NAME CHAUNOITA SIMBARASHE

REG NUMBER H210638B

COURSE HIT 300

SUPERVISOR Ms C. MACHOKOTO

DEPARTMENT POLYMER TECHNOLOGY ENGINEERING

YEAR 2023

TOPIC : DEPOLYMERIZATION OF CORNCOB STARCH FOR ETHANOL

PRODUCTION.
TABLE OF CONTENT

Contents
TABLE OF CONTENT................................................................................................................................................i
CHAPTER 1................................................................................................................................................................ 1
TITLE......................................................................................................................................................................1
BACKGROUND.....................................................................................................................................................1
PROBLEM STATEMENT......................................................................................................................................1
AIM......................................................................................................................................................................... 1
OBJECTIVES......................................................................................................................................................... 1
JUSTIFICATION....................................................................................................................................................1
SCOPE OF STUDY................................................................................................................................................ 1
DELIVERABLES................................................................................................................................................... 1
HYPOTHESIS.........................................................................................................................................................1
CHAPTER 2................................................................................................................................................................ 2
LITERARURE REVIEW........................................................................................................................................2
Introduction:........................................................................................................................................................2
The composition of feedstock biomass................................................................................................................2
PHYSICAL PROPERTIES OF ETHANOL.......................................................................................................3
Properties Values of ethanol................................................................................................................................4
CHEMICAL PROPERTIES................................................................................................................................4
OVERVIEW OF THE ETHANOL PRODUCTION PROCESS.........................................................................5
PRETREATMENT.............................................................................................................................................5
PHYSICAL PRETREATMENT.........................................................................................................................5
PHYSICO-CHEMICAL PRETREATMENT......................................................................................................6
CHEMICAL PRETREATMENT........................................................................................................................7
OZONOLYSIS....................................................................................................................................................7
OXIDATIVE DELIGNIFICATION...................................................................................................................8
ORGANOSOLV PROCESS...............................................................................................................................8
BIOLOGICAL PRETREATMENT....................................................................................................................8
HYDROLYSIS................................................................................................................................................... 9
FERMENTATION............................................................................................................................................11
DISTILLATION...............................................................................................................................................12
DEHYDRATION..............................................................................................................................................12
BY PRODUCTS OF CORNCOB BIOETHANOL PROCESS AND USES.....................................................13
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CHAPTER 3.............................................................................................................................................................. 14
METHODOLOGY................................................................................................................................................14
Introduction to Research...................................................................................................................................14
EXPERIMENTAL WORK...............................................................................................................................14
EXPERIMENT 1.............................................................................................................................................. 15
EXPERIMENT 2.............................................................................................................................................. 15
EXPERIMENT 3:.............................................................................................................................................16
EXPERIMENT 4.............................................................................................................................................. 16
EXPERIMENT 5.............................................................................................................................................. 17
EXPERIMENT 6.............................................................................................................................................. 17
EXPERIMENT 7.............................................................................................................................................. 17
EXPERIMENT 8.............................................................................................................................................. 17
EXPERIMENT 9.............................................................................................................................................. 18
CHARACTERIZATION..........................................................................................................................................18
BLOCK FLOW DIAGRAM.............................................................................................................................19
CHAPTER 4.............................................................................................................................................................. 20
RESULTS AND DISCUSION..............................................................................................................................20
EXPERIMENT 1.............................................................................................................................................. 20
EXPERIMENT 2 RESULTS............................................................................................................................22
EXPERIMENT 3 RESULTS............................................................................................................................23
EXPERIMENT 4 RESULTS............................................................................................................................24
EXPERIMENT 5 RESULTS............................................................................................................................25
EXPERIMANT 6 RESULTS............................................................................................................................26
EXPERIMENT 7 RESULTS............................................................................................................................26
EXPERIMENT 8 RESULTS............................................................................................................................27
EXPERIMENT 9 RESULTS............................................................................................................................27
CHARACTORIZATION.........................................................................................................................................29
CHAPTER 5.............................................................................................................................................................. 31
ECONOMIC ANALYSIS.....................................................................................................................................31
CHAPTER 6.............................................................................................................................................................. 32
CONCLUSION AND RECOMMENDATIONS...................................................................................................32
References................................................................................................................................................................. 33

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CHAPTER 1
TITLE: Depolymerization of Corncob for ethanol production.
BACKGROUND
Depolymerization of cellulose from biomass is an important step in the production of biofuels
such as bioethanol. Corncob is a promising source of cellulose, but its structure is composed of
three main polymer components, that is; cellulose, hemicellulose, and lignin. Cellulose is a
polymer of glucose monomers held together by hydrogen bonding in a crystalline form.
Hemicellulose is a heterogeneous low molecular weight polymer of five carbon sugars e.g.
(xylose and arabinose) and six carbon sugars that is (mannose, glucose and galactose). Lignin is
a complex polymer of aromatic compounds that provides rigidity and structure of the corncob
that makes it difficult to depolymerize. A two-step pretreatment process, combining alkaline
pretreatment with acid hydrolysis, has been proposed as a means of overcoming or breaking the
lignin structure, so as to make the cellulose accessible for hydrolysis.
PROBLEM STATEMENT
Shortage of effective ways for producing bio-monomers for ethanol production in Zimbabwe.
AIM
To depolymerize corncob into monomeric fermentable sugars for ethanol production.
OBJECTIVES
 To investigate the efficiency of pretreatment.
 To produce reduced sugars.
 To produce ethanol.
 To conduct characterization test
JUSTIFICATION
The research is important in that it is going to ease demand of reduced sugars and ethanol and
also improves the ethanol blending ratios. The research will also help in the utilization of
corncob which are considered as agricultural waste after harvesting.
SCOPE OF STUDY
The research is going to focus on the depolymerization of corncob into simple monomeric sugars
for ethanol production.
DELIVERABLES
This study will include a technical report describing the depolymerization process for producing
bioethanol from corncob, including the specific conditions used, and the yield of ethanol.
HYPOTHESIS
H0 – corncob can be depolymerized into simple monomeric fermentable sugars.
H1 – corncob cannot be depolymerized simple monomeric fermentable sugars.

