CHAPTER II

REVIEW OF RELATED LITERATURE

Renewable energy sources on Earth provide alternatives and solutions to the major
circumstances that humans are experiencing today.

Renewable resources (such as solar

radiation, wind, and biomass) will replenish themselves within lifetime and may be used with
suitable technology to produce sufficient energy quantities. In fact, they are more evenly
distributed than fossil and nuclear resources. (Gupta & Demirbas, Gasoline, Diesel and Ethanol
Biofuels from Grasses and Plants, 2010)
From one perspective, renewable energy into the energy system of human settlements on
Earth is nearly 100%, in which some of these energy sources have been used by humans for over
five thousand years. The energy system seen by humans is dominated by the environmental heat
associated with the greenhouse effect, which captures solar energy and stores it within a surfacenear sheet of topsoil and atmosphere around the Earth. Only 0.02% of this energy system is
currently managed by human society. Within this economically managed part of the energy
sector, renewable energy sources currently provide about 25% of the energy supplied. A large
part of this renewable energy is in the form of biomass energy, either in food crops or in
managed forestry providing wood for industrial purposes or for incineration (firewood used for
heat and cooking in poor countries, or for mood-setting fireplaces in affluent countries, residue
and waste burning in combined power and heat plants or incinerators). A global average of 222
W/cap., the traditional use of biomass for combustion is still the dominating use of renewable
energy, although it takes more efficient forms in many industrialized countries. (Sorensen, 2004)
During the process of photosynthesis, plants absorb atmospheric carbon dioxide (CO2)
and ground water to produce oxygen (O2) and biomass. Dry biomass mostly contains carbon,

hydrogen and oxygen with overall chemical formula

[ CH 1.4 O0.6 ] n

as a carbohydrate polymer.

The fuel and feed use of biomass results in the release of CO2 back into the atmosphere. CO2 is
then reused by the growth of the next crop of biomass in a cyclical manner. Because the annual
average concentration of CO2 in the atmosphere theoretically remains constant in this cycle,
biomass energy is expected to become one of the key sources of sustainable energy in the future.
There has been an increase in interest in the production of biomass. Also, replacing fuel with
biomass would prevent the increase of CO2 in the atmosphere and would help meet the
obligations of the Kyoto Protocol.
Biomass refers to the nonfood part of plants. Various biomass resources include woody
and herbaceous species, wood wastes, agricultural and industrial residues, waste paper,
municipal solid waste, biosolids, waste from food processing, animal wastes, aquatic plants and
algae, and so on. Major organic components of biomass can be classified as cellulose,
hemicelluloses, and lignin.
World production of biomass is estimated at 146 billion metric tons per year, mostly in
the form of wild plant growth. However, there is a significant potential for producing biomass
from farm crops, as some farm crops and trees can produce up to 20 metric tons of biomass per
acre each year. (Gupta & Demirbas, 2010)
Biomass is rich in carbon but is not yet a fossil material. All plants and animals in the
ecological system belong to biomass. Furthermore, nutrient, excrement, and bio-waste from
households and industry are biomass.
If the biomass has a very high water content (e.g., liquid manure, freshly harvested
plants), it is best to select and accept a process which provides only about 70% of the energy

resulting from the combutsion of dry material. As an advantage, the residues can be easily
retirmed to nature, especially since no materials enriched with minerals and this plantincompatible ash are generated. If biomass is to serve as a source for liquid fuel, it is best to
produce ethanol and/or methanol via alcoholic fermentation. This process is more efficient than
anaerobic fermentation referring to the hectare yield. (Deublein & Steinhauser, 2011)
The most commonly used biofuel, ethanol, is currently produced from the food portion of
crops (sugarcane, corn, and other grains). To reduce the pollution from automobile exhausts,
ethanol is added to gasoline in many cities. The recalcitrance (i.e., high resistance to
decomposition or alteration) of cellulosic materials is mainly responsible for the poor efficiency
of cellulose to ethanol conversion. Hence, ethanol produced from biomass at present is more
expensive than gasoline. Research efforts are underway to produce cost-effective ethanol from
grasses, trees, bark, sawdust, paper, and farming wastes. (Gupta & Demirbas, 2010)
Ethanol (C2H5OH) is a clear, colorless, flammable chemical. It is also biodegradable,
high-octane chemical compound made from the sugars found in crops such as corn, sugar beets,
sugar cane, and from almost any plant matter capable of fermentation.

Ethanol has been

produced and used from several industrial applications from detergents and pharmaceuticals to
alcoholic beverages, and has been used as transportation fuel for more than a century. Nicholas
Otto used ethanol in the internal combustion engine invented in 1897 (Rothman et. al., 1983).
However, ethanol did not have a major impact in the fuel market until the 1970s, when two oil
crisis occurred in 1973 and 1979. Since the 1980s, ethanol has been a major actor in the fuel
market as an alternative fuel as well as an oxygenated compound for gasoline (Taherzadeh,
2008).

