International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016)
Production of Ethanol from Waste Newspaper
Pooja H.#1, Rashmi A.#1, Sabeena K.#1, Abhijit Bhatkal#2, D. N. Sastry#3
#1
Dept. of Biotechnology, KLE Dr. MSSCET, Belgaum
Assistant Professor, Dept. of Biotechnology, KLE Dr. MSSCET, Belgaum
Udyambag, Belgaum -590008, Karnataka, India
#3
Assistant professor, Dept. of Pharmaceutical Biotechnology, KLE College of pharmacy, Belgaum, Karnataka,
India
#2
Abstract: The presence of conventional energy
sources are decreasing day by day and this inevitable
situation has leads us to search for alternate fuels.
The present work illustrates the synthesis of BioEthanol from waste papers in particular, newspapers,
since it contains 40-55% of cellulose contents. Several
experiments were carried out to describe the BioEthanol synthesis from waste papers by conducting
series of chemical and biochemical reactions
including acid pre-treatment, Delignification,
Distillation and Fermentation. This work also
summarizes the systematic study of Bio-Ethanol
synthesis by fermentation process and the purity
comparison of results obtained from various
lignocellulosic sources. The Bio-ethanol obtained by
treating waste papers with different concentration of
H2SO4 was analysed by Gas Chromatography (GC).
Alternately the by-product in the form of solid residue
obtained from the fermentation tank is used as a Solid
Fuel. This project demonstrates that Saccharomyces
cerevisiae can be effectively used for production of bio
ethanol from pre-treated waste paper.
Keywords — Bio-ethanol, GC, Waste
lignocellulose, Saccharomyces cerevisiae
paper,
I. INTRODUCTION
Energy consumption is inevitable for human existence.
There are various reasons for the search of an
alternative fuel that is technically feasible,
environmentally acceptable, economically competitive,
and readily available. The first foremost reason is the
increasing demand for fossil fuels in all sectors of
human life, be it transportation, power generation,
industrial processes, and residential consumption.
Depletion of world petroleum reserves and the impact
of environmental pollution due to increasing exhaust
emissions have led to the search for suitable
alternative fuels for diesel engines. The requirement of
fuels for the production of electricity and running of
vehicles is increasing day by day. Today every
country draws its energy needs from a variety of
sources. The sources can be broadly categorized as
commercial and non-commercial. The commercial
sources include the fossil fuels (coal, oil and natural
gas), hydroelectric power and nuclear power, while
the non-commercial sources include wood, animal
wastes and agricultural wastes. In an industrialized
country like, U.S.A., most of the energy requirements
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are met from commercial sources, while in an
industrially less developed country like India, the use
of commercial and non-commercial sources is about
equal.
Fuel ethanol as an alternative fuel is replacing the
fossil fuels and it has been attracting worldwide
interest because of the increasing demand for energy
resources. Ethanol (C2H5OH) is produced naturally by
certain micro-organisms from sugars under acidic
conditions at the pH level of 4 to 5. This alcoholic
fermentation process is used worldwide to produce
alcoholic drinks.
The ethanol industry of today utilizes raw materials
rich in saccharides, such as sugar cane or sugar beets,
and raw materials rich in starch, such as corn and
wheat. The concern about supply of liquid
transportation fuels, which has brought the crude oil
price above 100$/barrel during 2006, together with the
concern about global warming, have turned the
interest towards large-scale ethanol production from
lignocellulosic materials, such as agriculture and
forestry residues. Baker's yeast Saccharomyces
cerevisiae is the preferred fermenting microorganism
for ethanol production because of its superior and
well-documented industrial performance.
Bioethanol is produced by the biochemical reaction
called fermentation. Fermentation is a well-established
and widely used technology for the conversion of
grains and sugar crops into ethanol. It is intended for
mixing with gasoline to produce gasohol (90 percent
gasoline, 10 percent ethanol). This process requires
high cost and high energy.
One scheme considered for reducing costs of ethanol
production by fermentation is in finding less
expensive grains or sugars and a process that requires
less energy. Glucose produced by hydrolysis of an
abundant carbohydrate polymer called lignocellulose
is being considered for the former. Various studies
have been carried out in the production of bio ethanol
from the waste paper. The bio ethanol content depends
upon the various compositions in the waste paper. The
presence of 70.12±4.88% of carbohydrates
(holocellulose) makes waste paper a prospective and
renewable biomass for bio ethanol production. The
Glucose production was further enhanced by using
diluted sulphuric acid during pretreatment. Different
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incubation periods were tested for saccharification and
subsequent Bio ethanol fermentations were carried out.
The possibility of using waste paper as a cheap
feedstock for ethanol production arose from the wellpublicized concern about rising landfill costs resulting
from shrinking landfill capacity. Shrinking landfill
capacity is a result of tighter environmental controls
on their site, construction, operation and of the
unwillingness of communities to have new landfills
sited nearby. Tighter environmental regulations are
responsible for the premature closure of existing
landfills and higher costs for constructing new ones.