1
CHAPTER 2
LITERARURE REVIEW
Introduction:
Cellulosic ethanol, derived from lignocellulosic biomass, has gained significant attention as a
sustainable alternative to fossil fuels. The production of cellulosic ethanol involves the
conversion of cellulose and hemicellulose into fermentable sugars, followed by fermentation and
distillation processes.
Cellulosic resources are generally widely distributed and plentiful. For instance, nearly 80% of
the biomass in the globe comes from forests. Cellulosic materials are relatively cheap feedstocks
for ethanol production because they are plentiful and not part of the human food chain. The
amazing organic polymer known as cellulose is made entirely of glucose units that are bound
together by a massive straight chain molecule. (Rosalin Pradhan, 2007)
Cellulosic materials, also known as lignocellulosic materials, are made up of cellulose,
hemicellulose, and lignin. Giving the plant structural support is one of lignin's main purposes. As
a result, trees generally contain more lignin than grasses. Sadly, lignin, which has no
carbohydrates, surrounds the cellulose and hemicellulose molecules, making it challenging to
access them. (Rosalin Pradhan, 2007)
Starch and cellulose molecules both contain long chains of glucose molecules, however cellulose
has a different structural makeup. Cellulosic materials are more challenging to hydrolyze than
starchy materials because of these structural features and the lignin's encapsulation. (Rosalin
Pradhan, 2007)
Long chains of sugar molecules likewise make up hemicellulose, but pentose (5-carbon sugars)
is also present in addition to glucose (a 6-carbon or hexose sugar). To further complicate matters,
depending on the type of plant, hemicellulose's precise sugar composition can change. The
capacity to recover and ferment them into ethanol is crucial for the effectiveness and economics
of the process since 5-carbon sugars make up a significant portion of the accessible sugars.
(Rosalin Pradhan, 2007)
The composition of feedstock biomass
Feedstock Cellulose % Hemicellulose % Lignin %
Hardwood stems 40-55 24-40 18-25
Softwood stems 45-50 5-35 25-35
Nut Shells 25-30 25-30 30-40
Corncob 45 35 15
Grasses 25-40 35-50 10-30
Paper 85-99 0 0-15
Wheat straw 30 50 15
Sorted Refuse 60 20 15
2
 Leaves 15-20 80-85 0
Cotton Stalks 45 20 21
Cotton Stalk hair 80-95 5-20 0
News paper 40-55 25-40 18-30
Waste Paper from 60-70 10-20 5-10
chemical pulps
Solid cattle manure 1.6-4.7 1.4-3.3 2.7-5.7
Switchgrass 45 31.5 12
(Cheng, 2002), (Mekonnen, 2012) (Ashter, 2018)
The Technological hurdles that are presented by the materials are: the separation of Lignin from
the cellulose and hemi-cellulose to make the material susceptible to hydrolysis.
The hydrolysis of cellulose and hemi-cellulose takes place at different rates and over reaction can
degrade the sugars into materials that are not suitable for ethanol production. The hydrolysis of
these materials produces a variety of sugars. Not all of these sugars are fermentable with the
standard yeast that is used in the grain ethanol industry. The pentose sugars are particularly
difficult to ferment. (Rosalin Pradhan, 2007)
PHYSICAL PROPERTIES OF ETHANOL
Ethyl alcohol under ordinary condition is volatile, flammable, clear, colorless liquid. (Rosalin
Pradhan, 2007)
The physical and chemical properties of ethyl alcohol are primarily dependent upon hydroxyl
group. This group imparts polarity to the molecule and gives rise to hydrogen bonding. These
two properties account for the abnormal physical behavior of lower molecular weight alcohols as
compared to hydrocarbons of equivalent weight. Infra-red 2 6 6 spectrographic studies have
shown that, in the liquid state, hydrogen bonds are formed by the attraction of the hydroxyl
hydrogen of one molecule and the hydroxyl oxygen of a second molecule. The net effect of this
bonding is to make liquid alcohol behave as though it were largely dimerized. This behavior is
analogous to the behavior of water, which however is more strongly bonded and appears to exist
in liquid clusters of more than two molecules. The association of ethyl alcohol, it should be
noted, is confined to the liquid state in the vapor state, this alcohol is monothetic. The molecular
association of liquid ethyl alcohol gives rise to an abnormally high boiling point and a high heat
of vaporization. Trouton’s constant for ethyl alcohol is 26.9 as compared to 21 for unassociated
liquids. This constant is the entropy of vaporization at atmospheric pressure and is obtained by
dividing the molecular heat of vaporization by the absolute temperature of the atmospheric
boiling point. Ethyl alcohol’s polarity and association also manifest themselves in the non-ideal
behavior of many ethyl alcohol solutions and in the fact that ethyl alcohol forms a large no of
azeotropes. Many other examples of ethyl alcohol abnormalities may be found in the properties

3
of ethyl alcohol solutions appearing in the literature. A summary of physical properties of ethyl
alcohol is presented below. (Rosalin Pradhan, 2007)
Properties Values of ethanol
Freezing point 114.10C
Normal boiling Point 78.320C
Flash point, open cup 140C
Auto-ignition temperature 3650C
Specific heat, at 200C 0.579cal/kg°C
(Rosalin Pradhan, 2007)

CHEMICAL PROPERTIES
The chemical properties of ethanol are primarily concerned with the hydroxyl group, namely
reactions involving dehydration, dehydrogenation, oxidation, and esterification. The H 2 atom of
the hydroxyl group can be replaced by active group I metals, such as sodium, potassium with the
formation of a metal ethoxide (ethylate) and the evolution of H2 gas. (Rosalin Pradhan, 2007)
2C2H5OH + 2Na 2C2H2Ona + H2
Sodium ethoxide can be prepared by the reaction between absolute ethanol and sodium or by
refluxing absolute ethyl alcohol with anhydrous sodium hydroxide, as shown
CH3CH2OH + NaOH CH3CH2ONa + H2O
(Rosalin Pradhan, 2007)

Sodium ethoxide is used in organic synthesis as a condensing and reducing agent. The reaction
between sodium ethoxide and Sulphur monochloride results in the formation of diethyl
thiosulphate.
2CH3CH2Ona + S2CL2 (CH3CH2)2S2O2 + 2NaCL
The commercial production of barbiturates (vernal, Barbital, luminal, amytal), ethyl
orthoformate and other chemicals are dependent upon the use of sodium ethoxide. Aluminum
and magnesium also react to form ethoxides, but the reaction must be catalyzed by amalgamating
the metal (adding a small amount of mercury)
6 CH 3 CH 2 ONa+2 AL →2 ( CH 3 CH 2 O ) 3 AL+ 3 H 2
2 CH 3 CH 2 OH + Mg →(CH 3 CH 2 O)2 Mg+ H 2
(Rosalin Pradhan, 2007)

