TITLE

Ultrasound assisted alkali pretreatment of cellulose

BY:
PRANAV SUNDARAM
BTECH,3rd YEAR,
CHEMICAL ENGINEERING,
NIT TRICHY

OVERVIEW

Introduction-Conventional Vs Non-conventional pre-treatment techniques.

Ultrasound: Its principles and theory.
Alkali pre-treatment
Objective
Experimental Setup
Results and Discussion
Conclusion

Introduction

Conventional physical pre-treatment techniques.

Comminution - Coarse size reduction, chipping, shredding,
grinding, milling are amongst the different mechanical size
reduction methods These treatments increase the available
specific surface area, and reduce cellulose crystallinity.
Major disadvantages include: High energy requirement on
an industrial scale. Due the rise in energy demands, it is
unlikely that these methods are still economically feasible.

Advantages of ultrasound pre-treatment technique are:

1.
2.
3.
4.

The use of water as a solvent.

Short reaction time.
No need of external source of heating.
No polluting gas or effluent is present.

Other kinds of pretreatment methods include: hydrothermal,

acidic, alkaline, wet oxidation, ammonia fiber explosion,
organosolv and ionic liquid pretreatment.They are
expensive and energy intensive and utilize chemicals which
require special disposal, handling, or production methods.

*Agbor VB, et al, Biomass pretreatment: Fundamentals toward application, Biotechnol Adv (2011), doi:10.1016/
j.biotechadv.2011.05.005

Ultrasound: Theory and Principles

Ultrasound occurs at frequencies beyond the audible range, typically between

20 and 1000 kHz. It is usually generated by piezoelectric transducers.
Ultrasonic waves create pressure differences within a solution for the
enhancement of physical (mechanoacoustic) and chemical (sonochemical)
processes.
Ultrasound provides physical augmentation via shear forces, mass transfer,
and surface erosion as well as chemical effects of producing oxidizing
radicals.
If physical effects must be dominant, then low frequencies should be selected.
However, if oxidizing radicals are necessary, then high frequencies must be
selected.

* dx.doi.org/10.1021/ie3022785 | Ind. Eng. Chem. Res. 2013, 52, 35633580

Mechanoacoustic Effects.

Sonochemical Effects.

Mechanoacoustic effects are caused

by the pressure differentials in the
ultrasonic wave. The normally
spherical bubble is distorted by the
asymmetrical liquid motion near the
boundary. The microjets produced
are responsible for cleaning
applications of ultrasound due to the
erosion capabilities.

Ultrasound is also used to enhance

chemical reactions or to choose a
certain reaction pathway. These
pathways are normally radical driven
processes.Ultrasound treatment
increases the rate of reaction at lower
temperatures than otherwise possible
and can reduce the amount of
chemicals required in a process.An
example :

* dx.doi.org/10.1021/ie3022785 | Ind. Eng. Chem. Res. 2013, 52, 35633580

ALKALI PRE-TREATMENT
Mercerization: Treatment with NaOH which causes swelling of
cellulose thereby increasing surface area, breaking H-bonds and
increasing accessibility. Cellulose 1 is converted to Cellulose 2.
1. Natural cellulose is cellulose I, with structures I and I.
All-parallel chains
I-Tricinic structure(one chain), I-Monoclinic structure(two
chains).
Not the lowest free energy organization of the (14) glucan
chains. Metastable cellulose I.
Smaller d-spacing.
(101)

(101^)

(002)

5.94

5.33

3.90

* Kokol, V. et al. Cellulose (2011) 18:15271541

DOI 10.1007/s10570-011-9601-4

2. Cellulose II
Monoclinic unit cell.(regenerated or mercerised)
Lower free energy organizations.
Anti-parallel chains.
The transition from cellulose I to cellulose II is irreversible, and this
implies that cellulose II is a more stable form.
Cellulose II has greater d-spacing.
(101)

(101^)

(002)

7.50

4.41

4.10

OBJECTIVE

Develop the combined ultrasound and NaOH pre-treatment method.

Study the structural changes in cellulose due to these pre-treatment
methods.
Relate these changes to the enzymatic hydrolysis yields.

