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Chapter 1

1.1 Background of Study

Ethanol and ethanol-gasoline mixtures have been considered for use as fuel since the
early days of the automobile. The abundant and less expensive petroleum supply precluded
extensive use of ethanol as fuel and only in the last few years has the general public become
aware of and concerned about the dwindling and increasingly expensive petroleum supplies.
Interest in extending gasoline supplies with ethanol-gasoline mixtures has increased greatly.

Mankind since early recorded history has produced ethanol from simple sugars by
anaerobic yeast fermentation. Fermentation is the anaerobic or aerobic conversion of sugar to
carbon dioxide and alcohol by microorganisms. A variety of products can be produced by
fermentation, such as pharmaceuticals, organic acids, and alcohols. The most widely known
fermentation product is ethanol. Ethanol can be produced from a variety of plant-derived raw
materials, including agricultural wastes and also from starch, rise husk and sugarcane.
Bioethanol is produced using familiar methods, such as fermentation. Two steps are involved on
how biomass is converted to bioethanol:

 Hydrolysis of complex polysaccharides in the raw feedstock to simple sugars. The


feedstock must first be hydrolyzed into glucose molecules before ethanol production
can begin. Biomass-to-bioethanol process, acids and enzymes are used to catalyze this
reaction.

 Fermentation is a series of chemical reactions that convert sugars to ethanol. The


fermentation reaction is caused by yeast or bacteria, which feed with sugars. Ethanol
and carbon dioxide are produced while the sugar is consumed. The reaction for the 6-
carbon sugar (glucose) to produce ethanol shown in the following equation.

C6H12O6 → 2 CH3CH2OH + 2 CO2

(Glucose) (Ethanol) (Carbon Dioxide)

One of the greatest challenges for society in the 21st century is to meet the growing
demand of energy for transportation, heating and industrial processes and to provide a raw
material for those industries. Importantly, the future energy supply must be met with a
simultaneous substantial reduction of greenhouse gas emissions.

Ethanol can be blended with petrol or used as neat alcohol in dedicated engines, taking
advantage of the higher octane number and higher heat of vaporization; furthermore it is an
excellent fuel for future advanced flexi-fuel hybrid vehicles.

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Bioethanol is an excellent alternative to fossil fuels, either as a pure fuel with high
efficiency and performance or as a gasoline additive. Bioethanol is produced by fermentation.
Bioethanol can also be produced from a variety of plant-derived raw material. Ethanol has
several attractive features as an alternative fuel. As a liquid it is easily transported and it also can
be blended with gasoline to increase the octane rating of the fuel.

1.2 Problem Statement

The increased concern for the security of the oil supply and the negative impact of fossil
fuels on the environment, particularly greenhouse gas emissions, has put pressure on the society
to find renewable fuel alternatives. Ethanol usually produces using cheap raw materials such as
starch, rise husk and also sugarcane bagasse.

However this raw material base will not be sufficient. Consequently, future large scale
use of ethanol will most certainly have to base on production from starch materials. This project
gives an overview of the new technologies required and the advances achieved in recent years to
bring starch ethanol towards industrial production.

1.3 Project Objective

Objective of this study is to develop an efficient method of ethanol production by


hydrolysis or fermentation of starch.

This paper describes the process path ways of producing ethanol from corn briefly.

Specific objective

 Our specific objective here in our literature is to come up with a best method of
production of ethanol from corn .The method must be economically feasible, efficient to
produce ethanol.
 Showing process block diagram, process flow diagram and process description of ethanol
production from corn.

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CHAPTER 2
LITERATURE REVIEW

2.1 Introduction

Ethanol plays a key role in policy discussions about energy, agriculture, taxes, and the
environment. Mostly it is made from corn; it is often made from cane sugar. Fuel ethanol is
generally blended in gasoline to reduce emissions, increase octane, and extend gasoline stocks.
Recent high oil and gasoline prices have led to increased interest in alternatives to petroleum
fuels for transportation. Further, concerns over climate change have raised interesting developing
fuels with lower fuel-cycle greenhouse-gas emissions. Ethanol is substitutes for transportation
fuel when oil crisis arise. It considered as one of alternative way to overcome this problem. Fuel
ethanol still taking place at a research institute but in Brazil it already produced on a large scale
for the market. From research ethanol performs well as a fuel in cars it also friendly
environmental. Another reason to be mentioned the world demand for fuel in this era is predicted
to be more than the capacity of global oil production.

2.2 Starch
Starch is one of the most abundant bio macromolecules on earth as renewable resources
and green resource. It is a polysaccharide originated from plants as renewable resources. Native
starch consists of two different types of glucose polymers, amylose and amylopectin. The main
glucosidic linkage between glucose units in amylose is α-1, 4 configuration, while in
amylopectin additional α-1,6 glucosidic bonds make branch points in the macromolecule. Starch
is stored as granules in the plant and the morphology and crystallinity of a starch granule are
determined by the amylopectin fractionm, which constitutes about 70-80% of normal starch.
With an increasing awareness of environmental problems in recent years, versatile application
has been found for starch in many areas such as flocculants, adhesives, biodegradable plastics
and drug-delivery systems.

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2.2.1 Physicochemical properties of starch

Starch is a highly functional carbohydrate in its unmodified state. It is also a highly


reactive carbohydrate, which may be modified physically, chemically or enzymatically to meet
specific needs. Starches have four major physicochemical properties that make them useful in
food and industrial applications. Both types of starch molecules—amylose and amylopectin —
are polyhydroxy compounds and hydrate when heated in water, combining with individual water
molecules. As the molecules hydrate, they increase in size, immobilize much of the water
present, thicken the aqueous system and form a paste.

The first useful physicochemical property, thickening, gives many food products such as
puddings, gravies, sauces and pie fillings their desired physical characteristics. This property is
also useful in many industrial starch applications.

The second useful physicochemical property is the ability of the starch paste to disperse
and suspend other ingredients or particulate matter. In many foods, fats and proteins are
suspended and/or emulsified in starch pastes. In coatings for paper and in some adhesives, clay
particles are suspended in thick starch pastes. When starch pastes are allowed to cool, they
thicken and can congeal into a semisolid gel.

The third useful physicochemical property, gel formation, provides the body typical of
starch-based puddings, salad dressings and some types of adhesives.

The fourth useful physicochemical property of starch paste is its ability to produce strong
adhesive films when spread on smooth surfaces and dried. The major industrial uses of starch,
such as paper coating and sizing, textile sizing, corrugated board manufacture and all adhesive
applications utilize this property. These four important properties vary in degree from one starch
source to another.

