powdered.
ISBN-13: 978-1537584836
www.iaetsd.in
Proceedings of ICAER-2016
©IAETSD 201627
B. Extraction
Extraction of resins, fatty matter, polar compounds was done by soxhlet extraction using hexane, methanol and
methanol.
C. Hydrogen Peroxide treatment (Method A)
Alkali treatment was carried out using sodium hydroxide followed by delignification step using different
concentration of hydrogen peroxide.
D. Sodium chlorite treatment (Method B)
Prehydrolysis was carried out using distilled water at 90 °C for 45min followed delignification by addition of
different concentration of acidified sodium chlorite. Delignified samples were oven dried and treated with
sodium hydroxide by varying process time temperature.
E. Chemical modification and optimization
Cellulose isolated was derivatized chemically by acetylation reaction using acetic anhydride and pyridine.
Reaction temperature was varied from 30 °C to 100 °C and time was varied from 6hr to 18hr.
S/N Treatment Parameters Conditions
1 Hydrogen peroxide Concentration of hydrogen peroxide 5 mL-35 mL
2 Sodium chlorite
Sodium hydroxide
Concentration of sodium chlorite 10%- 60%
3 Time for sodium hydroxide treatment 60 min-120 min
4 Temperature for sodium hydroxide treatment 30 °C -60 °C
5 Acetylation Time for acetylation reaction 6h-18h
6 Temperature for acetylation reaction 30°C-90°C
Table 1: Optimization parameters
F. Characterization
FTIR analysis was performed for characterization of isolated cellulose and cellulose acetate synthesized.
III. RESULTS AND DISCUSSION
Graph 1 shows FTIR spectra of isolated cellulose which shows the presence of pectin and lignin indicating
incomplete delignification from hydrogen peroxide treatment. Graph 3 shows the FTIR spectra of cellulose
isolated by sodium chlorite treatments at different time indicates the absence of lignin and pectin with the
absence of few peaks from 1870 cm-1
to 1550 cm-1
. Table 1 shows the parameters optimized during hydrogen
peroxide and sodium chlorite treatment.
ISBN-13: 978-1537584836
www.iaetsd.in
Proceedings of ICAER-2016
©IAETSD 201628
CELLULOSE-3
CELLULOSE-3
CELLULOSE-3
CELLULOSE-3
4006008001000120014001600180020002400280032003600
Wavenumber cm-1
0.00.51.01.52.02.53.0
AbsorbanceUnits
CELLULOSE-3
CELLULOSE-3
3444.73
3350.48
2898.28
2895.98
1643.45
1640.82
1434.26
1370.11
1326.41
1160.76
1060.66
899.24
4006008001000120014001600180020002400280032003600
Wavenumber cm-1
0.00.51.01.52.02.5
AbsorbanceUnits
CELLULOSE-3
CELLULOSE-3
CELLULOSE-3
4006008001000120014001600180020002400280032003600
Wavenumber cm-1
0.00.51.01.52.02.53.0
AbsorbanceUnits
CELLULOSE ACETATE STD
CELLULOSE ACETATE
4006008001000120014001600180020002400280032003600
Wavenumber cm-1
0.00.51.01.5
AbsorbanceUnits
Colour of isolated cellulose slightly improved with increasing temperature of sodium hydroxide treatment from
30-90°C. Texture was improved with variation of sodium hydroxide reaction time from 60min to 120 min
[Graph 3]. Further increase in time and temperature led to degradation of reaction mixture and hence optimized
process condition were fixed at 90 °C and 120 min for sodium hydroxide treatment. Comparison of Fourier
transform infrared spectroscopy of isolated cellulose from Prosopis juliflora with that of standard cellulose
obtained from Sigma-Aldrich indicated strong resemblance between the isolated cellulose with that of cellulose
standard [Graph 2]. FTIR spectra showed slight modification in the structure of cellulose to cellulose acetate at
30 °C for 6h, 12h and 18h and 60 °C after 6h. Prominent peaks at 1753 cm1
shows the progress of acetylation at
5ml
H2O2
15ml
H2O2
25ml
H2O2
35ml
H2O2
60min
120min
30 min
Graph 1: FTIR spectra of isolated cellulose from
hydrogen peroxide treatment
Graph 2: Comparison of FTIR spectra of cellulose
standard and isolated cellulose
Graph 3: FTIR spectra of cellulose isolated from sodium
chlorite treatment at 90°C
Graph 4: Comparison of FTIR spectra of standard cellulose
acetate and isolated cellulose acetate
Cellulose
standard
Fig 1: Prosopis juliflora chopped Fig 2: Cellulose isolated
ISBN-13: 978-1537584836
www.iaetsd.in
Proceedings of ICAER-2016
©IAETSD 201629
60°C for 6h, 12h and 18h where as significant change in the reaction of cellulose to cellulose acetate is seen at
100 °C for 18h [Graph 4].