Experimental Setup

Ultrasound
Treatment

Filtration and
Drying

Ultraound Treatment - Ultrasound Reactor.

Ultrasound Treatment done at 25 kHz.
Crystallinity Measurement - X-ray Diffration Studies.
Glucose Yields - DNS Analysis.
Enzyme used is Trichoderma reesei.

Enzymatic
Hydrolysis

RESULTS AND DISCUSSION

Formulae :.

Baseline correction : -500

1.

Im ax I 20 I 22.5

2.

3.

I12.0
CII
(I12.0 + 0.5(I14.7 + I16.1))

4.

CI X CII

5.

XII X * CII

6.

XI X XII

7.

Amor 1 X

Im ax Iam
Im ax

SAMPLE XRD PLOT

XRD PLOT
10000

Intensity

8000

6000

4000

10

20

30

Degree

40

XRD PLOTS
TCI
Amorp frac
Cellulose II frac
Cellulose I frac

EFFECT OF PARTICLE SIZE

1.8

V alue

1.2

0.6

0.0

20u

50u

100u

P article size

180u

EFFECT OF NaOH CONCENTRATION

TCI
Amorp frac
Cellulose II frac
Cellulose I frac

1.8

Values

1.2

0.6

0.0

Avicel
2pc-4hr

Avicel
5pc-4hr

Sigmacel
2pc-4hr

Sigmacel
5pc-4hr

EFFECT OF ULTRASOUND TIME

TCI
Amorp frac
Cellulose II frac
Cellulose I frac

1.8

Values

1.2

0.6

0.0

Avicel
5pc-2hr

Avicel
5pc-4hr

FTIR
FTIR P LOT
100

90

%T

80

70

4000

3500

3000

2500

2000

Wavenumber cm-1

1500

1000

3333.92

Stretching vibrations of OH
and CO

2886.89

Antisymmetric and symmetric

vibration of CH2 groups

1635.87

Adsorbed water (HOH

deformation)

1441.16

CH deformation

1368.35 and 1314.89

CH asymmetric deformation

1205.54

C-O-C symmetric stretching, OH

plane
deformation

1159.54

C-O-C asymmetrical stretching

1052.83

C-C, C-OH, C-H ring and side

group
vibrations

1027.81

C-C, C-OH, C-H ring and side

group
vibrations

*Mizi Fan, Dasong Dai and Biao Huang (2012). Fourier Transform
Infrared Spectroscopy
for Natural
Fibres,
COC,CCO
and CCH
deformation
Fourier Transform - Materials Analysis, Dr Salih Salih (Ed.), ISBN: 978-953-51-0594-7

896.087

and

Literature Review for further analysis:

1. The relative absorbance ratio (A40002995/A993) representes the hydrogenbond intensity (HBI). HBI is associated wiht the degree of intermolecular regularity
as well as the amount of bound water. As HBI increases crystallinity decreases.
2. The absorbance ratio of the bands at 1375 and 2900 cm-1(A1375/A2900) gives
the total crystallinity index (TCI).
3. Hydrogen bonds for cellulose I include two intramolecular bonding, namely,
O(2)H---O(6) bonding and O(3)H---O(5) bonding and one intermolecular bonding,
O(6)H---O(3) . Hydrogen bonds in cellulose II contains three intramolecular
bonds: O(2)H---O(6) bonding, O(3)H---O(5) bonding and O(2)H---O(2) bonding,
and two intermolecular bonding: O(6)H---O(2) and O(6)H---O(3). Hence using the
table below the presence or absence of these peaks will give an insight into the
presence or absence of cellulose II.

*Sang Youn Oh et al. Carbohydrate Research 340 (2005) 417428

CONCLUSION

From the XRD plots, it can be concluded that with increase in initial particle
size the conversion from cellulose I to cellulose II increases. Also the
decrease in Total Crystallinity Index(TCI) is more prominent for larger
particle sizes than smaller particles sizes.
With increase in NaOH concentration the conversion from cellulose I to
cellulose II increases.
With increase in ultrasonication time the conversion from cellulose I to
cellulose II increases.
From FTIR plots, the various vibrational bonds can be identified by referring
to literature. Further analysis of the FTIR plots is to be done for a deeper
understanding.

THANK YOU