When the structures of linear and branched starches were elucidated and methods were
developed for detecting and quantifying the two types of molecules, their functional properties
were finally explained. Straight chain amylose molecules tend to line up parallel to each other in
solution. As the solution cools, there is less energy available to keep the molecules apart. The
hydroxyl groups on parallel amylose molecules exert attractive forces and the molecules are
pulled together. The overall result is a gelled paste. The oriented areas are called micelles.
Starches with a high percentage of amylose are difficult to gelatinize because of the extra energy
needed to hydrate and disintegrate the firmly- bonded, crystalline aggregates of amylose. After
gelatinization such starches form firm gels and when properly prepared, yield strong, tough
films. A t the opposite end of the functional spectrum are the waxy starches, which are nearly
100% amylopectin. They gelatinize easily and yield nearly-transparent, viscous pastes that
retrograde slowly to weak gels. Between these extremes is found a wide range of natural starches

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as well as many starch modifications and derivatives. Based on the behavioral diversities of
native starches, the starch chemist, by selection of the proper raw material, followed by
application of selected modification or derivatization techniques, can devise products with a
broad range of functional characteristics.

2.2.2 Composition and structure of starch

Starch is produced as granules in most plants cells and is referred to native when in this
particular granular state. Native starches from different botanical sources vary widely in structure
and composition, but all granules consist of two major molecular components, amylose and
amylopectin, both of which are polymers of -D-glucose units in the 4C1 conformation. Molecule
structure of amylose shown in (Figure 2.1)

Figure 2.1 Amylose molecule structure

These are linked - (1 _ 4)-, with the ring oxygen atoms all on the same side, whereas in
amylopectin about one residue in every twenty is also linked - (1 _ 6) - forming branch-points as
shown in (Figure 2.2)

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Figure 2.2: Amylopectin molecule structure

Baker’s yeast, Saccharomyces cerevisiae, is widely used in ethanol production due to its high
ethanol yield and productivity, no oxygen requirement, and high ethanol tolerance. These
unusual capabilities are the result of adaptation to efficient ethanol production from hexose sugar
during thousands of years. However, S. cerevisiae cannot transport and use xylose as a substrate,
whereas the isomers of xylose (xylulose and ribulose) can be fermented. Cell metabolic
engineering and modification have been extensively carried out to give the ability of xylose
assimilation to yeast due to the wide availability of xylose resources. However, the development
is still in progress and there is no known recombinant yeast strain that is efficient enough to
ferment glucose, xylose and other minor sugars in hydrolysates to ethanol. Nevertheless, native
S. cerevisiae is probably still the best choice for softwood hydrolysates, where glucose and
mannose are dominant among other sugars. In addition, the native yeasts are inexpensive and
widely available. Saccharomyces cerevisiae is the only yeast that can rapidly grow under aerobic
as well as well as anaerobic conditions. This unique ability plays a major role in various
industrial applications of S. cerevisiae, including beer fermentation, wine fermentation and large-
scale production of fuel ethanol. Bioethanol is most commonly produced by anaerobic
fermentations with S. cerevisiae. Many attempts have been made to increase the overall
conversion yield from glucose to ethanol.

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2.3 STRUCTURE, COMPOSITION AND QUALITY OF CORN

Corn is one of nature's more amazing success stories, beginning life as a nutritionally useless
plant and coming to dominate the diets of humans and the animals they eat. Almost all packaged
foods contain corn products, no small accomplishment for a humble weed.

Starch is a primary foodstuff and acts as a key source of carbohydrate in global food production.
Commercial starch production is a wet milling process and filtration plays a major role in the
production of ethanol. In order to understand the milling process, it is necessary to examine the
structure of the corn kernel. Principal parts of the kernel are the tip cap (0.8%), pericarp or hull
(5%), germ or embryo (11%), and the endosperm (82%). The germ is comprised mainly of
protein and lipids, whereas the endosperm consists of starch granules embedded in a
proteinaceous cellular matrix. Floury endosperm at the grain center has loosely packed starch in
less dense proteinaceous cells, whereas horny endosperm at the grain periphery contains densely
packed starch granules in a region of high protein content. Starch granules in the denser horny
endosperm are polygonal as opposed to the more round granules in the floury endosperm. Most
dent corn has a ratio of floury to horny endosperm of about 1:2. Horny endosperm requires
thorough steeping to soften the protein matrix and ensure maximum starch recovery. The germ
next to the endosperm is the scutellum, a repository for enzymes required for hydrolyzing the
endosperm during embryonic development during germination to produce a new corn plant.
Because the scutellar epithelium is strongly bound to the endosperm, long steeping times are
required for separation. The average composition of corn grain on a dry basis is 71.3% starch,
9.91% protein, and 4.45% fat (56, 57). Normal water content is 10–15%.

Corn kernels have starch, which is an alpha-linked glucose polymer that can be easily broken
down to glucose monomers and fermented to ethanol. The fiber portion of the kernels encases
the starch. Corn used for ethanol production typically contains about 15% moisture.

2.3.1 STRUCTURE OF CORN

Mature corn kernels are unique, well-organized entities that exist for the purpose of reproducing
the species. Descriptions of the structures and compositions are helpful in understanding the
process of disruption that is achieved during the wet milling process.

The corn kernel is a one-seeded fruit classified as a grain, borne on a female inflorescence
commonly known as the ear. Each ear is comprised of a central stem, the cob, on which up to
1000 seeds develop. The seeds (kernels) mature about 60 days after pollination and are harvested
in late summer when kernel moisture content has dropped below 30% (wet weight basis). The
mature corn kernel is composed of four principle parts: tip cap, 0.8%; pericarp, 5.3%; germ,
11.9%; and endosperm, 82% (Figure 2.1; Table 2.1). The tip cap is the remnant of the pedicel
which attaches the seed to the cob. It is composed of insoluble fibrous elements arranged in a
spongy structure well adapted for rapid water adsorption. When the tip cap is removed, a black
tissue known as the hilar layer, which apparently functions as a sealing layer across the base of

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the germ upon kernel maturation, is revealed. The tip cap acts as the major pathway for the
entrance of water or other liquids or gases into the kernel.

The pericarp is the smooth, dense, outer covering of the kernel. The pericarp is often referred to
in the industry as the ‘hull,’ which is a misnomer since a hull is a distinctly different
morphological entity. The pericarp’s outer layer has a thin coating of wax-like cutin, beneath
which are several layers of dead, hollow, elongate cells compressed into a dense tissue. Beneath
this layer is a spongy tissue known as the tube cell and a cross-cell layer which acts as a natural
channel for absorption of water. Directly beneath the spongy layer is a very thin suberized
membrane known as the seed coat or testa. This layer is thought to act as a semipermeable
membrane, limiting passage of large molecules into or out of the endosperm and germ. Liquids
or gases which enter the tip cap region diffuse rapidly through the cross and tube cells, so that
the region between the outer pericarp and the seed coat quickly becomes saturated with the liquid
or gas. Diffusion into the endosperm then occurs across the seed coat from around the total
periphery, rather than from just the tip cap end. This pathway gives the appearance that the
diffusivity of the pericarp is much higher than it actually is. A second major pathway of passage
of gases and liquids into the endosperm via naturally occurring connections between the germ
and the center of the soft endosperm has also been identified. Diffusion through the germ is 18
times higher than through the pericarp; this pathway effectively provides for endosperm
penetration from the inside out.