According to the National Solid Wastes Management
Association (NSWMA), half of the existing 6,034
landfills will be closed by 1995 and, assuming the
current rates of landfill closures and openings continue,
"disposal requirements will exceed existing capacity
by around 1998" (NSWMA 1988). The effect on
tipping fee costs is shown by the rise in the national
average landfill tipping fee between 1984 and 1988 by
a factor of 2.5 to $26.93/ton, a trend expected to
continue. Just examining the national average,
however, hides the problem's very regional nature,
which is seen in the broad range of local tipping fees
($4.75 to $120.00/ton) and regional averages
(Northeast $45.48, South $15.87, Midwest $17.95,
and West $13.06) (NSWMA 1988).
At 50.1 MM tons discarded in 1986, waste paper
accounted for 35.6% of the total municipal solid waste
(MSW) discarded, and these figures are expected to
rise to 66.0 MM tons and 39.1 %, respectively, in the
year 2000 (Franklin Associates, Ltd. 1988). Because
waste paper is the single largest material category in
the MSW stream, it is the main target of efforts to
reduce the MSW burden. This is evidenced by the
numerous laws being enacted and under consideration
by state and local governments aimed at increasing the
recovery and recycling of waste paper.
We will now focus on the effect that the physical and
chemical properties of waste paper will have on the
process design and cost, in comparison with a more
traditional wood-to-ethanol plant. The chemical
composition will determine the amount of
polysaccharide or sugar potential present and,
therefore, quantity of ethanol produced per ton of
paper. The amount of lignin present determines how
much energy can be produced from the feedstock to
supply the steam and electricity requirements of the
process. The physical properties of the waste paper
and the amount of extraneous mineral matter mixed in
with the waste paper will have an impact on the frontend processing or the milling and pretreatment steps
that prepare the material for the saccharification and
fermentation step.
Table 1: Composition of Waste paper samples
Because of the nature of the analysis, any materials
that burn but are not hydrolysed by concentrated
sulfuric acid end up in the lignin category. Plastics and
ink are examples. Those materials that neither burn
nor are hydrolysed by concentrated sulfuric acid end
up in the ash category. Examples are the inerts such as
clay in the fillers and coatings. Although the materials
in the lignin category cannot be converted to ethanol,
they can be burned to produce steam and electricity to
run the process, and any excess electricity can be sold.
The materials in the ash category have no value and,
in fact, are a liability because they must be moved
through the process and disposed.
The glucose is easily and efficiently converted into
ethanol, while the xylose is more difficult to convert.
The higher percentage of xylose in wood,
approximately 25%, makes it worthwhile to include
xylose fermentation in the process. But because of the
much lower amounts in waste paper, it does not
appear economical to include this step in the waste
paper process. Some of the xylose is consumed in the
production of enzymes, but most of it and the other
nonglucose sugars are anaerobically digested to
methane, which is burned for process energy. The
factors for converting each of the waste paper
categories used were based on the conversion of 90%
of the glucose content into ethanol product
approximately corresponding to the ethanol program
conversion efficiency goal.
II. MATERIALS AND METHODS
Waste newspapers were collected from in and
around college and hostel campus. In order to increase
the surface area of the paper they were cut manually in
to small pieces using scissors (300gms of these shreds
were weighed).
Fig 1: Collected Raw material
The shreds of the newspaper were then soaked in 6
liter (ratio of 1:20) of water for 24 hours. During this
period the fibers of newspaper loosens and it makes it
easier to separate the cellulose which is the major
component of newspaper.
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Fig 2: Shreds soaked in water
After completion of one day the water was filtered
and the paper was crushed mechanically and
converted to a pulp and dried in the shade.
Fig 3: Dried Shreds
Deinking Process: 6 liter of 15% H2SO4 was taken
in a plastic vessel of volume 8 liters. And dried pulp
was added to it. This mixture was kept for 24 hours
for the deinking process.
In the deinking process ink pigments were removed
from the slurry because the ink pigments may affect
the yield of ethanol. The ink used for printing in waste
papers are mostly carbon based one. It can be easily
eliminated by added concentrated sulfuric acid.
Fig 4: Deinking of the pulp
After deinking process the slurry was washed
thoroughly with water and dried again.
Estimation of Cellulose content: After the
completion of pre-treatment, it was essential to
determine the cellulose content in the sample because
it gives an idea about the appropriate volume of bioethanol obtained from the sources i.e., waste papers.
The Carboxyl Methyl Cellulose was used as a
standard component to determine the cellulose content
in the raw material. Cellulose undergoes acetolysis
with acetic/nitric acid reagent forming acetylated
cellodextrins which gets dissolved and hydrolysed to
form glucose molecules on treatment with 67% H2SO4.
This glucose molecule is dehydrated to form hydroxyl
methyl furfural which forms green colour product with
anthrone method and the colour intensity is measured
at 630nm.
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Acid Hydrolysis: The cellulose molecules are
composed of long chains of sugar molecules. In the
hydrolysis process, these chains are broken down to
free the sugar before it is fermented for alcohol
production. There are two major cellulose hydrolysis
processes a chemical reaction using acids, and an
enzymatic reaction. In acid hydrolysis method highly
concentrated acid can be used at lower temperatures
and atmospheric pressure. During this process the
cellulose will be converted into sugar components.