IV. CONCLUSION
This study explores the potential application of cellulose through the utilization of weed plant, thus reducing an
obnoxious plant weed posing threat to environment.
V. ACKNOWLEDGEMENT
I would like to express my heartfelt thanks to faculty of Department of Chemical engineering, RVCE and
Director, Institute of wood science and technology for their support in the completion of the work successfully.
VI. REFERENCES
1. J R Southon1, A L Magana, “A Comparison Of Cellulose Extraction And Aba Pretreatment Methods for Ams 14C Dating Of Ancient
Wood”, Proceedings of the 20th International Radiocarbon Conference, 2010, Vol 52, Nr 2–3, p 1371–1379
2. Rajwant Kaur, Wilfredo L. Gonzales, Luis Daniel Llambi, Pascual J. Soriano, Ragan M. Callaway, Marnie E. Rout, Timothy J. Gallaher,
Inderjit, Community Impacts of Prosopis juliflora Invasion:Biogeographic and Congeneric Comparisons, Plus one, September 2012,
Volume 7, Issue 9
3. Pragnesh N. Dave, Jaya Bhandari, Prosopis julifera: A revi ew, International Journal of Chemical Studies, Volume 1, Issue 3, 2013, p
181-187
4. Tewodros T. Wakie , Dana Hoag c, Paul H. Evangelista , Matthew Luizza, Melinda Laituri, Is control through utilization a cost effective
Prosopis juliflora management strategy?, Journal of Environmental Management ,2016, p 74-86
5. Adinugraha, M.P. and Marseno, D.W. and Haryadi, “Synthesis and characterization of sodium carboxymethyl cellulose from cavendish
banana pseudo” Carbohydrate Polymers, 2005, 62, pp. 164-169.
6. Aguirre-Cruz, A., Mendez-Montealvo, G., Solorza-Feria, J. and Bello-Perez, L.A., 2005. Effect of carboxymethylcellulose and xanthan
gum on the thermal, functional and rheological properties of dried nixtamalized maize masa. Carbohydrate Polymers, 62 (3), pp. 222-231.
7. Alves, V., Costa, N., Hilliou, L., Larotonda, F., Goncalves, M. and Sereno, A., 2006. Design of biodegradable composite films for food
packaging. Desalination,2006, 199 (1), pp. 331-333.
8. Amen-Chen, C., Pakdel, H. And Roy, C., 2001. “Production of monomeric phenols by thermochemical conversion of biomass”
Bioresource Technology, 2001, pp. 277-299.
9. H.D. Heydarzadeh, G.D . Najafpour and A. Nazari-Moghaddam, “Catalyst-Free Conversion of Alkali Cellulose to Fine Carboxymethyl
Cellulose at Mild Conditions” World Applied Sciences 2009, Journal 6 (4): 564-569.