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Figure 2.1 Longitudinal 10- μm bisection of corn kernel

Immediately beneath the testa is the first layer of the endosperm, the aleurone, asingle layer of
highly proteinaceous cells having thick, tough cell walls. It is possible that the aleurone’s thick
dense cell walls may be responsible for the observed semi permeabilityattributed to the seed coat
simply by a size limiting diffusional process. Aleurone comprises about 3% of the weight of the
kernel. Although structurally part of the endosperm, the aleurone, along with the pericarp and tip
cap, is included in the ‘fiber’ fraction from wet-milling and in the bran fraction from dry-milling.
In alkali debranning, the aleurone layer is not removed with the pericarp, because the alkali
dissolves the weak bonds between the loose cells of the cross and tube cell layer.

Mature endosperm is comprised of a large number of cells, each packed with starch granules
embedded in a continuous matrix of protein; all the cell contents are surrounded by a cellulosic
cell wall. Mature endosperm of dent corns contains a central core of soft or floury endosperm
extending to the crown, which shrinks on drying, causing a ‘ dent. ’ The floury endosperm is
surrounded by a glassy-appearing region known as horny or hard endosperm. The average ratio
of floury to horny regions is about 1:2, but it varies considerably depending on the protein
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content of the kernel. Flour corns contain virtually no horny endosperm, while flint corn and
popcorn endosperms are comprised of a small core of floury endosperm entirely surrounded by
horny endosperm which resists denting when the kernel dries. Although the dividing line
between horny and floury regions of the endosperm is morphologically indistinct, the floury
region is characterized by larger cells, large spherical starch granules and a relatively thin protein
matrix. The thin strands of protein matrix rupture during kernel drying, causing air pockets,
which give the floury region a white opaque appearance and a porous texture which results in
easy starch recovery.

Table 2.1 Weight and composition of component parts of corn kernels

In the horny endosperm, the thicker protein matrix shrinks during drying, but does not rupture.
The resulting pressure produces a dense glassy structure in which starch granules are forced into
an angular, close-packed conformation. The dense nature of horny endosperm requires adequate
steeping to ensure recovery of starch. The horny endosperm contains only ∼1.5 – 2.0% higher
protein content and a greater concentration of the yellow carotenoid pigments than the floury
region. Just under the aleurone layer is a dense row of cells known as subaleurone or dense
peripheral endosperm containing as much as 28% protein. These small cells comprise probably
less than 5% of the endosperm. They contain very small starch granules and athick protein
matrix. Starch from this area can be difficult to isolate and purify.

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The germ is comprised of two major parts: the scutellum and the embryonic axis. The embryonic
axis is the structure that grows into the seedling on germination and makes up only ∼10% of the
weight of the germ. The scutellum functions as a storage organ from which nutrients can be
quickly mobilized during initial seedling growth. The surface of the scutellum adjacent to the
endosperm is covered by secretory epithelium, a layer deeply furrowed by canals or glands lined
with elongated secretory cells. The function of these cells is to secrete enzymes which diffuse
into the endosperm where they digest starch and other constituents to provide nourishment for
the embryo.

The scutellar epithelium adheres to the endosperm by an insoluble cementing substance,


apparently consisting of degradation products of crushed cells and composed largely of
pentoglycans and protein. This layer provides a strong bond that resists many chemical and
physical means of separating the germ and endosperm; hence, prolonged steeping is required for
an effective separation of whole intact germ from the endosperm. The major portion of the
scutellum is composed of thick-walled isodiametric cells densely packed with cytoplasm. Oil
droplets may be seen in sections of such cells and have been shown to be nearly identical to the
spherosome bodies observed in the repository of oil in cottonseed and peanut cotyledons. A
simple mental picture of the corn kernel can be created by visualizing the pericarp as a plastic
bag similar to those used to package groceries. The bag, like the pericarp, protects the contents
inside by limiting exposure to the external elements. In the bag is the germ which, to a miller, is
like a large sponge soaked with oil. The majority of the bag is filled with marbles, which are
starch granules. Visualize glue poured into this marble and oil-laden, sponge-filled bag, so that
all void areas are filled. When the glue hardens, it totally encapsulates the marbles (starch), and
adheres the bag (pericarp) to the marbles (starch), the bag to the oily sponge (germ), and the oily
sponge to the marbles. The purpose of wet-milling is to chemically loosen the glue and
mechanically (primarily by density) separate the kernel into nearly homogeneous piles of oily
sponges (germs), marbles (starch), glue (gluten meal) and bags (gluten feed).

2.3.2 COMPOSITION OF CORN

The chemical composition of commercial corn based on proximate analysis is shown in Table
2.1.Commercial corn, which is a thorough mixture from many sources, has a much narrower
range.There are three classes of corn recognized: yellow, white and mixed. White corn and
mixed white and yellow corn classes are generally not purchased by the wet-milling industry
because yellow corn is what the vast majority of farmers produce, as white corn hybrids
generally give lower yields. Furthermore, the yellow pigment which is concentrated in the gluten
meal fraction is highly valued as poultry feed, and commands a price approximately 1.5 times
the value of starch. Even at comparable production yields, wet-millers would prefer to purchase
yellow hybrids. Currently, some specialty starch wet-milling companies process white corn to
produce starches with enhanced whiteness. Processing corn of mixed classes is not desirable.

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2.3.4 QUALITY OF CORN GRAIN

Corn grain quality is increasingly important as more grain is used for processing and other
specialty end uses. Optimal quality of corn is affected by three main factors: genetics;
environmental or growing conditions; and postharvest handling and storage.

2.3.4.1 Harvest Practices

Harvesting grain at too high of moisture can result in severe kernel damage during threshing and
drying. Conversely, allowing corn to field dry too long can lead to reduced yield and quality if

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stalk or ear rot diseases or insect feeding damage are increasing. Monitor stalk quality. If stalks
lodge, ears can come in contact with the ground which can lead to ear root development.

2.3.4.2 Hybrid Selection

Selecting hybrids rated highly for grain quality traits is the first step in producing highest quality
grain. High test weight is a grain trait that helps kernels resist breakage during threshing and
handling.

2.3.4.3 Grain Handling and Drying

Broken kernels and fines can create problems during grain storage, and lower quality for many
end uses. A rotary screen, gravity screen or perforated auger housing section can be used to
screen out the fines. The wetter the grain the lower the temperature must be to maintain a better
kernel quality and density. High temperature drying followed by fast cooling can have a
devastating effect on stress-cracking of corn kernels. For most grain uses, this drying method is
unacceptable. When using a continuous-flow grain dryer and as colder temperatures approach,
take caution in not over-cooling the grain. This can cause stress fractures. Cracked and broken
kernels don't store as well as whole kernels. Freezing temperatures can cause stress fractures in
grain, especially in higher density kernels. After harvest, it's important to check your grain on a
weekly basis for four to six weeks until you are sure it's stable.