The pretreated pulp was separated into three parts
and then acid hydrolysis was carried out with different
concentration of H2SO4 namely 10%, 15% and 20%.
Estimation of glucose content: 3, 5Dinitrosalicylic acid (DNSA) is used extensively in
biochemistry for the estimation of reducing sugars. It
detects the presence of free carbonyl group (C=O) of
reducing sugars. This involves the oxidation of the
aldehyde functional group (in glucose) and the ketone
functional group (in fructose). During this reaction
DNSA is reduced to 3- amino- 5-nitrosalicylic acid
(ANSA) which under alkaline conditions is converted
to a reddish brown coloured complex which has an
absorbance maximum of 540 nm.
Fermentation: Fermented can be performed as a
batch, fed batch or continuous process. The choice of
most suitable process will depend upon the kinetic
properties of microorganisms and type of
lignocellulosic hydrolysate in addition to process
economic aspects. After checking the pH level the
slurry was weighed and poured into the fermentation
tank. Then Saccharomyces cerevisiae was added in to
the fermentation tank and mixed well. The
fermentation process was an anaerobic batch type and
was maintained in the dark room for 3 days at pH 4.
Fig 5: Fermentation
Distillation: After the fermentation stage was
completed the clear liquid in the upper layer should be
collected. The ethanol and other constituents present
in the fermentation tank should be separated by the
filtrate. The fermented liquor should pour in to the
distillation column. The temperature range between
85-980C was maintained in the distillation column
setup. At this temperature ethanol has evaporated. At
the beginning the ethanol should come along with
some of the water vapour. It is impossible to measure
correctly the volume of ethanol present in the solution.
So we obtained ethanol only by reflux method.
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C. SIMPLE DISTILLATION
Fig 6: Distillation process
Alcohol detection test: The standard procedure is
applied.
GC analysis: The distilled samples were forwarded
to Regional Medical Research Centre, Belgaum for
qualitative and quantitative analysis of ethanol in the
samples.
Fig 8: Samples obtained after the distillation
process
D. GAS CHROMATOGRAPHY
The results obtained after subjecting the samples to
GC analysis.
III. RESULTS AND DISCUSSION
A. COMPARISON OF GLUCOSE CONTENT AT
VARIOUS CONC. OF H2SO4
By using DNSA method the glucose content at
various concentration of H2SO4 was estimated by
plotting the standard graph initially. The result
obtained for the various concentrations of sample from
UV Visible spectrophotometer at 540 nm were plotted,
by which the percentage of glucose was calculated.
Table 2: Represents % of glucose in different samples
Sl. No.
Samples
% of glucose
1
10% dil.
30.4
2
10% conc.
24.4
3
15% dil.
29.6
4
15% conc.
23.6
5
20% dil.
28.4
6
20% conc.
22.4
Fig 9: Results obtained for 10% washed samples
B. ALCOHOL DETECTION TEST
The disappearance of the red colour of chromic acid
and the formation of a blue green colour of Cr (III) ion
indicates a positive test. Fig. 7 indicates the presence
of blue green colour; hence we can conclude that the
sample contains alcohol and there may be presence of
ethanol.
Fig 10: Results obtained for 10% unwashed
samples
Fig 7: Ethanol confirmation test
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Fig 11: Results obtained for 15% washed samples
Fig 14: Results obtained for 20% unwashed
samples
From the GC results it was observed that sample
treated with 10% H2SO4 yielded better results
compared with the samples having 15 and 20% H2SO4
treated distillates.
The area under the curve for 10% sample indicated
this observation and this was higher in comparison
with the other samples. For 100 ml of fermentation
liquor 40 ml of ethanol was obtained with a purity of
68%.
Fig 12: Results obtained for 15% unwashed
samples
Fig 13: Results obtained for 20% washed samples
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IV. CONCLUSIONS
The present investigation has proved to be
successful in implementing the Bioethanol production
from waste papers of various cellulosic contents as
raw materials using Saccharomyces cerevisiae. The
reaction period for pre-treatment, hydrolysis,
fermentation are optimized to get the maximum
conversion of lignocellulosic materials into ethyl
alcohol. Experimentation on Bioethanol production
has been done using various concentration of H2SO4.
The highest yield of ethanol was observed for the
sample pretreated with 10% of concentrated H2SO4.
For 100 ml of fermentation liquor 40 ml of ethanol
was obtained. The purity of ethanol obtained was 68%.
This proves that the utilization of waste paper as a raw
material for production of biomass based fuels both
enhances the economic potential. The ethanol
synthesis from waste papers may replenish the fuel
availability and it may lead to the sustained
development.
ACKNOWLEDGMENT
We would like to express our immense gratitude to
our guide Mr. Abhijit Bhatkal and Prof. D. N. Sastry
(KLE College of Pharmacy, Belgaum) for their
support. Lastly, we also would like to thank the H.O.D.
and staff of Biotechnology department for their kind
co-operation.
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