10. Prasenjit Bhaumik, A K Deepa, Tanushree Kane And Paresh Laxmikant Dhepe, “Value addition to lignocellulosics and biomass-derived
sugars: An insight into solid acid-based catalytic methods”, J. Chem. Sci. Vol. 126, No. 2, March 2014, pp. 373–385
11. Ewa Kopania, Justyna Wietecha, Danuta Ciechańska., 2012 Studies on Isolation of Cellulose Fibres from Waste Plant Biomass Fibres &
Textiles In Eastern Europe 2012; 20, 6B (96): 167-17
12. Wan Rosli Wan Daud, Fauzi Muhammad Djuned, “Cellulose acetate from oil palm empty fruit bunch via a one step heterogeneous
acetylation” , Carbohydrate Polymers, 132 , 2015, 252-260
13. Jinghuan Chen, Jikun Xu, Kun Wang, Xuefei Cao, Runcang Sun, “Cellulose acetate fibers prepared from different raw materials
withrapid synthesis method”, Carbohydrate Polymers 137, 2016, 685-692
ISBN-13: 978-1537584836
www.iaetsd.in
Proceedings of ICAER-2016
©IAETSD 201630

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iaetsd Isolation of cellulose from non conventional source and its chemical modification

  • 1. Isolation of cellulose from non-conventional source and its chemical modification Sindhu R# , Surendra Singh Bisht* , Manjula Sarode# # Dept of Chemical Engineering, RVCE, Bangalore, Karnataka, India * Chemistry of Forest Products Division, IWST, Bangalore, Karnataka, India E mail: rsindhu79@yahoo.com Abstract- In present study cellulose was isolated from Prosopis juliflora, one of the obnoxious wild plants followed by its chemical modification into Cellulose acetate. The conditions optimized for isolation of cellulose were concentration of aqueous NaOH, concentration of sodium chlorite, process time and temperature with distilled water as solvent medium .Further reaction temperature for acetylation reaction were optimized. Best results obtained for isolation of cellulose were 50% sodium chlorite with 20% sodium hydroxide at 90°C for 120 min. Optimized conditions for acetylation of cellulose was found to be at 100 °C for 18hr examined. Cellulose and cellulose acetate were characterized by Fourier transform infrared spectroscopy. Keywords- Cellulose, Cellulose acetate, Prosopis juliflora, Fourier transform infrared spectroscopy I. INTRODUCTION: Natural polymers have various advantages over synthetic polymers. Furthermore, utilizing biopolymers from weed species will reduce its negative impacts on environment and also eradication cost. This study aims at isolation cellulose from weed plant and its chemical modification. Plant biomass consists of cellulose, hemicellulose, lignin, pectin and protein. Most of the plant biomass consists of about 33 % of cellulose as the major component of the rigid cell walls. Cellulose is a linear and high molecular weight polymer as well as natural, renewable and biodegradable material. However, due to its high crystallinity and strong inter- and intra- molecular hydrogen bond, cellulose neither melts nor dissolves in the most common organic solvents, therefore, reduces its applicability. In order to increase the cellulose applicability, an alternative pathway is to convert the cellulose to its derivatives such as cellulose acetate through chemical reaction. Cellulose acetate is important for its soluble property in organic solvents where several applications are utilized in frame coatings in manufacture of eye glasses, membranes for waste water treatment . II. MATERIALS AND METHODS A. Selection and processing of plant weed Prosopis juliflora was selected based on its availability in local regions and abundance, through extensive literature survey. Raw material collected was chopped and powdered. ISBN-13: 978-1537584836 www.iaetsd.in Proceedings of ICAER-2016 ©IAETSD 201627