It has been used as fuel or additive since the early 1900s during the time of Henry Ford
and his creation, the Ford Model T. Almost every gallon of gasoline consumed in the united
states today contains fuel ethanol. Unlike gasoline which came from fossil fuels, ethanol is
biodegradable. It quickly breaks down into harmless substances if spilled. Adding small amounts
of ethanol to gasoline, usually less than 10 percent, will deliver advantages compared to gasoline
only. (agclassroom.org, 2008)
Currently, ethanol is the most widely used liquid biofuel. It is produced by fermentation
of sugars, which can be obtained from natural sugars, starches, or cellulosic biomass. The most
common feedstock is sugarcane or sugar beet, and the second common feedstock is cornstarch.
Currently, cellulosic biomass use is very limited due to expensive pretreatment that is required
for breaking the crystalline structure of cellulose. Bioethanol is already an established
commodity due to its ongoing nonfuel uses in beverages and in the manufacture of
pharmaceuticals and cosmetics. In fact, ethanol is the oldest synthetic organic chemical used by
mankind. According to Gupta and Demirbas book regarding ethanol, United states has the
highest global ethanol production with 43.8% in 2008 while Brazil in second place with 33.9%
(Gupta & Demirbas, 2010). According to Moreira, et al., USA uses corn for ethanol production
while Brazil uses sugarcane.
According to Wyman (1996) and Breidenich, et. al. (1998), applications of bioethanol has
very limited or almost no net emission of CO 2 and is able to fulfill the Kyoto Climate Change
Protocol (1997) to decrease the net emission of CO2. Ethanol reduces the emissions of carbon
monoxide and other toxic pollutants. It keeps engines running smoothly without the need for
other chemical additives. Because ethanol is made from crops that absorb carbon dioxide and

give off oxygen, it helps reduce the total volume of greenhouse gas emission by planting more
crops for ethanol production.
Ethanol is produced from a variety of feedstocks. It can be produced synthetically from
oil and natural gas, or biologically from sugar, starch, and lignocellulosic materials. The
biologically produced ethanol is sometimes called fermentative ethanol or bioethanol.
Fermentative ethanol is produced from grains, molasses, sugarcane juice, fruits, surplus wine,
whey and some other similar sources, which contain simple sugars and their polymers.
According to Bunge & Newman (2015), Ethanol production in 2014 increased by about 6.2
billion liters, with a total produce of 94 billion liters/year at the end of the period.
According to Licht (2006), synthetic ethanol as part of the world ethanol production was
less than 4% in 2006, down from 7% in the 1990s. The increase in oil price induces a decrease in
ethanol price, which affects the economic competition of synthetic ethanol production. The
increase in ethylene prices in 2005 was $1000 per ton, while ethanol costs $500 per ton during
that time. Furthermore, the theoretical yield of ethanol from ethylene is only 1.64 kg/kg, and so
the price of raw materials (ethylene) was higher than that of the product (ethanol). Seemingly,
bioethanol is more economically feasible to produce rather than synthetic.
The worlds bioethanol supply is mainly derived from US corn or Brazilian sugarcane.
Corn and other grain prices have soared internationally, and the corn-to-ethanol industry has
been blamed for driving up food prices worldwide. These facts are supported by the Food and
Agriculture Organization of the United Nations and the World Bank, in which they stated that
one of the reasons why theres soaring of world food prices is the increased demand for biofuels.
(Gupta & Demirbas, Gasoline, Diesel and Ethanol Biofuels from Grasses and Plants, 2010)
Cellulose from biomass are the key materials in ethanol production, The initial process

would require hydrolysis (can be acid or enzymatic hydrolysis) to convert it to glucose (C 6H12O6)
before fermentation to ethanol.
Biomass/crops

Fermentation

CH3CH2OH (Ethanol)

The necessary processes in converting fermentable sugar from starchy raw materials are
usually milling, and hydrolysis. Specifically, converting starch into sugar monomers would
require a two-stage hydrolysis treatment. The first stage involves liquefaction of large starch
molecules to oligomers, and then second stage is saccharification process of the oligomers to
sugar monomers.
Sugar(s)

Microorganisms

Ethanol + By-products

Sugar compounds mainly hexose and pentose found in sugarcane and molasses, and
starchy materials (e.g. corn, wheat) are the raw components used for bioethanol production.
Microorganisms that produces ethanol utilizes general sugars that includes glucose, fructose,
galactose, and mannose and also number of disaccharides. Microorganisms act as catalyst in the
process.
C6H12O6 (Hexose)

Microorganisms

2C2H5OH (Ethanol) + 2CO2

The theoretical yield of ethanol is 0.51 g/g if entire sugar is converted into ethanol based
on the reaction above. This means that if a 1.0 g of glucose is fermented, the ethanol yield will be
just 0.51 g. However, the actual yield of ethanol is 90-95% of theoretical yield, due to conversion
of by-products such as glycerol and acetic acid.
On the other hand, pentose has a relatively larger yield than hexose. It would require two
process namely pentose phosphate pathway and glycolysis.

