A dissertation submitted to the Faculty of Engineering and the Built
Environment, University of the Witwatersrand, Johannesburg, in fulfilment of
the requirements for the degree of Master of Science in Engineering.
October 2017 / Increasing concerns over environmental and geo-political issues on resources’ sustainability
have driven the industries to shift their efforts to produce chemicals from renewable biomass.
Amongst the lignocellulosic biomass, corncob contains cellulose, hemicellulose and lignin
that are built in a compact structure which makes it difficult to access. Pre-treatment is then
applied to make the content to be accessible to enzymatic hydrolysis which breaks down the
polysaccharides to monomers. The sugar monomers can be converted to a wide range of bioproducts
such as biofuels and bio-chemicals. The objective of the study was to determine,
evaluate and optimize the best solvent system to pre-treat corn cob. In addition, the study
evaluated the effect of pre-treatment parameters on the yield of cellulose and hemicellulose
and attempt to develop a kinetic model to explain the dissolution.
Lithium perchlorate, zinc chloride, phosphoric acid, sulphuric acid and sodium hydroxide
were used during the pre-treatment, which was carried out at 70-80 ° C for 6 hours.
Characterization of pre-treated samples showed a significant change in structure after pretreatment
indicating disruption in cell wall of the lignocellulosic material. FTIR revealed a
reduction in phenolic group; indicating that the lignin content has been reduced. The XRD
patterns show that crystallinity was considerably reduced; this was shown by an increase in
calculated crystallinity index (CrI) after LiClO4, ZnCl2, H3PO4 and NaOH pre-treatment. The
CrI of raw corncob (CrI= 32.7%) increased to 46.2 %, 42.3 %, 55.6 % and 53.4 % of LiClO4,
ZnCl2, H3PO4 and NaOH, respectively. The crystallinity index increased for pre-treated
material, indicating that the amorphous cellulose is dissolved in the liquor, as well as lignin
and hemicellulose removal
This study has shown that LiClO4.2H2O pretreatment agent is an efficient solvent system to
pretreat corncob which consecutively increase the accessibility of cellulose and hemicellulose
from the solid fractions. The accessibility was confirmed by an ease hydrolysis of cellulose &
hemicellulose to glucose & xylose respectively. An increase of nearly four times compared to
the untreated corncob. The effect of reaction operating parameters i.e. Reaction time,
temperature and solvent concentration was carried out and then optimized by response
surface methodology (RSM) using Minitab 16. The target was to maximize the yield of
cellulose and hemicellulose. It was discovered that the increase in temperature and reaction
time increase the accessibility of cellulose and hemicellulose until an equilibrium is reached
at 3 & half hours and 176 °c. The pretreatment solvent concentration was discovered to have
an effect on the accessibility but not as much as temperature and time. The best pretreatment
conditions to obtain high polysaccharides conversions to monomers were at 176°c for 3.5
hours using LiClO4.2H2O for 10 g of corncob.
The results obtained from RSM were used to evaluate the temperatures profile, kinetic model
for the corncob pretreatment as a function of temperature. The kinetics of pretreatment were
studied by the amount of glucose, xylose and the lignin removed from the pretreated solids.
The kinetic model of lignin removal and sugars accessibility was identified as a first-order
reaction corresponding to the bulk phase for pretreatment time up to 24 hours. The rate
constant results show that the kinetic rate increased with temperature. The activation energy
for glucose, xylose and lignin were calculated to be 15.0 kJ/mol, 14.2 kJ/mol and 36.54
kJ/mol, respectively. / MT 2018
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:wits/oai:wiredspace.wits.ac.za:10539/24033 |
| Date | January 2018 |
| Creators | Mudzanani, Khuthadzo Edna |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | Online resource (xiii, 113, 22 leaves), application/pdf, application/pdf |
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