  • 2. B. Extraction Extraction of resins, fatty matter, polar compounds was done by soxhlet extraction using hexane, methanol and methanol. C. Hydrogen Peroxide treatment (Method A) Alkali treatment was carried out using sodium hydroxide followed by delignification step using different concentration of hydrogen peroxide. D. Sodium chlorite treatment (Method B) Prehydrolysis was carried out using distilled water at 90 °C for 45min followed delignification by addition of different concentration of acidified sodium chlorite. Delignified samples were oven dried and treated with sodium hydroxide by varying process time temperature. E. Chemical modification and optimization Cellulose isolated was derivatized chemically by acetylation reaction using acetic anhydride and pyridine. Reaction temperature was varied from 30 °C to 100 °C and time was varied from 6hr to 18hr. S/N Treatment Parameters Conditions 1 Hydrogen peroxide Concentration of hydrogen peroxide 5 mL-35 mL 2 Sodium chlorite Sodium hydroxide Concentration of sodium chlorite 10%- 60% 3 Time for sodium hydroxide treatment 60 min-120 min 4 Temperature for sodium hydroxide treatment 30 °C -60 °C 5 Acetylation Time for acetylation reaction 6h-18h 6 Temperature for acetylation reaction 30°C-90°C Table 1: Optimization parameters F. Characterization FTIR analysis was performed for characterization of isolated cellulose and cellulose acetate synthesized. III. RESULTS AND DISCUSSION Graph 1 shows FTIR spectra of isolated cellulose which shows the presence of pectin and lignin indicating incomplete delignification from hydrogen peroxide treatment. Graph 3 shows the FTIR spectra of cellulose isolated by sodium chlorite treatments at different time indicates the absence of lignin and pectin with the absence of few peaks from 1870 cm-1 to 1550 cm-1 . Table 1 shows the parameters optimized during hydrogen peroxide and sodium chlorite treatment. ISBN-13: 978-1537584836 www.iaetsd.in Proceedings of ICAER-2016 ©IAETSD 201628
  • 3. CELLULOSE-3 CELLULOSE-3 CELLULOSE-3 CELLULOSE-3 4006008001000120014001600180020002400280032003600 Wavenumber cm-1 0.00.51.01.52.02.53.0 AbsorbanceUnits CELLULOSE-3 CELLULOSE-3 3444.73 3350.48 2898.28 2895.98 1643.45 1640.82 1434.26 1370.11 1326.41 1160.76 1060.66 899.24 4006008001000120014001600180020002400280032003600 Wavenumber cm-1 0.00.51.01.52.02.5 AbsorbanceUnits CELLULOSE-3 CELLULOSE-3 CELLULOSE-3 4006008001000120014001600180020002400280032003600 Wavenumber cm-1 0.00.51.01.52.02.53.0 AbsorbanceUnits CELLULOSE ACETATE STD CELLULOSE ACETATE 4006008001000120014001600180020002400280032003600 Wavenumber cm-1 0.00.51.01.5 AbsorbanceUnits Colour of isolated cellulose slightly improved with increasing temperature of sodium hydroxide treatment from 30-90°C. Texture was improved with variation of sodium hydroxide reaction time from 60min to 120 min [Graph 3]. Further increase in time and temperature led to degradation of reaction mixture and hence optimized process condition were fixed at 90 °C and 120 min for sodium hydroxide treatment. Comparison of Fourier transform infrared spectroscopy of isolated cellulose from Prosopis juliflora with that of standard cellulose obtained from Sigma-Aldrich indicated strong resemblance between the isolated cellulose with that of cellulose standard [Graph 2]. FTIR spectra showed slight modification in the structure of cellulose to cellulose acetate at 30 °C for 6h, 12h and 18h and 60 °C after 6h. Prominent peaks at 1753 cm1 shows the progress of acetylation at 5ml H2O2 15ml H2O2 25ml H2O2 35ml H2O2 60min 120min 30 min Graph 1: FTIR spectra of isolated cellulose from hydrogen peroxide treatment Graph 2: Comparison of FTIR spectra of cellulose standard and isolated cellulose Graph 3: FTIR spectra of cellulose isolated from sodium chlorite treatment at 90°C Graph 4: Comparison of FTIR spectra of standard cellulose acetate and isolated cellulose acetate Cellulose standard Fig 1: Prosopis juliflora chopped Fig 2: Cellulose isolated ISBN-13: 978-1537584836 www.iaetsd.in Proceedings of ICAER-2016 ©IAETSD 201629
