AU J.T. 9(2): 106-110 (Oct.

2005)

The Production of Ethanol from Maize Cobs and Groundnut Shells

U.G. Akpan, A.S. Kovo, M. Abdullahi, and J. J. Ijah*
Department of Chemical Engineering, Federal University of Technology
Minna, Nigeria

Abstract
The possibility of producing ethanol from biomass such as maize cobs and
groundnut shells was investigated. Different concentrations of sulphuric acid (H2SO4)
were used to determine the acid concentration that could produce an optimal yield of
glucose. The results revealed that 4.5M H2SO4 produced the optimal yield of glucose
and ethanol. This acid concentration was then used for the study of temperature effects
on yield of glucose. The results indicated that glucose yield increased with temperature
within the experimental set-up. The maize cobs and groundnut shells were mixed at
various ratios and pretreated to remove all extractives. The ratio of 3:1 of maize cobs
to groundnut shells and at 4.5M acid gave a better glucose yield than those obtained
from individual biomass. The ultimate product (glucose) was hydrolyzed and 8%
ethanol was obtained within three hours.
Keywords: Alcohol, glucose, biomass, hydrolysis, fermentation.

Introduction used as a solvent for chemicals. Ethanol is used

The rapid growth of industries and
technological advancement in the world call for
development in the chemical sector. The
production of industrial chemicals will enhance
the economic progress of any nation. Ethanol,
one of the important industrial chemicals, can
be produced extensively from biomass such as
maize cob and groundnut shell. The main
constituents of this class of crop by-product are
cellulose (Chang, et al. 1981) and
hemicelluloses, making them lignocelluloses
(Cowling 1976) that can be excellent energy
sources.
The practice of mechanized farming has
led to extensive discharge of agricultural
wastes that have had negative effects on the
environment. The utilization of such wastes has
been a source of concern to many researchers
(Oyenuga 1959; Akpan 1999; Amosun 2000).
Therefore, this work was designed to look into
the possibility of converting some of such by-
products into industrial chemicals of economic
importance. Ethanol is one such chemical. It is
* Department of Biological Sciences, Federal
University of Technology, Minna, Nigeria
as an intermediate in the production of liquid
detergents. It is also used in the manufacture of
drugs, plastics, polishes, plasticizers, perfumes,
cosmetics, rubbers, accelerators, and cellulose
nitrate. It is further used as an anti-freeze.
Ethanol produced from regenerable sources is
an attractive petrochemical feedstock in
petroleum for poor countries (Gordon, et al.
1979). The various uses of ethanol and the
importance of ridding the environment of the
harmful effects of these agricultural by-
products (biomass) underscore the significance
of this work.
Ethanol is produced from palm wine by
fermentation process (Harris 1963).
Fermentation is one of the oldest processes
known to man, and it is used in making a
variety of products including foods, flavorings,
beverages, pharmaceuticals, and chemicals.
Ethanol is made from a variety of products
such as grain, molasses, fruit, cobs, and shell;
its production, excluding that of beverages, has
been declining since the 1930s because of the
low cost (Othman 1981). In 1975, only
76106L of proof industrial ethanol were
produced by fermentation compared to
7.95106L by synthesis.