Table 2.3 Maximum recommended kernel temperature during drying

2.4 Ethanol
Ethanol (ethyl alcohol, C2H5OH) is an alcohol made by fermenting and distilling
simple sugars. Ethanol is produced by the fermentation of monosaccharaides such as glucose and
fructose. The monosaccharaides are typically formed through the hydrolysis of any number of
biomass options. Ethanol can be manufactured from biomass via the fermentation of sugar
derived from grain starches of many crops including wheat wastes and sugar, biomass via the

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utilization of the lignocellulosic fraction of crops or petroleum and natural gas. Ethanol is used in
the manufacture of alcoholic beverages and it is denatured (made unfit for human consumption)
when used for fuel and a variety of other manufactures such as methylated spirits. The biomass
source for ethanol production varies depending primarily on local economics and resources. This
can be considered an advantage in that regional development of fuel production facilities can
optimize for the economics and resources of their own particular surroundings. Other cellulose
feed sources are possible as well, such as grass or woodchips.

2.4.1. PHYSICAL PROPERTIES

Ethanol's hydroxyl group is able to participate in hydrogen bonding. At the molecular level,
liquid ethanol consists of hydrogen-bonded pairs of ethanol molecules; this phenomenon renders
ethanol more viscous and less volatile than less polar organic compounds of similar molecular
weight. In the vapor phase, there is little hydrogen bonding; ethanol vapor consists of individual
ethanol molecules. Ethanol, like most short-chain alcohols, is flammable, colorless, has a strong
odor, and is volatile. Ethanol has a refractive index of 1.3614. Ethanol is a versatile solvent. It is
miscible with water and with most organic liquids, including nonpolar liquids such as aliphatic
hydrocarbons. Organic solids of low molecular weight are usually soluble in ethanol. Among
ionic compounds, many monovalent salts are at least somewhat soluble in ethanol, with salts of
large, polarizable ions being more soluble than salts of smaller ions. Most salts of polyvalent
ions are practically insoluble in ethanol. Furthermore, ethanol is used as a solvent in dissolving
medicines, food flavorings and colorings that do not dissolve easily in water. Once the non-polar
material is dissolved in the ethanol, water can be added to prepare a solution that is mostly water.
The ethanol molecule has a hydrophilic -OH group that helps it dissolve polar molecules and
ionic substances. The short, hydrophobic hydrocarbon chain CH3CH2- can attract non-polar
molecules. Thus ethanol can dissolve both polar and non-polar substances. Several unusual
phenomena are associated with mixtures of ethanol and water. Ethanol water mixtures have less
volume than their individual components: a mixture of equal volumes ethanol and water has only
95.6% of the volume of equal parts ethanol and water, unmixed. The addition of even a small
amount of ethanol to water sharply reduces the surface tension of water. This property partially
explains the tears of wine phenomenon: when wine is swirled inside a glass, ethanol evaporates
quickly from the thin film of wine on the wall of the glass. As its ethanol content decreases, its
surface tension increases, and the thin film bead’s up and runs down the glass in channels rather
than as a smooth sheet.

Physical Properties
Formula C2H6O
Molecular weight 46.07 g mol−1
Appearance Colorless, clear liquid

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Boiling point 172.9°F, 78.3°C, 351.5°K at 1 atm
Melting Point −114.3 °C, 159 K, -174 °F
Freezing Point –173°F, –114°C, 159°K
Acidity (pKa) 15.9
Density 0.789 g/cm3
Specific Gravity 0.790 at 20°C
Solubility in water Fully miscible
Vapor Pressure 50 mm Hg at 77° F
Heat of Formation - 276.5 kJ/mol
Gibbs Free Energy -162.62 MJ/kmol
Critical temperature 469.6°F, 243.1°C, 516.3K

2.4.2 CHEMICAL PROPERTIES

Alcohols are reactive compounds. They are attacked by polar or ionic reagents. This is because:
a) The C – O and O – H bonds of alcohols are polar since oxygen is highly electronegative.
b) The oxygen atom of alcohols is an electron – rich centre
becauseithastwounsharedpairsofelectrons.

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2.4.3 TYPES OF ETHANOL

A.Denatured alcohol:

In most jurisdictions, the sale of ethanol, as a pure substance, or in the form of alcoholic
beverages, is heavily taxed. In order to relieve non-beverage industries of this tax burden,
governments specify formulations for denatured alcohol, which consists of ethanol blended with
various additives to render it unfit for human consumption. These additives, called denaturants,
are generally either toxic (such as methanol) or have unpleasant tastes or odors (such as
denatonium benzoate). Specialty denatured alcohols are denatured alcohol formulations intended
for a particular industrial use, containing denaturants chosen so as not to interfere with that use.
While they are not taxed, purchasers of specialty denatured alcohols must have a government-
issued permit for the particular formulation they use and must comply with other regulations.

Completely denatured alcohols are formulations that can be purchased for any legal
purpose, without permit, bond, or other regulatory compliance. It is intended that it be difficult to
isolate a product fit for human consumption from completely denatured alcohol. For example,
the completely denatured alcohol formulation used in the United Kingdom contains (by volume)
89.66% ethanol, 9.46% methanol, 0.50% pyridine, 0.38% naphtha, and is dyed purple with
methyl violet.

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B.Absolute ethanol:

Absolute or anhydrous alcohol generally refers to purified ethanol, containing no more than one
percent water. It is not possible to obtain absolute alcohol by simple fractional distillation,
because a mixture containing around 95.6% alcohol and 4.4% water becomes a constant boiling
mixture (an azeotropic mixture). In one common industrial method to obtain absolute alcohol, a
small quantity of benzene is added to rectified spirit and the mixture is then distilled. Absolute
alcohol is obtained in the third fraction that distills over at 78.2 °C (351.3 K). Because a small
amount of the benzene used remains in the solution, absolute

alcohol produced by this method is not suitable for consumption as benzene is carcinogenic.

There is also an absolute alcohol production process by desiccation using glycerol. Alcohol
produced by this method is known as spectroscopic alcohol - so called because the absence of
benzene makes it suitable as a solvent in spectroscopy. Currently, the most popular method of
purification past 95.6% purity is desiccation using adsorbents such as starch or zeolites, which
adsorb water preferentially. Azeotropic distillation and extractive distillation techniques also
exist.

C.Neutralized ethanol:

Neutralized ethanol is used for some analytical purposes. The pH indicators are acid/base
molecules that change their color requiring certain amount of acid or base. Neutralized ethanol is
used in order to compensate for this error. The indicator (phenolphthalein, for example) is added
to the ethanol solvent first and KOH is added until the color of the solution turns pale pink. The
so obtained "neutralized ethanol" is then added to the target of the titration, which may be sample
of neat organic acid. The titration stops when the same pale pink color is achieved. This way, the
indicator neutralization error is eliminated.

2.4.4 USES OF ETHANOL

A. As a fuel:

The largest single use of ethanol is as a motor fuel and fuel additive. In order for ethanol to be
suitable for use as a replacement to petrol in its pure form, it must be distilled to at least 70-80%
purity by volume before use. For use as an additive to petrol, almost all water must be removed;
otherwise it will separate from the mixture and settle to the bottom of the fuel tank, causing the
fuel pump to draw water into the engine, which will cause the engine to stall.