Ethyl alcohol also reacts with acid anhydrides or acid halides to give corresponding esters
CH 3 CH 2 OH +(RCO)2 O → RCOOCHCH 3 + RCOOH
CH 3 CH 2 OH + RCOCL → RCOOCH 2 CH 3 + HCL
CH 3 CH 2 OH + RCOCL+ RCOO CH 2 CH 3 + HCL
4
Ethyl alcohol may be dehydrated intramolecularly to form ethylene or ethyl ether
CH3CH2OH → CH2=CH2 + H2O
(Rosalin Pradhan, 2007)

Ethyl alcohol reacts with sodium hypochlorite to give chloroform – the haloform reaction.
CH 3 CH 2 OH + NaOCL→ CH 3 CHO+ NaCL+ H 2 O
CH 3 CHO+3 NaOH → C CL3 CHO+3 NaOH
CL3 CHO+ NaOH → CH CL 3+ HCOONa
Similarly, bromoform (CHBr3) and iodoform (CHI3) are obtained from sodium hypobromite and
hypoiodite respectively. Ethyl alcohol is the only primary alcohol that undergoes this reaction.
(Rosalin Pradhan, 2007)
OVERVIEW OF THE ETHANOL PRODUCTION PROCESS
Ethanol can be produced in two diverse ways. Either chemically, by hydration of ethylene, which
is derived from crude oil or natural gas, or by fermentation of sugar containing feeds, starchy
feed materials or lignocellulosic materials. About 5% - 10% of the ethanol produced in the world
is a petroleum product. Petroleum ethanol product is made by the catalytic hydration of ethylene
with sulfuric acid as the catalyst. It can also be obtained via ethylene or acetylene, from calcium
carbide, coal, oil gas, and other sources (Mekonnen, 2012). The two primary ways of producing
fuel ethanol from cellulosic feedstock are: Biochemical conversion process and Thermochemical
conversion process (Wondale, 2004)
PRETREATMENT
Pretreatment is required to alter the biomass macroscopic and microscopic size and structure as
well as its submicroscopic chemical composition and structure so that hydrolysis of carbohydrate
fraction to monomeric sugars can be achieved more rapidly and with greater yields (Cheng,
2002)
The effect of pretreatment of lignocellulosic materials has been recognized for a long time. The
purpose of the pretreatment is to remove lignin, reduce cellulose crystalline and increase the
porosity of the materials. Pretreatment must meet the following requirements: Improve the
formation of sugars or the ability to subsequently form sugars by acidic or enzymatic hydrolysis;
avoid the degradation or loss of carbohydrate; avoid the formation of byproducts inhibitory to the
subsequent hydrolysis and fermentation processes. (Mekonnen, 2012)
Physical, chemical, physio-chemical, and biological processes have been used for pretreatment
of lignocellulosic materials (Cheng, 2002)
PHYSICAL PRETREATMENT
Mechanical Comminution
Waste materials can be comminuted by a combination of chipping, grinding, and milling to
reduce cellulose crystallinity. The size of the materials is usually 10–30 mm after chipping and
0.2–2 mm after milling or grinding. Vibratory ball milling has been found to be more effective in

5
breaking down the cellulose crystallinity of spruce and aspen chips and improving the
digestibility of the biomass than ordinary ball milling. (Rosalin Pradhan, 2007)
The power requirement of mechanical comminution of agricultural materials depends on the
final particle size and the waste biomass characteristics. (Cheng, 2002)
Pyrolysis has also been used for pretreatment of lignocellulosic materials. When the materials are
treated at temperatures greater than 300°C, cellulose rapidly decomposes to produce gaseous
products and residual char. The decomposition is much slower and fewer volatile products are
formed at lower temperatures. Mild acid hydrolysis (1 N H 2 SO4 , 97 °C, 2.5 h) of 20 the
residues from pyrolysis pretreatment has resulted in 80–85% conversion of cellulose to reducing
sugars with more than 50% glucose. The process can be enhanced with the presence of oxygen.
(Rosalin Pradhan, 2007)
When zinc chloride or sodium carbonate is added as a catalyst, the decomposition of pure
cellulose can occur at a lower temperature. (Cheng, 2002)
PHYSICO-CHEMICAL PRETREATMENT
Steam explosion (auto hydrolysis)
Steam explosion (uncatalyzed or catalyzed) is one of the most applied pretreatment processes
owing to its low use of chemicals and limited energy consumption. With this method high-
pressure saturated steam is injected into a batch or continuous reactor filled with biomass.
During the steam injection, the temperature rises to 160-260 ºC. Subsequently, pressure is
suddenly reduced, and the biomass under-goes an explosive decompression with hemicellulose
degradation and lignin matrix disruption as result. (Jin, 2012)
Results of steam-explosion pretreatment depend on residence time, temperature, particle size and
moisture content (J. Cheng, 2002)
Studies have been carried out to try to improve the results of steam explosion by addition of
chemicals such as acid or alkali (Rochford, 2008)
Limitations of steam explosion include the formation of degradation products that may inhibit
downstream processes (Garcia-Aparicon, 2006)
team explosion is recognized as one of the most cost-effective pretreatment processes for
hardwoods and agricultural residues, but it is less effective for softwoods (J. Cheng, 2002)
Ammonia fiber explosion (AFEX)
To reduce the cost and protect the environment, ammonia must be recycled after the
pretreatment. In an ammonia recovery process, a superheated ammonia vapor with a temperature
up to 2000C was used to vaporize and strip the residual ammonia in the pretreated biomass and
the evaporated ammonia was then withdrawn from the system by a pressure controller for
recovery. The ammonia pretreatment does not produce inhibitors for the downstream biological
processes, so water wash is not necessary. (Rosalin Pradhan, 2007)
AFEX pretreatment does not require small particle size for efficacy (J. Cheng, 2002)