  • 4. 60°C for 6h, 12h and 18h where as significant change in the reaction of cellulose to cellulose acetate is seen at 100 °C for 18h [Graph 4]. IV. CONCLUSION This study explores the potential application of cellulose through the utilization of weed plant, thus reducing an obnoxious plant weed posing threat to environment. V. ACKNOWLEDGEMENT I would like to express my heartfelt thanks to faculty of Department of Chemical engineering, RVCE and Director, Institute of wood science and technology for their support in the completion of the work successfully. VI. REFERENCES 1. J R Southon1, A L Magana, “A Comparison Of Cellulose Extraction And Aba Pretreatment Methods for Ams 14C Dating Of Ancient Wood”, Proceedings of the 20th International Radiocarbon Conference, 2010, Vol 52, Nr 2–3, p 1371–1379 2. Rajwant Kaur, Wilfredo L. Gonzales, Luis Daniel Llambi, Pascual J. Soriano, Ragan M. Callaway, Marnie E. Rout, Timothy J. Gallaher, Inderjit, Community Impacts of Prosopis juliflora Invasion:Biogeographic and Congeneric Comparisons, Plus one, September 2012, Volume 7, Issue 9 3. Pragnesh N. Dave, Jaya Bhandari, Prosopis julifera: A revi ew, International Journal of Chemical Studies, Volume 1, Issue 3, 2013, p 181-187 4. Tewodros T. Wakie , Dana Hoag c, Paul H. Evangelista , Matthew Luizza, Melinda Laituri, Is control through utilization a cost effective Prosopis juliflora management strategy?, Journal of Environmental Management ,2016, p 74-86 5. Adinugraha, M.P. and Marseno, D.W. and Haryadi, “Synthesis and characterization of sodium carboxymethyl cellulose from cavendish banana pseudo” Carbohydrate Polymers, 2005, 62, pp. 164-169. 6. Aguirre-Cruz, A., Mendez-Montealvo, G., Solorza-Feria, J. and Bello-Perez, L.A., 2005. Effect of carboxymethylcellulose and xanthan gum on the thermal, functional and rheological properties of dried nixtamalized maize masa. Carbohydrate Polymers, 62 (3), pp. 222-231. 7. Alves, V., Costa, N., Hilliou, L., Larotonda, F., Goncalves, M. and Sereno, A., 2006. Design of biodegradable composite films for food packaging. Desalination,2006, 199 (1), pp. 331-333. 8. Amen-Chen, C., Pakdel, H. And Roy, C., 2001. “Production of monomeric phenols by thermochemical conversion of biomass” Bioresource Technology, 2001, pp. 277-299. 9. H.D. Heydarzadeh, G.D . Najafpour and A. Nazari-Moghaddam, “Catalyst-Free Conversion of Alkali Cellulose to Fine Carboxymethyl Cellulose at Mild Conditions” World Applied Sciences 2009, Journal 6 (4): 564-569. 10. Prasenjit Bhaumik, A K Deepa, Tanushree Kane And Paresh Laxmikant Dhepe, “Value addition to lignocellulosics and biomass-derived sugars: An insight into solid acid-based catalytic methods”, J. Chem. Sci. Vol. 126, No. 2, March 2014, pp. 373–385 11. Ewa Kopania, Justyna Wietecha, Danuta Ciechańska., 2012 Studies on Isolation of Cellulose Fibres from Waste Plant Biomass Fibres & Textiles In Eastern Europe 2012; 20, 6B (96): 167-17 12. Wan Rosli Wan Daud, Fauzi Muhammad Djuned, “Cellulose acetate from oil palm empty fruit bunch via a one step heterogeneous acetylation” , Carbohydrate Polymers, 132 , 2015, 252-260 13. Jinghuan Chen, Jikun Xu, Kun Wang, Xuefei Cao, Runcang Sun, “Cellulose acetate fibers prepared from different raw materials withrapid synthesis method”, Carbohydrate Polymers 137, 2016, 685-692 ISBN-13: 978-1537584836 www.iaetsd.in Proceedings of ICAER-2016 ©IAETSD 201630