Flex fuel engines are able to work with all ethanol, all gasoline or any mixture of both, giving
the buyer a choice for a perfect balance between price/performance issues.

Ethanol creates very little pollution when burned.Substitution of Petroleum by ethanol as a motor
fuel has already gained universal recognition.

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B.Rocket Fuel:

Ethanol has been used as fuel in bipropellant rocket vehicles, in conjunction with an oxidizer.
For example, the German V-2 rocket of World War 2 used ethanol fuel.

C. Alcoholic beverages:

Alcoholic beverages vary considerably in their ethanol content and in the foodstuffs from which
they are produced. Most alcoholic beverages can be broadly classified as fermented beverages,
beverages made by the action of yeast on sugary foodstuffs, or as distilled beverages, beverages
whose preparation involves concentrating the ethanol in fermented beverages by distillation. The
ethanol content of a beverage is usually measured in terms of the volume fraction of ethanol in
the beverage, expressed either as a percentage or in alcoholic proof units. Fermented beverages
can be broadly classified by the foodstuff from which they are fermented. Beers are made from
cereal grains or other starchy materials, wines and ciders from fruit juices, and meads from
honey. Cultures around the world have made fermented beverages from numerous other
foodstuffs, and local and national names for various fermented beverages abound. Fermented
beverages may contain up to 15–25% ethanol by volume, the upper limit being set by the yeast's
tolerance for ethanol, or by the amount of sugar in the starting material. Distilled beverages are
made by distilling fermented beverages. Broad categories of distilled beverages include
whiskeys, distilled from fermented cereal grains; brandies, distilled from fermented fruit juices,
and rum, distilled from fermented molasses or sugarcane juice. Vodka and similar neutral grain
spirits can be distilled from any fermented material (grain or potatoes are most common); these
spirits are so thoroughly distilled that no tastes from the particular starting material remain.

Numerous other spirits and liqueurs are prepared by infusing flavors from fruits, herbs, and
spices into distilled spirits. A traditional example is gin, the infusion of juniper berries into
neutral grain alcohol. In a few beverages, ethanol is concentrated by means other than
distillation.

Applejack is traditionally made by freeze distillation: water is frozen out of fermented apple
cider, leaving a more ethanol-rich liquid behind.

Eisbier (most commonly, eisbock) is also freeze-distilled, with beer as the base beverage.
Fortified wines are prepared by adding brandy or some other distilled spirit to partially-
fermented wine. This kills the yeast and conserves some of the sugar in grape juice; such
beverages are not only more ethanol-rich, but are often sweeter than other wines.

Alcoholic beverages are sometimes added to food in cooking, not only for their inherent flavors,
but also because the alcohol dissolves flavor compounds that water cannot.

19
D. Other Uses:-

1) As A solvent:

Ethanol is easily soluble in water in all proportions with a slight overall decrease in volume when
the two are mixed. Absolute ethanol and 95% ethanol are themselves good solvents, somewhat
less polar than water and used in perfumes, paints and tinctures. Other proportions of ethanol
with water or other solvents can also be used as a solvent. Alcoholic drinks have a large variety
of tastes because various flavor compounds are dissolved during brewing. When ethanol is
produced as a mixing beverage it is a neutral grain spirit.

2) Medical Uses:

Ethanol is used in medical wipes and in most common antibacterial hand sanitizer gels at a
concentration of about 62% (percentage by weight, not volume) as an antiseptic. The peak of the
disinfecting power occurs around 70% ethanol; stronger and weaker solutions of ethanol have a
lessened ability to disinfect. Solutions of this strength are often used in laboratories for
disinfecting work surfaces.

Ethanol kills organisms by denaturing their proteins and dissolving their lipids and is effective
against most bacteria and fungi, and many viruses, but is ineffective against bacterial spores.
Alcohol does not act like an antibiotic and is not effective against infections by ingestion.
Ethanol in the low concentrations typically found in most alcoholic beverages does not have
useful disinfectant or antiseptic properties, internally or externally. Ethanol is often used as an
antidote in cases of methanol poisoning.

3) Wine Preservation:

Wine with less than 16% ethanol is vulnerable to bacteria. Because of this, port is often fortified
with ethanol to at least 18% ethanol by volume to halt fermentation for retaining sweetness and
in preparation for aging, at which point it becomes possible to prevent the invasion of bacteria
into the port, and to store the port for long periods of time in wooden containers that can
'breathe', thereby permitting the port to age safely without spoiling. Because of ethanol's
disinfectant property, alcoholic beverages of 18% ethanol or more by volume can be safely
stored for a very long time.

4) Metabolism and toxicology:

Pure ethanol is a tasteless liquid with a strong and distinctive odor that produces a characteristic
heat-like sensation when brought into contact with the tongue or mucous membranes. When
applied to open wounds (as for disinfection) it produces a strong stinging sensation. Pure or
highly concentrated ethanol may permanently damage living tissue on contact. Ethanol applied
to unbroken skin cools the skin rapidly through evaporation.

20
2.5 Ethanol production

Raw materials containing sugars or materials which can be transformed into sugars
can be used as fermentation substrates. The fermentable raw materials can be grouped as directly
fermentable sugary materials, starchy, lignocellulosic materials and urban/industrial wastes.
Sugar containing materials require the least costly pretreatment, where starchy, lignocellulosic
materials and urban/industrial wastes needed costly pretreatment, to convert into fermentable
substrates. Sugar containing materials which can be transformed into glucose, can be used as
fermentation substrates under anaerobic conditions, glucose is converted to ethanol and carbon
dioxide by glycolysis. The phosphorylation of carbohydrates is carried out through the metabolic
pathway and the end products are two moles of ethanol and carbon dioxide. Although fungi,
bacteria, and yeast microorganisms can be used for fermentation, specific yeast (S. cerevisiae
also known as Bakers’ yeast, since it is commonly used in the baking industry) is frequently used
to ferment glucose to ethanol. Ethanol production from grain involves milling of grain,
hydrolysis of starch to release fermentable sugar, followed by inoculation with yeast. Chemically
starch is a polymer of glucose .Yeast cannot use starch directly for ethanol production.
Therefore, grain starch has to be wholly broken down to glucose by combination of two
enzymes, viz., amylase and amyloglucosidase, before it is fermented by yeast to produce ethanol.
Alcohol produced from fermented broth and remaining spillages is processed to produce
Distiller’s Dried Grain and Soluble (DDGS), which is an excellent ingredient for animal feed.
Ethanol can be produced by four main types of industrial operations: batch, continuous, fed-
batch and semi-continuous. In batch fermentation, substrate and yeast culture are charged into
the bioreactor together with nutrients. Most of the ethanol produced today is done by the batch
operation since the investment costs are low, do not require much control and can be
accomplished with unskilled labor.