3C5H10O5 (Pentose)

Microorganisms

5C2H5OH (Ethanol) + 5CO2

Six-carbon sugar, or hexose can be readily fermented to ethanol by common

microorganisms such as yeast (Saccharomyces cerevisiae). Five-carbon sugar (pentose), requires
special organisms that has been genetically engineered that can ferment it easily to ethanol, and
the process of conversion is relatively slow compared to hexose. Pentose molecules comprise a
good percentage of available sugars (as implied from the chemical equation above), and so the
ability to recover and ferment them into ethanol is important for efficiency and economics of the
process.
Raw Materials
Milling & size
reduction
Large polymer structures
Pretreatment
or liquefaction
Small polymers
Hydrolysis or
saccharification
Sugar solution
Detoxification

Fermentation

Yeast
Fermented solution

Distillation
Solid separation,
evaporation, drying
Dried by-products

Ethanol (~90-95%)

Wastewater
Dehydration
Ethanol
(>99%)

Fig 1. Schematic for ethanol production (Taherzadeh & Karimi, 2008)

An experiment conducted in Brazil, by CENBIO (Brazilian Reference Center on
Biomass), named as BEST (BioEthanol for Sustainable Transport) Project that aimed to promote
the ethanol usage, replacing diesel, in the urban public transport. They evaluated ethanol usage as
diesel fuel replacement in public transport buses through a comparative study of the operational
output of the experimental fleet taking as reference an equivalent diesel powered bus. The diesel
engine that was converted to ethanol engine was developed by Scanias Swedish company. The
manufacturer indicated that the adaptation of the diesel engine to ethanol doesnt require
significant changes. The modifications done resulted to a compression rate of 28:1, with
electronic injection and injectors with bigger volumetric capacity. In addition to this information,
the engine to be used also attends to the EURO 5 specifications. Their study mentioned that the
use of ethanol in these engines required an additive of 5% because ethanol lack the auto-ignition
by compression property, which is the technology from the diesel cycle engines. The project was
also conducted simultaneously in Sweden. Their data showed that the average consumption of
the ethanol buses was about 0.697L/km; on the other hand, diesel buses average consumption
was 0.413L/km. The costs of the kilometers travelled were equivalent, about 0.373/km for
ethanol against 0.376/km for diesel. In the environmental viewpoint, they estimated a reduction
of more than 80% of the emissions of gases responsible for the global warming, 90% of
particulate material and 62% of NOx released in the atmosphere. Also, it will not have emission
of Sulphur that composes SOx, responsible for acid rain. The reduction of local pollutants
emission reduces the occurrence of cardio-respiratory diseases, that must be taken into account,
mainly in the metropolitan regions where the population is plentiful, there is great concentration

of vehicles and atmospheric pollution sources. They concluded that the bus consumes around
60% more ethanol than diesel to go through the same distance. Although it consumes more
ethanol fuel, the price difference of diesel fuel and ethanol fuel is about 50% with ethanol being
the cheaper one. (Moreira, et al., 2008)
The Recent researches focusing on lowering the concentration of toxic components in
combustion product and decreasing fuel consumption by using renewable, sustainable and nonpolluting fuels. (Al-Baghdadi, 2004) The stringent pollution regulations and increasing energy
demand as a result of technological development in the world promote research on alternative
fuels. (S.Y. Liao, 2005)
The high heat of vaporization of ethanol and their high octane rating have made them
preferred fuel for use in high compression ratio, high output SI engines. High octane values
which can permit significant increase of compression ratio and high heats of evaporation which
can provide fuel-air charge cooling and density increase and thus higher mass throughout. (P.W.
McCallum) The alcohol-gasoline blended fuels can effectively lower the pollutant emission
without major modifications to engine design. (B., 1984) (F., 1996)
The increase of ethanol blending leads to slightly increase the Engine power output,
torque and significantly increase the Specific fuel consumption (SFC). CO and HC emission
decreases dramatically, CO2 and Nox emissions decrease significantly. It was also observed that
the increase of ethanol blending allows the engine to operate at higher compression ratio without
knock occurrence. (Manikandan, 2013)
As the Ethanol Content in the blended fuel increases power also increases slightly when
compared with E0 (Zero Ethanol Content) fuel, the power increases of 1.2%, 2.5% and 4% are
obtained with E10 (10% Ethanol Content), E20 (20% Ethanol Content) and E30 (30% Ethanol