6
Carbon dioxide explosion
The yields were relatively low compared to steam or ammonia explosion pretreatment, but high
compared to the enzymatic hydrolysis without pretreatment. (Mekonnen, 2012)
Compared CO2 explosion with steam and ammonia explosion, found that CO 2 explosion was
more cost-effective than ammonia explosion and did not cause the formation of inhibitory
compounds that could occur in steam explosion (J. Cheng, 2002)
CHEMICAL PRETREATMENT
Alkaline pretreatment
Some bases can also be used for pretreatment of lignocellulosic materials and the effect of
alkaline pretreatment depends on the lignin content of the materials. The mechanism of alkaline
hydrolysis is believed to be saponification of intermolecular ester bonds cross linking xylan 1 8 9
15 11 hemicelluloses and other components, for example, lignin and other hemicellulose. The
porosity of the lignocellulosic materials increases with the removal of the crosslinks. Dilute
NaOH treatment of lignocellulosic materials caused swelling, leading to an increase in internal
surface area, a decrease in the degree of polymerization, a decrease in crystallinity, separation of
structural linkages between lignin and carbohydrates, and disruption of the lignin structure. The
digestibility of NaOH-treated hardwood increased from 14% to 55% with the decrease of lignin
content from 24% to 20%. (Mekonnen, 2012)
However, no effect of dilute NaOH pretreatment was observed for softwoods with lignin content
greater than 26% (J. Cheng, 2002)
Dilute-sulfuric acid pre-hydrolysis (Daph)
Acid pretreatment firstly developed in Germany in 1898. They used concentrated or dilute
sulfuric acid to breakdown the hemicellulose polymer into monomeric sugars and at the same
time removing part of lignin. This reaction a small amount of water was used since less energy
was required to get optimum temperature.
Some advantages of this method are:
High yield of hemicelluloses sugar, remove of lignin and hemicelluloses in this method increases
exposing of cellulose to enzyme, remove of heavy metals in the raw materials. (Dehnavi, 2009)
Some disadvantages of this method are:
Neutralization of acids is necessary, degradation of hemicelluloses sugar produce some inhibitors
like acetic acid and furfural, high cost of reactor due to high pressure and temperature and
resistance to low PH (Sanchez, 2004)
OZONOLYSIS
Used to degrade lignin and hemicellulose in many feedstocks such as wheat straw, bagasse,
green hay, peanut, pine, cotton straw, and poplar sawdust. The degradation was essentially
limited to lignin and hemicellulose was slightly attacked, but cellulose was hardly affected.
Enzymatic hydrolysis yield increased from 0% to 57% as the percentage of lignin decreased
from 29% to 8% after ozonolysis pretreatment of poplar sawdust.

7
Ozonolysis pretreatment has the following advantages: it effectively removes lignin; it does not
produce toxic residues for the downstream processes and the reactions are carried out at room
temperature and pressure. However, a large amount of ozone is required, making the process
expensive (J. Cheng, 2002)
OXIDATIVE DELIGNIFICATION
Lignin biodegradation could be catalyzed by the peroxidase enzyme with the presence of H2O2.
The pretreatment of cane bagasse with hydrogen peroxide greatly enhanced its susceptibility to
enzymatic hydrolysis. (Rosalin Pradhan, 2007)
About 50% lignin and most hemicellulose were solubilized by 2% H2O2 at 30 0C within 8 h, and
95% efficiency of glucose production from cellulose was achieved in the subsequent
saccharification by cellulase at 450C for 24 h used wet oxidation and alkaline hydrolysis of wheat
straw (20 g straw/l, 1700C, 5–10 min), and achieved 85% conversion yield of cellulose to
glucose (J. Cheng, 2002)
ORGANOSOLV PROCESS
In the organosolv process, an organic or aqueous organic solvent mixture with inorganic acid
catalysts (HCl or H2 SO4) is used to break the internal lignin and hemicellulose bonds. The
organic solvents used in the process include methanol, ethanol, acetone, ethylene glycol, and
triethylene glycol and tetrahydrofurfuryl alcohol. Organic acids such as oxalic, acetylsalicylic,
and salicylic acid can also be used as catalysts in the organosolv process. At high temperatures,
the addition of catalyst was unnecessary for satisfactory delignification. Usually, a high yield of
xylose can be obtained with the addition of acid. Solvents used in the process need to be drained
from the reactor, evaporated, condensed and recycled to reduce the cost. (Rosalin Pradhan, 2007)
Removal of solvents from the system is necessary because the solvents may be inhibitory to the
growth of organisms, hydrolysis, and fermentation (J. Cheng, 2002)
BIOLOGICAL PRETREATMENT
In biological pretreatment processes, microorganisms such as brown, white and soft-rot fungi are
used to degrade lignin and some hemicellulose in waste materials. Brown rots mainly attack
cellulose, while white and soft rots attack both cellulose and lignin. White-rot fungi are the most
effective basidiomycetes for biological pretreatment of lignocellulosic materials.
The white-rot fungus P. Chrysosporium produces lignin-degrading enzymes, lignin peroxidases
and manganese- dependent peroxidases, during secondary metabolism in response to carbon or
nitrogen. Both enzymes have been found in the extracellular filtrates of many white-rot fungi for
the degradation of wood cell walls. Other enzymes including polyphenol oxidases, laccases,
H2O2 producing enzymes and quinone-reducing enzymes can also degrade lignin. The
advantages of biological pretreatment include low energy requirement and mild environmental
conditions. (Ankita, 2012).
However, the rate of hydrolysis in most biological pretreatment processes is very low (J. Cheng,
2002)

8
HYDROLYSIS
After the pretreatment process, there are two types of processes to hydrolyze the feedstocks for
fermentation into ethanol, most commonly used are acid (dilute and concentrated) and enzymatic
hydrolysis. In addition, there are some other hydrolysis methods in which no chemicals or
enzymes are applied. For instance, lignocellulose may be hydrolyzed by gamma ray or electron-
beam irradiation, or microwave irradiation. However, those processes are commercially
unimportant. (Mekonnen, 2012)
Acid hydrolysis
Dilute Acid Hydrolysis
The dilute acid process is conducted under high temperature and pressure, and has a reaction
time in the range of seconds or minutes, which facilitates continuous processing. The
combination of acid and high temperature and pressure dictate special reactor materials, which
can make the reactor expensive. The first reaction converts the cellulosic materials to sugar and
the second reaction converts the sugars to other chemicals. Unfortunately, the conditions that
cause the first reaction to occur also are the right conditions for the second to occur. (Mekonnen,
2012)
The biggest advantage of dilute acid processes is their fast rate of reaction, which facilitates
continuous processing. Since 5-carbon sugars degrade more rapidly than 6-carbon sugars, one
way to decrease sugar degradation is to have a two-stage process. (Mekonnen, 2012)
The first stage is conducted under mild conditions to recover the 5-carbon sugars while the
second stage is conducted under harsher conditions to recover the 6-carbon sugars (Demirbas,
2005)
A range of temperatures between 170-190°C in the first stage and 200-230°C in the second stage
is commonly used (Zacchi, 2002)
Concentrated Acid Hydrolysis
Hydrolysis of cellulosic materials by concentrated sulfuric or hydrochloric acids is an old
process. The concentrated acid process uses relatively mild temperatures, and the only pressures
involved are those created by pumping materials from vessel to vessel. (Mekonnen, 2012)
Reaction times are typically less than for dilute acid (Demirbas, 2005)
This method generally uses concentrated sulfuric acid followed by a dilution with water to
dissolve and hydrolyze or convert the substrate into sugar. This process provides a complete and
rapid conversion of cellulose to glucose and hemicelluloses to 5-carbon sugars with little
degradation. The critical factors needed to make this process economically viable are to optimize
sugar recovery and cost effectively recovers the acid for recycling. The solid residue from the
first stage is dewatered and soaked in a 30 to 40% concentration of sulfuric acid for one to four
hours as a pre-cellulose hydrolysis step. The solution is again dewatered and dried, increasing the
acid concentration to about 70% (Mekonnen, 2012)