Complete sterilization and management of feedstock are easier than in the other processes. The
other advantage of batch operation is the greater flexibility that can be achieved by using a
bioreactor for various product specifications. In the continuous process, feed, which contains
substrate, culture medium and other required nutrients, is pumped continuously into an agitated
vessel where the microorganisms are active. The product, which is taken from the top of the
bioreactor, contains ethanol, cells, and residual sugar. The fed-batch operation, which may be
regarded as a combination of the batch and continuous operations, is very popular in the ethanol
industry. In this operation, the feed solution, which contains substrate, yeast culture and the
required minerals and vitamins, are fed at constant intervals while effluent is removed
discontinuously. The main advantage of the fed-batch system is that intermittent feeding of the
substrate prevents inhibition and catabolite repression. If the substrate has an inhibitory effect,
intermittent addition improves the productivity of the fermentation by maintaining a low
substrate concentration. It is essential to keep the culture volume constant in continuous
operation, whereas there is volume variation in the fed-batch processes. In semi-continuous
processes, a portion of the culture is withdrawn at intervals and fresh medium is added to the

21
system. In the continuous processes it is essential to maintain a constant culture volume, whereas
there is volume variation in semi-continuous processes. This method has some of the advantages
of the continuous and batch operations. There is no need for a separate inoculum vessel, except
at the initial startup. Time is also not wasted in nonproductive idle time for cleaning and
resterilization. Another advantage of this operation is that not much control is required.
However, there is a high risk of contamination and mutation due to long cultivation periods and
periodic handling. Furthermore, since larger reactor volumes are needed, slightly higher
investment costs are required.

Areas of scientific research address the establishment of new higher-value ethanol co-products,
the development of microbes capable of converting various biomass materials into ethanol,
improved processes for the enzymatic saccharification of corn fibers into sugars, and various
methods of improving corn ethanol process efficiencies.

The mature corn-to-ethanol industry has many similarities to the emerging lignocellulose to-
ethanol industry. It is certainly possible that some of the early practitioners of this new
technology will be the current corn ethanol producers. The feedstock used for each process is
different but related.

2.5.1 History of the Corn Ethanol Industry

Ethanol is produced by either a wet milling or dry milling process and utilizes shelled corn
as the principal feedstock. Facilities using the wet milling process have greater production
capacities, are more capital intensive and produce a greater variety of products than dry milling
facilities. The wet milling process converts corn into corn oil, two animal feed products (corn
gluten feed and corn gluten meal), and starch-based products such as ethanol, corn syrups, or
cornstarch. Approximately 60% of the ethanol produced is from wet mills .However, the dry mill
is preferable since it requires less capital to build, a smaller staff to run, and tends to receive tax
advantages due to smaller capacity. The dry milling process traditionally generates two products
only .Ethanol and DDG, an animal feed product. Both processes also generate carbon dioxide
(CO2) which is captured and marketed in some plants.

A. Corn Wet Milling process

The process of wet milling takes the corn grain and steeps it in a dilute combination of sulfuric
acid and water for 24 to 48 hours in order to separate the grain in to many components. The
slurry mix then goes through a series of grinders to separate out the corn germ. Corn oil is a by-
product of this process and is extracted and sold. The remaining components of fiber,gluten and
starch are segregated out using a screen, hydroclonic and centrifugal separators. The gluten
protein is dried and filtered to make a corn gluten meals co-product and is highly sought after by
poultry broiler operators as a feed ingredient. The steeping liquor produced is concentrated and

22
dried with the fiber and sold as corn gluten feed to the livestock industry. The heavy steep water
is also sold as a feed ingredient and is used as an environmentally friendly alternative to salt in
the winter months. The corn starch and remaining water can then be processed in one of the three
ways; 1) fermented in to ethanol, through a similar process as dry milling, 2) dried and sold as
modified corn starch 3) made into corn syrup

The production of corn ethanol uses water in two ways-irrigation and processing. There are two
types of ethanol processing, wet milling and dry milling, and the central difference between the
two processes is how they initially treat the grain. In wet milling, the corn grain is steeped in
water, and then separated for processing in the first step. Dry milling, which is more common,
requires a different process.

Today the corn-wet milling process is one of the most productive; best characterized and well
understood industrial food processes in the world. Unlike dry-grind ethanol plants that ferment
the entire ground corn kernel, wet mills separate the corn kernel into various fractions, which
allows for the production of multiple food and industrial. The wet milling process effectively
separates protein-containing and non-protein-containing products. The basic steps for wet
milling include steeping, germ separation, fine grinding, starch separation, fermentation, and
syrup conversion. Corn processed by wet milling is typically separated into 5 basic components:
starch, germ, gluten, fiber and steep liquor. By-products of wet milling along with corn germ and
most corn gluten are used for animal feed products.

B. Corn Dry Milling process

In the dry milling process the entire corn kernel is ground in to flour and referred to as ‘’meal’’.
The meal is then slurred by adding water. Enzymes are added to the mash that converts starch to
dextrose, a simple sugar. Ammonia is added to control the PH and as a nutrient for the yeast
which is added later. The mixture is processed at high-temperatures to reduce the bacteria levels
and transferred and cooled in fomenters. This is where the yeast is added and conversion from
sugar to ethanol and carbon dioxide begins. The entire process takes between 40 to 50 hours,
during which time the mash is kept cool and agitated in order to facilitate yeast activity. After the
process is complete, everything is transferred to distillation columns where the ethanol is
removed from the ‘’stillage’’. The ethanol is dehydrated to about 200 proof using a molecular
sieve system and a denaturant such as gasoline is added to render the product undrinkable. With
this last addition, the process is complete and the product is ready to ship to gasoline retailers or
terminals. The remaining stillage then undergoes a different process to produce nutritious
livestock feed. The carbon dioxide released from the process is also utilized to carbonate
beverages and to aid in the manufacturing of dry ice.

Unlike the elaborate wet milling process, corn dry milling is basically a simple grinding
procedure. As in the wet milling process, the corn is initially cleaned. Once clean, the moisture
content of corn is raised to about 20%. The corn germs are then removed for oil extraction and

23
the remaining corn is ground and sieved into many fractions which vary in particle size and
composition. The primary products of dry milling are flour, cornmeal and grits. Additional
products include corn bran and feed mixtures. These products are used in brewing, foods,
building products (binders), fermentations (pharmaceuticals and fuel), and animal feeds

Wet milling process has been chosen in this particular project due to the fact that wet milling
process produces a variety of products along with ethanol although the capital expenditure is a
bit too high. The corn kernel is fractionated into primary components (germ, fiber, and starch);
and this results in several process streams and co-products.

24
CHAPTER 3
PROCESS FLOWSHEET FOR CORN TO ETHANOL PRODUCTION

Fig.3.1 simplified flow sheet of fuel ethanol production from corn

25
3.1 Process Descriptions
Milling

Corn passes through hammer mills that grind it into a fine powder called meal. . Initially, the corn
kernel is mechanically broken down in a hammer mill to expose the starch cell walls since the bonds
between starch molecules are not very strong.

Mashing

In this pre-cook section, water is mixed with the meal to form a mash. Water for mashing comes
from the moisture in the corn, makeup water, recycled water (such as thin stillage), CO2 scrubber
water, hot process condensate from the evaporators and flash tank condensate. Added á-amylase in
the slurry mixer begins the breakdown of starch to limit the maximum viscosity during cooking.