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AU J.T. 9(2): 106-110 (Oct. 2005)
During 1974, Nigeria was spending N 2
million annually on spirits and alcohol
(Madrella, et al. 1981). This expenditure
represents a big market for a country like
Nigeria, with a population of over 120 million
people. A crude estimate of the total market for
alcoholic beverages in Nigeria is about
2,500,500 L/year. Therefore, provision must
be made to balance the shortfall to complement
the imported, hence the need for this work.
Neverthless, the production of chemical
feedstock from biomass making use of locally
sourced material that is very cheap and within
reach can be accomplished (Eweke, et al.
1979). In this work, agricultural wastes, which
are readily available, were used for ethanol
production.
Methodology
Collection and Processing of Substrate Used
Maize cobs and groundnut shells were
collected in polythene bags from the farm of
Government Technical School, Kontagora,
Niger State, Nigeria and transported to the
laboratory. A serrated disc grinder was used to
reduce the maize cobs and groundnut shells
into very small sizes of particle. These particles
were then sieved to obtain average particle
sizes of 300m in diameter. The cellulose was
isolated by the procedure described by
Layokun (1981). To 10g of each sample of the
agricultural waste was added 20ml of diethyl
ether in a 250ml Erlenmeyer flask in order to
remove extractives and the residue left was
washed with distilled water. 20ml of 14M
H2SO4 was added to the residue to isolate
lignin. The hemicelluloses and cellulose were
dissolved leaving lignin as a hard precipitate.
This modified procedure described by Layokun
(1981) was used to isolate the sample of maize
cobs and groundnut shells individually. This
procedure was repeated for mixture of both
samples in the ratio 1:1, 1:2, 1:3 and 3:1 in
order to obtain best mixture that could produce
high quality of ethanol.
To determine the effect of different acid
concentrations on the hydrolysis 2M solution
of concentrated H2SO4 was prepared and 10g of
the leached maize cobs and groundnut shells
107
were added to 50ml of the 2 M solution of
H2SO4, respectively under room temperature in
a stirred 250ml conical flask which serve as a
reactor. This reaction was allowed to proceed
for 2.5 hrs. Some quantities of the hydrolyzed
sample at an interval of 30 min was collected
and filtered, the resulting filtrates analyzed for
the glucose using a refractometer (Abbe 60).
The entire procedure was repeated for
3M, 4M, 4.5M and 5M of H2SO4 and the
various acid concentrations recorded. Using the
best concentration of H2SO4 (4.5M), a mixture
of maize cobs and groundnut shells in the ratio
of 1:1, 1:2, 2:1, 1:3 and 3:1 were leached and
the hydrolyzed samples were filtered. The
resulting filtrate was analyzed for glucose and
the best ratio determined.
Using the best maize cobs to groundnut
shells of 3:1, the effect of temperature on its
hydrolysis was investigated using a
thermostated water bath (Gallenkamp,
England) at 40o, 50o, 60o, 70o and 80oC 4.5M
H2SO4 was used for the hydrolysis, and 10g of
the mixture were pretreated by a modified
procedure described by Layokun (1981). The
reaction was allowed to proceed for 2.5 at
constant temperature.
The resulting hydrolyzed sample was
filtered leaving a filtrate with high percentage
of glucose and this acted as the substrate. The
substrate in the fermentation medium was
inoculated with S. cerevisiae as the started
culture and the time noted. The conical flask,
which has been sterilized, was tightly sealed
with glass stopper to avoid air entering the
reactor medium. The entire process was
allowed to remain for three hours. Every 30
minutes, a sample was withdrawn and both
glucose and the ethanol concentration were
determined using a refractometer.
In order to obtain a large quantity of pure
ethanol, the quantity of maize cobs and
groundnut shells were increased using the same
ratio (3:1). The entire hydrolysis process was
carried out to produce large quantity of
glucose, which was fermented simultaneously.
After the fermentation process, alcohol
was recovered using a simple batch distillation
method. Confirmatory tests were carried out to
ascertain that the distillate was actually
ethanol.
AU J.T. 9(2): 106-110 (Oct. 2005)

Results and Discussion There was a drop in glucose

concentration for both biomasses when
Acid hydrolysis of maize cobs and hydrolyzed at 5M H2SO4. This could be
groundnut shells at different acid attributed to the fact that at a higher
concentrations and at ambient temperatures concentration of acid, glucose can be converted
showed an increase in glucose concentration to levulinic and formic acid (Ghose 1956),
with time (Tables 1 and 2). The concentration which leads to decrease in glucose yield. These
of glucose was higher for both biomass when then suggest that highest glucose yield can be
the concentration of 4.5M H2SO4 was used. obtained at moderate acid concentration of
The glucose yield of maize cobs was higher 4.5M H2SO4, which also serves as the optimal
than that of groundnut shells, and ranged from pH condition for yeasts to metabolize its
0 to 0.89g/cm3 for maize cobs (Table1) and 0 substrate (Fan, et al. 1980; Adams and Moses
to 0.53g/cm3 for groundnut shells (Table2) 1995).
Acid hydrolysis of maize cobs and
Table 1. Glucose yields for acid hydrolysis of groundnut shell at varying temperature using
maize cobs at ambient temperature using the optimal acid concentration of 4.5M H2SO4
different acid concentrations brought about increase in glucose yield with
time as shown in Tables 3 and 4.
Time Glucose yield (g/cm3 Tables 3. Glucose yields for acid hydrolysis of
[min] 2Ma 3Ma 4Ma 4.5Ma 5Ma maize cobs at varying temperatures using
0 0 0 0 0 0 4.5M H2SO4
6 0.02 0.03 0.04 0.05 0.02
12 0.07 0.11 0.14 0.17 0.13 Time Glucose yield (g/cm3)
18 0.15 0.19 0.20 0.28 0.26 (min) 40oC 50oC 60oC 70oC 80oC
30 0.21 0.24 0.26 0.46 0.35 0 0 0 0 0 0
60 0.33 0.34 0.42 0.67 0.49 6 0.11 0.15 0.21 0.35 0.43
90 0.39 0.41 0.53 0.79 0.57 12 0.30 0.35 0.50 0.62 0.67
120 0.42 0.46 0.60 0.86 0.60 18 0.50 0.61 0.65 0.81 0.85
150 0.43 0.48 0.64 0.89 0.02 30 0.71 0.73 0.74 0.76 0.87
60 0.73 0.74 0.78 0.80 0.93
a = acid concentration 90 0.75 0.76 0.79 0.83 0.95
120 0.78 0.78 0.82 0.84 0.97
Table2. Glucose yields for acid hydrolysis of 150 0.80 0.83 0.85 0.87 0.98
groundnut shells at ambient temperature
using different acid concentrations Table 4. Glucose yield for acid hydrolysis of
groundnut shells at varying temperatures
Time Glucose yield (g/cm3) using 4.5M H2SO4
(min) 2Ma 3Ma 4Ma 4.5Ma 5Ma
Time Glucose yield (g/cm3)
0 0 0 0 0 0 (min)
6 0.01 0.02 0.03 0.04 0.05 40oC 50oC 60oC 70oC 80oC
12 0.04 0.05 0.06 0.07 0.09 0 0 0 0 0 0
18 0.06 0.08 0.10 0.14 0.15 6 0.09 0.11 0.14 0.19 0.21
30 0.10 0.13 0.17 0.28 0.23 12 0.20 0.23 0.30 0.35 0.38
60 0.17 0.21 0.29 0.37 0.37 18 0.31 0.34 0.40 0.43 0.47
90 0.23 0.28 0.36 0.43 0.45 30 0.42 0.44 0.45 0.49 0.52
120 0.28 0.36 0.40 0.49 0.45 60 0.42 0.45 0.47 0.50 0.54
150 0.34 0.37 0.43 0.53 0.46 90 0.43 0.47 0.49 0.51 0.55
120 0.44 0.48 0.50 0.52 0.56
a = acid concentration 150 0.45 0.49 0.51 0.53 0.63