9
After reacting in another vessel for 1 to 4 h at low temperatures, the contents are separated to
recover the sugar and acid. The sugar/acid solution from the second stage is recycled to the first
stage to provide the acid for the first stage hydrolysis. (Mekonnen, 2012)
The primary advantage of the concentrated acid process is the potential for high sugar recovery
efficiency. The acid and sugar are separated via ion exchange and then acid is re-concentrated
via multiple effect evaporators. The low temperatures and pressures employed allow the use of
relatively low-cost materials such as fiberglass tanks and piping. (Mekonnen, 2012)
The low temperatures and pressures also minimize the degradation of sugars (Demirbas, 2005)
Unfortunately, it is a relatively fast process and cost-effective acid recovery systems have been
difficult to develop. Without acid recovery, large quantities of lime must be used to neutralize
the acid in the sugar solution. (Mekonnen, 2012)
This neutralization forms massive quantities of calcium sulfate, which requires disposal and
creates additional expense (Demirbas, 2005).
Enzymatic hydrolysis
The hydrolysis of cellulose by cellulolytic enzymes has been investigated intensively since the
early 1970s, with the objective of developing a process for the production of ethanol. Enzymatic
hydrolysis methods have shown distinct advantages over acid-based hydrolysis. (Mekonnen,
2012)
The very mild process conditions give potentially higher yields, the utility cost is low (no
corrosion problems). Therefore, this is the method of choice for future cellulosic-to-ethanol
processes (Murray, 1996)
Enzymatic hydrolysis involves soluble enzymes working on insoluble substrates, so a better
understanding of the action of cellulase enzyme systems and their substrates is required as this
complex reaction involves multiple cellulose-hydrolyzing activities and substrate features.
(Murray, 1996)
Cellulase enzymes, which are incredibly specialized, perform the enzymatic hydrolysis of
cellulose (Murray, 1996)
Products of hydrolysis often include glucose and other reducing sugars. Cellulases can be
produced by fungi and bacteria for the hydrolysis of lignocellulosic materials. These microbes
can be mesophilic or thermophilic, aerobic or anaerobic. The majority of research for
commercial cellulase production has concentrated on fungi since anaerobes have an unusually
slow development rate and need anaerobic growth conditions (Murray, 1996)
Cellulases break down cellulose during the enzymatic hydrolysis process into reducing sugars,
which yeasts or bacteria can ferment to produce ethanol. Due to the tough crystalline structure,
the enzymes currently available require several days to achieve good results. Since long process
times tie up reactor vessels for long periods, these vessels have to either be quite large or many
of them must be used. Either option is expensive. Currently the cost of enzymes is also too high,
and research is continuing to bring down the cost of enzymes (James L. Badger, 2002)
10
However, if less expensive enzymes can be developed enzymatic processes hold several
advantages: Their efficiency is quite high and their byproduct production can be controlled; their
mild process conditions do not require expensive materials of construction; and their process
energy requirements are relatively low (James L. Badger, 2002)
FERMENTATION
Lignocellulose is often hydrolyzed by acid treatment. The hydrolysate obtained is then used for
bioethanol fermentation by microorganisms such as yeast. (Mekonnen, 2012)
Because such lignocellulose hydrolysate contains not only glucose, but also various
monosaccharides, such as xylose, mannose, galactose, arabinose, and oligosaccharides,
microorganisms should be required to efficiently ferment these sugars for the successful
industrial production of bioethanol (Hiroyuki Katahira, 2006)
In general, the conversion of lignocellulosic material to sugar and then ethanol is governed by
equation (3) below:
¿
According to the reactions, the theoretical maximum yield is 0.51 kg bioethanol and 0.49 kg
carbon dioxide per kg of xylose and glucose (Wilfried Hamelinck, 2003) (Vasile, 2005)
The overall reaction of this fermentation of hexose sugar (glucose) by yeast has been expressed
by Gay-Issac which forms the basis of calculating fermentation efficiency as:
3 C5 H 10 O5 →5 C 2 H 5 OH + 5C O2
C 6 H 12 O6 → 2C 2 H 5 OH + 2C O2
Fermentation involves microorganisms that use the fermentable sugars for food and in the
process produces ethyl alcohol and other byproducts. These microorganisms can typically use 6-
carbon sugars, one of the most common being glucose. Therefore, cellulosic biomass materials
containing high levels of glucose or precursors to glucose are the easiest to convert to bioethanol
(Mekonnen, 2012)To get an efficient fermentation severe inhibition should be avoided. There are
four different strategies to do this. (Mekonnen, 2012)
These are modifying the hydrolysis process, detoxification, in-situ detoxification and using less
sensitive microorganisms to inhibitors (Taherzadeh, 1999). Microorganisms, termed
ethanologens, presently convert an inadequate portion of the sugars from biomass to bioethanol.
(Demirbas, 2005)
One of the most effective bioethanol producing yeasts, S. cerevisiae, has several advantages
owing to its high bioethanol production from hexoses and high tolerance to bioethanol and other
inhibitory compounds in the acid hydrolysates of lignocellulosic biomass. However, because
wild-type strains of this yeast cannot utilize pentoses, such as xylose and arabinose, and cell
oligosaccharides, bioethanol production from a lignocellulose hydrolysate is inadequate
(Hiroyuki Katahira, 2006)

11
Therefore, bioethanol fermentation from xylose can be successfully performed by recombinant
S. cerevisiae carrying heterologous XR and XDH from P. stipitis, and xylulokinase (XK) from S.
cerevisiae (Hiroyuki Katahira, 2006)