Cooking

The treated slurry is cooked using one of two methods. In the first method, a hydro heater is used.
Steam enters the system across a steam jet to heat the slurry. A 20-40 psi pressure drop as the steam
enters the system helps to mechanically shear the starch molecules. The slurry is heated to 90-120 °C
(194-248 °F) and held at that temperature for 8-10 minutes in a cook tube at the saturation pressure
of 15-16 psig. The alternative method cooks the slurry at 125-140 ° C (257-284 ° F) using 150 psig
steams in a cooking tube. In this case retention time is 6-8 minutes, under 40-50 psig pressure. No
hydro heater is used. For both methods, high temperatures reduce bacteria levels in the mash.

Liquefaction

Liquefaction is the stage between the cooking and saccharification process. Gelatinized starch is
partially hydrolyzed by α-amylase (or occasionally by an acid) to give soluble dextrin. The α-
amylase converts all starch in the mash so it becomes a free-flowing liquid with reduced viscosity. A
second injection of α-amylase is made because previously added α-amylase is denatured and or
deactivated under cooking condition. The temperature is reduced to enable liquefaction at 86.7 °C
(190 °F) and the pH value is maintained at 5.0 to 6.5. The liquid is cooled following the liquefaction
phase with recovered heat used elsewhere in the process.

SSF (Simultaneous Saccharification and Fermentation)

Yeast and yeast food are combined with liquefied mash in the yeast tank. The yeast tank is aerated so
the yeast will propagate in the aerobic mode. While the yeast propagates, the SSF reactors are filled
with cooled mash. Gluco-amylase is added to the mash to begin the process of saccharification, that is,
the breakdown of dextrin to fermentable sugars. When the propagated yeast is ready, it is added to the
fermenter and saccharification continues during fermentation. In the fermentation reaction, yeast
ferments glucose to ethanol and carbon dioxide.

26
A typical corn-to-ethanol facility has three or more fermenters operating batch wise in staggered cycles
of 48-72 hours until the mash is fully fermented. The fermenter operates anaerobically. Commercial
yeast strains for ethanol production can effect fermentation at 32-35 °C (90-95 °F). At higher
temperatures metabolic activity rapidly declines. Yeast prefers an acid pH and the optimum pH is 5.0-
5.2. Released CO2 is removed from the system through the scrubber.

Distillation/Dehydration

Fermented mash, called "beer," contains 10-16 % alcohol by volume, as well as the non-fermentable
solids from the corn and yeast cells. Mash is pumped into the continuous distillation (typically two
columns) system where the alcohol is separated from the solids and most of the water as an azeotrope.
Alcohol leaves the top of the first column as 60-80% ethanol (by volume). Water can be recycled to the
á-amylase mixer from a stripper in the distillation column.

The azeotropic 95.6% ethanol from the top of the second column passes through a system where the
remaining water is removed. The energy balance for this project assumes a molecular sieve is used to
remove water in the ethanol to achieve 99.65% (weight) purity of ethanol. The ethanol product at this
stage is called anhydrous (pure, without water) ethanol. Denaturing involves adding a small amount (2-
5% by weight) of a product, like gasoline, to the ethanol to meet state tax regulations.

Solids Separation

The solids-containing bottoms from the beer column are called whole stillage (or thick stillage). Whole
stillage total solids content is 7-14% (typically 8% dry solids) [43]. The whole stillage is separated by
centrifuge into a somewhat diluted liquid (called thin stillage or backset, containing 1% or more
suspended solids and 3% or more total solids) that will be partly recycled to the slurry mixer or
fermenters. The balance of the thin stillage is concentrated to make syrup in the evaporation section.
The centrifuged solids are typically called wet cake that contains approximately 65-75% moisture and
25-35% solids. Syrup from the evaporators is added to the wet cake to make DDGS (distillers dried grains
with solubles) in the DDGS dryer.

Wet cake, mixed with syrup is fed to the dryer, where it is dried to a final moisture content of 9-10%.
The moisture content in the feed to the dryer is decreased by recycling some dry product and mixing it
with the wet cake and the syrup. This dryer feed “conditioning” prevents rapid fouling in the dryer,
which may result in dryer fires. The best DDGS dryer performance occurs when the total feed moisture
content is in the 25-30% range. [20] Corn normally contains 9-10% crude protein, but it is concentrated
in DDGS to 28-30% (or more) crude protein. The DDGS concentrates nutrients (fat, protein and minerals)
from corn by approximately a factor of 3. This makes DDGS a high-value animal feed.

Evaporation

Thin stillage is concentrated by evaporation to produce corn syrup. Syrup ranges from 25% to 50% total
solids, and the model assumes 30% total solids as a typical operating target. Hot condensed water

27
removed in evaporation (hot process condensate) can be reused in the mashing and fermentation
sections. Corn syrup is added to the DDGS before drying to increase the caloric value.

CO2 Scrubber

VOC (volatile organic compounds), mainly ethanol, are removed from the CO2 produced during
fermentation by a scrubber. Water passes through the scrubber in once-through operation. It is added
to the mashing section of the process for ethanol recovery and water integration. CO 2 can be
compressed for sale to the carbonated beverage industry, or more commonly, is vented.

3.2 Material Balance Calculations


Based on The block flow diagram of the corn to ethanol process, the conservation equation for the
liquefaction and SSF (Simultaneous Saccharification and Fermentation) blocks is written as:

Material out = Material in + Generation – Consumption

For the rest of the blocks, there is no chemical reaction, so the steady-state balance reduces to:

Material out = Material in


The weight basis reaction stoichiometry from literature research for the liquefaction is shown as
below:

Starch (long chain) + 0.012Water 1.012 Starch (short chain) (3.0)

The molar basis reaction stoichiometry from literature research for the SSF is listed here

Starch + Water Glucose (3.1)


Glucose 1.9 Ethanol + 1.9 CO2 + 0.06 NFDS
(3.2)
NFDS 1.136358 Protein (3.3)

The yield is a function of starch composition in corn, saccharification and


fermentation conversions
 starch content is 59.5% (w).