Content) fuels respectively. This is due to several reasons ethanol as an oxygenated fuel, so
complete combustion is possible, the heat of evaporation of ethanol is higher than that of
gasoline. High heat of evaporation can provide fuel-air change to cool and density to increase, so
volumetric efficiency is increased ultimately power increases slightly. (P.W. McCallum)
The SFC (Specific Fuel Consumption) increases with increase of ethanol content in the
blend. The reason is the heating value of ethanol is lower than that of gasoline. The increase of
4%, 8.5%, 13.2% in the SFC Observed when running with E10, E20 and E30 respectively.
(Manikandan, 2013)
Ethanol containing oxygen is mixed with gasoline, so the combustion of the engine
becomes better ultimately it reduces the CO emissions. The values of CO emissions are about
3.8% 3.36%, 2.9% and 2.47% forE0, E10, E20 and E30 fuel respectively. (Manikandan, 2013)
The CO2 emission decreases with when ethanol blend increases. Because the ethanol
contains lower carbon atoms than gasoline it gives net lower CO2. The values of CO2 are about
13.5%, 13.1%.12.6% and 12.2% for E0, E10, E20 and E30 fuel respectively. (C.W. Wu, 2004)
Increase of ethanol content in the blend fuel up to 30%, the CO and HC emissions
decrease because ethanol contains an oxygen atom, It can be treated as a partially oxygzied
hydrocarbon.
Ethanol has high heat of vaporization compared to gasoline so the mixture temperature at
the end of intake stroke decreases and ultimately causes temperature to decrease, so the engine
NOx emissions decrease. (B.-Q. He, 2003)
CO emission depends on air fuel ratio. When ethanol content increases, CO emission is
reduced due to oxygen enrichment resulting from the ethanol. When the engine is run with E30

fuel at the compression ratio of 8:1. 8% lower CO emission. When compared to the running with
E30 fuel at the compression ratio of 6:1. (Manikandan, 2013)
For E30 fuel CO2 emission obtained at the compression ratio of 8:1 is about 8% lower
than that with E0 fuel at the compression ratio of 6:1. CO2 increases as CO decreases with
increasing engine speed. CO and CO2 have complementary correlation that is with increasing
CO emission the amount of CO2 decreases. CO2 emission depends on air fuel ratio and CO
emission concentration. (C.W. Wu, 2004)
The effect of E0 and E30 fuels with two different compression ratio on NOx emission
obtained with E30 fuel at the compression ratio 6:1 is about 23% lower than that with E0 fuel at
the same compression ratio (6;1). For E30 fuel NOx emission increases by about 9% with
increasing compression ratio from 6:1 to 8:1. The compression ratio increases the combustion
temperature also increases ultimately it increases the NOx. Engine running with E30 fuel at
compression ratio 8:1, NOx decreases by 16% compared to E0 fuel at a compression ratio of 6:1.
(Manikandan, 2013)
For same compression ratio (6:1) HC emission obtained with E30 fuel is about 19%lower
than that with E0 fuel. E30 fuel HC emission increases by about 9% with the increase in
compression ratio from 6:1 to 8:1. As the compression ratio increases, the combustion chamber
surface/volume ratio also increases and this in turn, increases the HC emission. (M.B. Celik)
When engine running with E30 fuel at compression ratio 8:1, HC emission decreases by about
12% compared to E0 fuel at compression ratio 6:1. (Manikandan, 2013)

Another consideration of the study includes the adaptation of the alternative fuel with
respect to technology. As application, the specific combination or mixture of ethanol and
gasoline is important to the engines performance and limits when having a blended fuel.

Different patents have been made, engine systems for multi-fluid operations (Boyarsi, US Patent
No. US7584740B2, 2009), and detection methods for troubleshooting difficulties during engine
start-up (Ayame, US Patent No. US7523744B2, 2009). Some improvements have been made in
the fuel intake such as variable direct injection system that controls the amount of ethanol that
mixes with the gasoline, with automatic shutdown whenever engine experiences deceleration,
thus, promotes increased efficiency (Bromberg, US Patent No. US7637250B2, 2009). Moreover,
a paper published paper from Kansas State University which talks about converting gasoline
engines to ethanol engines. According to the research, more Ethanol fuel should be injected by
the EFI to the engine for it to run normally. This means that Ethanol ready cars hold their injector
open longer, have a larger set of injectors or re-jetting for carbureted engines. One problem of
using an ethanol fuel for a normal gasoline engine is that the ethanol fuel degrades the materials
of some of the parts in the engine like rubber and plastics. (Price, n.d.) Some innovations include
automotive vehicles that allows different blends with an instrumentation that can measure the
percentage of ethanol added in the fuel. The measurement (in percent ethanol and gasoline in the
tank) is then used to determine the air to fuel ratio control. This certain type of device has types
of sensors that are called fuel composition sensors (either hardware or software). (Hatch, 2012)

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