The performance parameters of fermentation are temperature range, pH range, alcohol tolerance,
growth rate, productivity, osmotic tolerance, specificity, yield, genetic stability, and inhibitor
tolerance (Demirbas, 2005)
DISTILLATION
Distillation is one of the steps of the purifications. Distillation is the method used to separate two
liquids based on their different boiling points. However, to achieve high purification, several
distillations are required. This is because all materials have intermolecular interactions with each
other, and two materials will co-distill during distillation. (Mekonnen, 2012)
This means that proportion between two materials, in this case ethanol and water can be
changed, and still, there are two materials in layers, the liquid and the vapor layers. (Mekonnen,
2012)
Whatever method of preparation is used, the ethanol is initially obtained in a mixture with water.
The ethanol is then extracted from this solution by fractional distillation. Although the boiling
point of ethanol, 78.30C, is significantly lower than the boiling point of water, 100 0C, these
materials cannot be separated completely by distillation. Instead, an azeotrope mixture (i.e. a
mixture of 95% ethanol and 5% water) is obtained, and the boiling point of the azeotrope is
78.15 0C. In a distillation, the most volatile material (i.e. the material that has the lowest boiling
point) is the first material to distill from the distillation flask, and this material is the azeotrope of
95% ethanol which has the lowest boiling point. If an efficient fractionating column is used, 95%
alcohol could be obtained first and then a small intermediate fraction of lower concentration, and
then water. (Mekonnen, 2012)
But no matter how efficient the fractionating column used, 95% alcohol cannot be further
concentrated by distillation because the vapor has exactly the same composition as the liquid;
towards distillation, then, 95% alcohol behaves exactly like a pure compound (Mekonnen, 2012).
DEHYDRATION
After distillation, about 5% of water remains in ethanol. Especially, this water is a big problem
for fuel ethanol because the presence of this amount of water enhances the molecular polarity of
ethanol when it is mixed with gasoline. Consequently, they separate into two phases, ethanol
phase and gasoline phase. It is easy to imagine that this inhomogeneous fuel is not acceptable.
(Mekonnen, 2012)
For the ethanol to be usable as a fuel, water must be removed. Most of the water is removed by
distillation, but the purity is limited to 95-96% due to the formation of a low boiling water
ethanol azeotrope. For blending with gasoline, purity of 99.5 to 99.9% is required, depending on
temperature, to avoid separation. Currently, the most widely used purification method is a
physical absorption process using molecular sieves. (Mekonnen, 2012)
12
BY PRODUCTS OF CORNCOB BIOETHANOL PROCESS AND USES
BY USES
PRODUCT
Stillage Fertilizer and animal feed
Lignin  Fuel,
 (PLA and PHA) polymers, used to make water bottles, shopping bags
 additive in cement, asphalt, and other construction materials to
improve their strength and durability.
Corbon  injected into oil wells, where it can help to push out the oil and
dioxide increase production.
 greenhouses to stimulate plant growth.
Hydrogen hydrogen that is produced during fermentation can be used in fuel cells to
generate electricity.
Ethanol  as a biofuel, blended with gasoline to reduce emissions and improve
engine performance
 production of pharmaceuticals, cosmetics, and food products
 as a solvent, a deicing agent, a disinfectant, and an ingredient in
personal care products.
 converted into ethylene and propylene, which can be used to make
plastics, textiles, and other materials.

13
CHAPTER 3
METHODOLOGY
Introduction to Research
Different methods and tools were utilized to determine the best route and conditions for
optimizing the depolymerization of corncob starch to production of ethanol. Experiments were
conducted to collect the necessary data for designing the process and selecting equipment.

Data collection methods

The following were the data collection methods carried out to come up with detailed and
informative research.

Primary data
 Experimental work was carried out to determine the necessary information
 Interviews: In this work interviews were conducted with business people and maize
famers.
 Suppliers who transport maize cobs from farms to the ethanol production facility.

Secondary data
Various sources were consulted to gather secondary data, such as:

 reports and project documents

 journals, books, articles
 Internet

Sample collection
To depolymerize corn starch, 3kgs of raw materials were obtained from Stratilone farm in
Goromonzi Zimbabwe and washed with tap water to remove impurities. The corns were then cut
into smaller pieces of 10-20 cm length and dried in an oven at 80° C for 24 hours to make them
easier to crush. Once dry, the sample was crushed using a shredding machine with a 2 mm sieve
to reduce the particle size and decrease cellulose crystallinity. The purpose of this research was
to investigate the potential effectiveness of two-step pretreatment in depolymerization of corncob
for ethanol production. Secondary data was gathered from various sources.

EXPERIMENTAL WORK
EXPERIMENTAL OBJECTIVES
 To determine the most effective pre-treatment reagent.
 To determine the effectiveness of concentration on pre-treatment
14
Experimental plan
Size reduction (pounding) and sieving of corncob were done prior to experiments to ensure large
surface area required for reactions to take place

Size reduction and sieving pictures

EXPERIMENT 1: To investigating the effectiveness of different pretreatment methods

AUTOCLAVING PRETREATMENT

Aim: to remove all the lignin and make cellulose accessible for hydrolysis.
Materials: conical flask, beaker, balance, measuring cylinder, distilled water, PH meter
Reagents: sulfuric acid, sodium hydroxide, acetic acid
Procedure:
Prepared 3sample corncob (A, B, C, E, F, G, H and I) of mass 134g, with 5%, 7%, 9%, 11%,
13% 15% 17%, and 21% sodium hydroxide solution, respectively. Autoclaved all the samples at
121 degrees Celsius for 30 minutes then cooled under room conditions, neutralized them using
acetic acid and used a digital PH meter. Filtered and neutralized samples and the residue was
then dried and weighed. The Autoclaving was repeated using 0.5%, 1%, 1.5%, 2%, 2.5%, 3%,
3.5%, and 4% of sulfuric acid respectively for all the 8 samples and for neutralization 5% sodium
hydroxide was used.
PH ADJUSTMENT
Before addition of sulfuric acid in second step pretreatment to the above prepared samples, pH of
these samples was to be adjusted. The PH was adjusted to a neutral PH so as to have a base
reference of the concertation used in the next stage.

EXPERIMENT 2 Two-step pretreatment using both acid and alkaline

Aim: to determine the effective method for the two-step pretreatment process
15
MAGNETIC STIRRER
Materials: conical flask, magnetic stirrer, beaker, balance, measuring cylinder, distilled water,
PH meter
Reagents: sulfuric acid, sodium hydroxide, acetic acid
Procedure:
5% sodium hydroxide solution was prepared and added it to 10g grounded corncob. The sodium
Hydroxide and grounded corncob was heated at 85 0C for 90 minutes simultaneous stirring. The
sample corncob was then cooled and neutralized using acetic acid and the digital PH meter. The
corncob was then neutralized using acetic acid and then filtered. The residue was then dried and
weighed. The whole procedure was repeated this time using 1% sulfuric acid and neutralization
by 5% sodium hydroxide to 5.5 PH. The experiment was repeated using a heating plat to
compare the effective between the magnetic stirrer and the hot plat.

EXPERIMENT 3: To separate the soluble extracted compounds after two-step pretreatment.