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AU J.T. 9(2): 106-110 (Oct. 2005)

At 80OC, glucose yield for both biomass glucose is due to the fact that, during
was at the peak and ranged 0 - 0.98g/cm3 for fermentation the yeast (S. ceresiae) utilized the
maize cobs and 0 - 0.63g/cm3 for groundnut glucose as a source of carbon and energy,
shells. This indicates that, at higher whereas ethanol is produced as a result (Nester,
temperatures and at moderate acid et al. 1995). A test was carried out using
concentrations, the yield of glucose increases. iodoform and dichromate solution confirmed
Consequently, acid hydrolysis of a mixture of that the distillate was ethanol.
maize cobs and groundnut shells at different
ratios using 4.5 M H2SO4 at ambient Table 6. Glucose yield for hydrolysis for
temperature shows an increase in glucose yield mixture of maize cobs and groundnut
as shown in Table 5. shells in ratio 3:1 using 4.5M H2SO4 at
different temperatures
Table 5. Glucose yield for acid hydrolysis for
mixture of maize cobs and groundnut shells Time Glucose yield (g/cm3)
using 4.5M H2SO4 at ambient temperature (min)
40oC 50oC 60oC 70oC 80oC
0 0 0 0 0 0
Time (min) Glucose yield (g/cm3)
6 0.03 0.10 0.25 0.28 0.31
1:1 1:2 2:1 1:3 3:1 12 0.28 0.40 0.58 0.62 0.65
0 0 0 0 0 0 18 0.56 0.62 0.68 0.76 0.94
6 0.05 0.04 0.09 0.01 0.12 30 0.83 0.86 0.90 0.93 1.07
12 0.13 0.10 0.17 0.04 0.22 60 0.85 0.89 0.92 0.95 1.25
18 0.23 0.19 0.33 0.06 0.36 90 0.86 0.90 0.95 0.98 1.29
30 0.36 0.25 0.43 0.14 0.51 120 0.88 0.92 0.96 1.00 1.43
60 0.54 0.39 0.63 0.23 0.73 150 0.90 0.93 0.97 1.01 1.53
90 0.65 0.49 0.75 0.31 0.86
120 0.71 0.55 0.83 0.35 0.89 Table 7. Percentage of ethanol produced and
150 0.75 0.58 0.86 0.36 0.94 glucose concentration

The ratio 1: 3 (maize cobs, groundnut Time Specific Ethanol Glucose

shells) shows a drastic decrease in glucose (h) gravity (%) concentration
yield from 0to0.36g/cm3 when compared to (g/cm3)
other ratios. This is probably due to high 0 1.00 0 1.53
amount of groundnut shells with structures, 0.5 1.008 0.6 1.32
which contain high degree of crystallinity and 1.0 1.014 2.6 1.16
polymerization thereby, limit accessibility to 1.5 1.021 3.8 1.10
acid attack. Ratio 3:1 of maize cobs and 2.0 1.028 4.7 0.93
groundnut shells and 4.5M H2SO4 at varying 2.5 1.038 8.2 0.68
temperature shows an increase in glucose yield, 3.0 1.043 8.0 0.06
as shown in Table 6. Though glucose yield
increases with temperature, it is important to
note that it may denature at temperature above Conclusion
its boiling point. Therefore, the experiment
above 80oC will not be advantageous. The results obtained from the experiment
During fermentation, the amount of reveal that glucose is present in a reasonable
ethanol produced and glucose used were amount in maize cobs and groundnut shells
determined and the results are shown in Table mixed together in the ratio 3:1. If the product
7. The ethanol in the product increased from 0 (glucose) is fermented under the stipulated
to 8.2, while that of glucose decreased from experiment conditions with Saccaharomyces
1.53g/cm3 to 0.07g/cm3 after 2.5 hours of the cerevisiae (bakers yeast), a substantial amount
fermentation. The increase in ethanol of ethanol, which is used as a chemical
production and decrease in the amount of feedstock, will be produced. Thus, the
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AU J.T. 9(2): 106-110 (Oct. 2005)
importation of ethanol can be reduced if
substantial energy is devoted to the production
of ethanol from biomass. This will also have a
multiplier effect such as jobs for the
unemployed.
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