SOLVENT EXTRACTION
Aim: to separate oligomers and monomers
Materials: pretreated sample corncob, beaker, conical flask, funnel, filter paper, measuring
cylinder, stirring rod and heating element.
Reagent: acetone and ethanol
Procedure
The two-step pretreated filtered corncob liquid solution was placed in a beaker and the solution
was heated to reduce excess water, then cooled at room temperature. Acetone was pipetted to the
cooled corncob solution until the first precipitate. The conical flask with acetone and precipitate
was stirred to ensure complete precipitation in acetone and the volume of acetone used was
recorded. The precipitate was filtered, dried and weighed.

EXPERIMENT 4
FEHLING’S TEST
Aim: to test for the presence of reduced sugars.
Materials
Test tube, beaker, dropper
Reagents
Copper sulfate and potassium tartrate (Fehling’s reagent)
Procedure

16
The dried precipitate was dissolved in a solvent (water) and the Fehling’s reagent was added.
The presents of xylose will be shown by the brick-red precipitate. The precipitate formed will be
insoluble in water. Therefore, the solution sample will contain xylose.

EXPERIMENT 5
ACID HYDROLYSIS
Aim: to depolymerize the cellulose and hemicellulose into monomeric simple fermentable
sugars.
Materials: magnetic stirrer, conical flask, beakers, measuring cylinder, distilled water, sulfuric
acid, funnel, filter paper, PH meter
Procedure
Dilute hydrolysis
1.5% dilute sulfuric acid was prepared and was added to the pretreated corncob. The corncob and
sulfuric acid were heated and simultaneously stirred at 55 0C for 90minutes, then air cooled. The
hydrostat was neutralized to 5.5PH for the fermentation. The hydrostat was hafted filtered, the
filtrate was the passed for the solvent extraction and the yield was then calculated.
Concentrated hydrolysis
5% sulfuric acid was prepared and added to the pretreated corncob. The corncob and sulfuric
acid were heated and simultaneously stirred at 55 0C for 90minutes, then air cooled. The
hydrostat was neutralized to 5.5PH for the fermentation and hafted for solvent extraction and
yield calculation.

EXPERIMENT 6
TESTING FOR REDUCING SUGARS
Aim: to determine the presence of reducing sugars.
Procedure
The brisk testing was performed to test for reducing sugars using benedict’s solution.

EXPERIMENT 7
UV-VIS SPECTROSCOPY CHARACTERIZATION
Aim: to monitor the change in concentration of sugars over time and to identify the unknown
compounds
EXPERIMENT 8
Fermentation
Aim: to ferment most of the reduced sugars and produce ethanol.
17
Materials: conical flask, fermentation yeast, beaker, electronic balance, incubator, stirring rod,
hydrolyzed corncob
Procedure
The hydrolyzed corncob is neutralized to a PH of 5-6 and 4g of yeast was added. The mixture
was then stirred to ensure all the yeast dissolves and mix well. The conical flask was sealed using
a cotton wool and aluminum foil then incubated at 37.5 oC. Then ferment was the tested for the
presence of ethanol after 5 days of incubation using potassium permanganate.

EXPERIMENT 9
Distillation
Aim: to separate ethanol based on boiling point from the fermented solution.
Materials: Conical flask, heating element, thermometer, distillation column, beakers
Procedure:
The apparatuses were set based on the standard distillation procedure. The ferment was heated
and the first condensate was discarded, and ethanol was collected at 78 degrees Celsius. The
distillation was repeated to further purify the ethanol. The purity of ethanol was then measured
and determined from the density of the pure ethanol by a Hygrometer.

CHARACTERIZATION

FTIR characterization of 5% NaOH pretreated corncob

Grind the sample to a fine powder using a mortar and pestle. Mix 5% sample with 95% KBr
powder. Press the mixture into a disk using a KBr die press. Place the disk in the FTIR
spectrometer. Record the spectrum with 32 scans in the frequency range of 4000-400 cm-1 at a
resolution of 4 cm-1. Identify the compounds by comparing the FTIR spectrum to the standard
FTIR spectra of compounds.

For transmission measurements, a small amount of the sample can be mixed with Nujol mineral
oil and spread between two mid-infrared transparent windows. The windows are then placed in a
monochromator to transmit light from a timing laser. The position of the moving mirror is
tracked using the precisely known wavelength of the laser.

18
BLOCK FLOW DIAGRAM

Washing with Milling/Size

Raw Corncob Drying
hot water reduction

Delignification
Filtration detoxification Separation
T=85oC

Dilute Acid
Neutralization Filtration Fermentation
Hydrolysis

Ethanol Distilation

19
CHAPTER 4
RESULTS AND DISCUSION
EXPERIMENT 1

AUTOCLAVING

Results for alkali pretreatment

NaOH CHANGE IN % CHANGE IN % LIGNIN
CONCENTRATION % MASS MASS REMOVED
5 2.368 23.68 3.55
7 2.587 25.87 3.88
9 2.847 28.27 4.24
11 3.369 33.69 5.05
13 3.544 35.44 5.32
15 3.765 37.65 5.65
17 4.626 46.26 6.94
19 4.358 43.58 6.39
21 4.261 42.61 6.39

20
Results for sodium hydroxide pretreatment

% Lignin against %NaOH concentration

8
7
6
5
% Lignin Yield

4
3
2
1
0
4 6 8 10 12 14 16 18 20 22
% Naoh concentration

Discussion

The graph above indicates that the quantity of lignin extracted from corncob rises as the
concentration of NaOH increases, reaching its maximum at 17%. However, when the
concentration of NaOH exceeds 20%, the degree of delignification begins to decline due to the
hydrolysis of hemicellulose and cellulose by NaOH. Consequently, it becomes difficult to
separate lignin from the more valuable hemicellulose and cellulose.

Results for sulfuric acid pretreatment

sulfuric acid % Change in % change in % lignin
CONCENTRATION mass mass removed
0.5 1.388 13.88 2.08
1 1.874 18.74 2.81
1.5 3.712 37.12 5.57
2 4.212 42.12 6.31
2.5 6.087 60.87 9.13
3 7.325 73.25 10.99
3.5 7.129 71.29 10.54
4 6.834 68.34 10.25

Results for sulfuric acid pretreatment

21
 % lignin Yield against sulfuric acid %concentration
12

10

8
%lignin Yield

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
%Concentration of sulfuric acid

Discussion

According to the data presented, the amount of lignin extracted from corncob by Sulfuric acid
increases as the acid concentration rises from 0.5% to 3%. However, concentrations higher than
3% result in a decrease in the amount of lignin removed because the acid begins to break down
cellulose, making it harder to separate lignin from cellulose and hemicellulose. As a result, the
optimal concentration of acid for removing lignin from corncob is 3%.

EXPERIMENT 2 RESULTS

22
 Two-step pretreatement

Stove 2.92 6.51

Source of heating

Magnetic Stirrer 3.27 7.77

Autoclaving 2.368 6.925

Change in Mass

sodium Hydroxide 5% Sulfuric acid 1%

Steps Autoclaving Magnetic Stirrer Stove % Total

sodium Hydroxide
5% 2.368 3.27 2.92 28.75%
Sulfuric acid 1% 6.925 7.77 6.51 71.25%
% Total 31.22% 37.09% 31.68% 0.00%

Discussion
From the data presented magnetic stirrer shows highest efficiency in extraction by the higher
changes in mass in both the first pretreatment having 3.27g and the second pretreatment having
7.77g amounting to 45% of the initial mass 10g. however, sodium hydroxide removes an average
total of 28.75% and sulfuric acid and average total of 71.25%.

EXPERIMENT 3 RESULTS
Description Mass m(g)
Reduced Sugars Extracted 3.5565
Oligomers Extracted 2.0728
Residue (unhydrolyzed cellulose) 2.2845
Omitted on filter paper 0.8512
Total 8,7950
23
SOLVENT EXTRACTION

Discussion
The acetone forms a white precipitate with the hydrolyzed liquid filtrate and the formed
precipitate was soluble in water. This indicated that the precipitate was made of simple cellulosic
and hemicellulose sugars for example glucose and xylose were the most promising available
sugars.

EXPERIMENT 4 RESULTS
FEHLING’S TEST

Discussion
The Fehling’s reagent shows a pale-yellow color indicating the presence of reduced sugars such
as glucose and xylose. The result is confirmed by the formation of a white precipitate which was
insoluble in water.

24
EXPERIMENT 5 RESULTS
HYDRPLYSIS
Description Mass m(g)
Reduced Sugars Extracted 3.5565
Oligomers Extracted 2.0728
Residue (unhydrolyzed cellulose) 2.2845
Omitted on filter paper 0.8512
Total 8,7950

Total extracted Residue left Mass left at filter paper

6.3805 2.2845 0.8512

73.68% 25.97% 9.678%

25
 Depolymerization Effi ciency
7 6.3805
6
5
4
3
2.2845
2
1
0
0
Total extracted Residue left Mass left at filter paper

Discussion
The acetone added to the hydrolyzed corncob filtrate, formed a white precipitate which was then
filtered and dried. The dried precipitate weighed to 3.5565g and the dissolve oligomers in
acetone after recovering by evaporating excess acetone weighed to 2.078g adding them together
produces a 73.6% efficiency of the extracted fermentable sugars. However, considering the
sugars left on the filter paper the hydrolysis was 82.2% efficiency.

EXPERIMANT 6 RESULTS

BRISK TEST FOR REDUCED SUGARS

Discussion
A pale-yellow color was formed. This showed a positive brisk test for reducing sugars. The
result was the presence of glucose and xylose. This indicated that depolymerization was
successful as the monomeric sugars’ tests positive.

26
EXPERIMENT 7 RESULTS
UV-VIS SPECTROSCOPY CHARACTERIZATION

EXPERIMENT 8 RESULTS
FERMENTATION

Discussion
A pale-yellow precipitate was observed in the test tube showing the presence of ethanol. Ethanol
is the only primary alcohol that gives a positive test of the triido test due to the formation of
iodoform.

Chemical reaction

C2H5OH+4I2 + 2Na2 CO3 → CHI3 + CHOONa + 5NaI + 5H2O

EXPERIMENT 9 RESULTS
DISTILLATION

27
Discussion
The hydrometer floated at 0.9247g/mol. When compared with density tables of ethanol the
percentage purity of the ethanol is approximated to be 54 % v/v ethanol.

OVERAL DEPOLMERIZATION

CORNCOB → LIGNIN + HEMICELLULOSE+ CELLULOSE →GLUCOSE + XYLOSE+ DEAD POLYMERS

CELLULOSE → GLUCOSE+ DEAD POLYMERS
HEMICELLULOSE → XYLOSE+ HYDROFURUL+ DEAD POLYMERS
LIGNIN → AROMATIC ALCOHOL+ PHENOLS + DEAD POLYMERS

28
Discussion

The dark brick-red color in the first conical flask shows the presence of lignin. This shows the
impact of alkaline pretreatment of sodium hydroxide in breaking down the bonding between
lignin, hemicellulose and cellulose, making cellulose accessible for hydrolysis. The second
conical flask contains a golden yellowish color. This is a result of the cellulosic and
hemicellulose oligomers and reduced sugars such as; glucose, xylose and other sugars. Lastly,
the hydrolyzed has a pale yellowish color. This shows the presence of simple monomeric sugars
(glucose and xylose) and very few oligomers.

CHARACTORIZATION

5% NaOH pretreated sample reference FTIR spectroscopy

29
(Umar Asghar, (Received 27 July 2014; final version received 31 August 2014))

30
 Di
scussion
The bands at 1110cm-1, 1160.90cm-1, 1450cm-1, reflected the bent and stretched C-H for the
deformation bonds in lignin and hemicellulose. The 1700cm -1, 1800cm-1, and 1900cm-1 shows the
C=C, and C=O deformed bent and stretched bonds in the lignin, hemicellulose and cellulose.
(Yokoi, 2003) (Meszaros, 2007)

The 1160cm-1, 899.9cm-1, and 680.5cm-1 reflected the C=O, C-H, C-O-C, and C-O deformations
for the stretched vibrations of various groups in cellulose (Yokoi, 2003). The band at 1420cm-1,
to 1430cm-1 was connected to the crystalline cellulose structure, whereas the 898cm -1 was
connected to the amorphous are in cellulose (Akerholt, 2004)

Moreover, the 2840cm-1 was of the C-H asymmetric stretching vibrations in lignin and the

31
1124cm-1 was the C-H aromatic unit deformation syringyl vibrations and C=O stretching
vibrations (Popescu, 2007). The band at 1445cm-1 attributed to the O-H stretching vibrations, the
875cm-1 was of the glycosidic bonds in hemicellulose (Sills, 2012).

The 3403.9cm-1 and 3779.4cm-1 refers to the O-H stretched vibrations in cellulose and
hemicellulose. Therefore, the FTIR shows significant changes in the NaOH pretreatment method
by the loss of C=O groups and the observed amorphous cellulose structure and the increased
aromatic share in structure.

32
CHAPTER 5
ECONOMIC ANALYSIS

33
CHAPTER 6
CONCLUSION AND RECOMMENDATIONS

34
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