 Basis: 100 tons/day of Ethanol

28
= 124517.4947 lit /day
= 32894.145 gallon/day
= 4166.66 kg/hr
=100000 kg/day
Data:
Yeast required = 1300kg/day

Steam required= 0.1155kg/kg of powder corn

Corn required

To convert the molar basis reaction stoichiometry to the weight basis reaction
stoichiometry, the three equations (3.1,3.2&3.3) are changed to:

Starch + 0.1111 Water 1.1111 Glucose (3.4)

Glucose 0.4859 Ethanol + 0.4641 CO2 + 0.0500 NFDS (3.5)

NFDS Protein (3.6)

Material balance on fermentation

29
Glucose 0.4859 Ethanol + 0.4641 CO2 + 0.0500 NFDS

X 100000 kg/day
100000 kg/day
X= 0.4859
= 205,803.66 kg/day

For conc. of alcohol 96% fermentable starch required


205,803.66 kg/day *0.96 = 197,571.5168 kg/day

Material balance for coking/liquefaction

Starch + 0.1111 Water 1.1111 Glucose

Y 197,571.5168 kg/day
197,571.5168 kg/day
Y= 1.111111
=177,816.143 kg/day

Amount of water required =19,755.37 kg/day

The corn required would be

(177,816.143 kg/day)*( 1/0.59 )

=301,383.25 kg/day
30
Steam required = (177,816.143 kg/day)*(0.1155)

=20,517.24 kg/day

Co2 produced

Based on eq 3.5
205,803.66∗0.4641
Amount of Co2 = 1
kg/day

=95,513.4786 kg/day

Balance on the distillation

D01=Fi = Product from fermenter


Fo2=Gi = Bottom from Distillation column
Fo1= Top product from Distillation column
Fo1 = 96% Alcohol from Distillation column
D01=Fo1- Fo2
197,571.5168 – 100000 = 97,571.5168 kg/day = DDGS

31
Material balance for evaporator
The literature survey reveals that for 1kg DDGS 0.8 kg of water
evaporates from the triple effect evaporator.

Go1=Hi=thin stillage from solid separation

Ho2=waste water

Ho1=Ji1=syrup to dryer

Thus from the total DDGS, (i.e 97,571.5168 kg/day) 78,057.21 kg/day
water evaporates and the syrup produced would be 19,514. 31 kg/day.

32
3.3 ENERGY BALANCE CALCULATIONS
Basis: Room temperature 25° C
Energy balance on the cooker
Q = mCpΔt
= (177,816.14)(0.85)(120-25)

=3,778,592.97 kcal/day = 157,441.374 kcal/hr.

Energy balance on Heat exchanger

T1,a T2, b

t2,c t1,d

Q, a= mCpΔt

= (177,816.14)(0.85)(T1-25) ,T1 =120℃

=14,358,653.31 kcal/day =598,277.221 kcal/hr.

Q, b= mCpΔt

= (177,816.14)(0.85)(T2-25) ,T2=86.7℃

=9,325,567.462 kcal/day =388,565.31 kcal/hr.

33
Heat gained =Q, a - Q, b

= (598,277.221 - 388,565.31) kcal/hr.

= 209,711.91 kcal/hr.

Out let temp of water


209,711.91 kcal/hr. =mCp (t2-25)
=19,755.37*1(t2-25)

t2 = 35.62℃

Energy balance around Distillation Column:

Q,Fi = mCpΔt

= (197,571.516) (0.9)(35-25)

= 1,778,143.644 kcal/day

Q, Fo1=mCpΔt

= (100000)(0.522)(78-25)

34
=2,766,600 kcal/day

Q, Fo2=mCpΔt

=97,571.5168(0.72)(100-25)

=5,122,504.59 kcal/day

The heat duty of the reboiler would be

Qs = (Q, Fo2+ Q, Fo1) – Q,Fi

= (5,122,504.59+2,766,600)- 1,778,143.644

=6,110,960.946 kcal/day = 254,623.37 kcal/hr.

Condenser
Heat provided by condenser = latent heat lost by vapors’

= mλ

=(100,000*260)kcal/day

=26,000,000 kcal/day

=1,083,333.333 kcal/hr.

Water Requirement
Assuming water is available at 25℃

Q = mCpΔt
1,083,333.333 kcal/hr. = m(1)(78-25)

m= 20,440.25 kg/hr.

35
Chapter 4

Equipment sizing
Design Calculations:
(For Co2 Scrubber, Fermenter, Heat Exchanger, Condenser,
Distillation Colum, Alcohol Storage Tank).

DESIGN CALCULATIONS FOR CO2 SCRUBBER

Water flow rate = 504.4 kg/hr


Vapor flow rate = 3979.72 kg/hr
Density of water = 1000 kg/m3
n P
Density of vapor= =
V RT
Average molecular weight of feed = 43.072 kg/kg mole

n P
PV= =
V RT
Density of vapor = lv
= 1.76 kg/m3
Then
Uv = 0.035 (ρL/ρv)1/2
= 0.035 (997.045/1.76)1/2
= 0.8326 m/sec
3979.72
Vapor volumetric flow rate Qv = =0.628
1.76∗3600

Vessel area = 0.628/0.832


= 0.754 m2

π 2
VA = (d)
4

d=

√ 4 VA
π

d=

√ 4∗0.628
π

d = 0.894 m Disengagement space

36
416.66
Liquid volumetric flow rate QL =
1000∗3600

QL = 1.401 x 10-4 m3/sec


Let that hold up time = 20 min
Volume for 20 min. hold up = 1.16 x 10-4 x 1200
= 0.168 m3
0.168 m3
Liquid depth =
0.754 m 2

= 0.222 m

Total height = Liquid depth +disengagement space


= 0.222 + 0.894
= 1.11 m

Let the thickness of cylindrical shell = Tm


Tm = {(d + 100)/1000} + C
let corrosion allowance C = 0.125 inch
Tm = {(40.04 + 100)/1000} + 0.125
= 0.265 inch
Outer diameter = O.D
= 40.04 + 2 x 0.265
= 40.57 inch
Volume of cylindrical shell = Vs
Vs = (π/4) {(O.D)2 – (I.D)2} x h
Vs = (π/4) {(40.57)2 – (40.04)2} x (0.967 x 3.2808 x 12)
Vs = 1277.63 inch3 or 0.739 ft3

Volume for top and bottom plates (flat)


Vb + Vt = 2 (π/4) (O.D)2 x Tm
= 2 (π/4) (40.57)2 x 0.265/(1/2) 2
= 0.311ft3

Total volume of material = VT


VT = Vs + (Vb + Vt)
= 0.739 + 0.311
= 1.05ft3 or 0.0266m3

Material of construction = Carbon steel


Density of carbon steel = 7855.42 kg/m3
Weight of the tank = 7855.42 x 0.0266
= 209.4 kg

37
Specifications:
Inner diameter of the scrubber = 40.57inch
Outer diameter of the scrubber = 40.04inch
Height of the scrubber = 1.11 m
Total volume of the material used = 0.0266m3
Total weight of the scrubber = 209.4 kg

FERMENTER:
Commercial fermentations are usually performed especially in vessels held under positive
pressure of sterile air to resist entry of contaminating micro-organism.
However, the production of pathogenic organisms for medical purposes or for biological, welfare
operates below atmospheric pressure because the safety of the plant operators is more important
than the integrity of the product. Fermentation formerly distinguished processes from which
oxygen was absent, but the term has now been extended to aerobic processes.
The function desired in fermentation are gas liquid contacting, on-line sensing of concentrations,
mixing, heat transfer, foam control, and feed of nutrients, or reagents such as those of pH
control. The workhorse of the fermentation industry is the conventional batch fermenter. There is
extensive process piping, and copper or brass fittings are avoided because of the highly
deleterious effects of copper on many biological systems. For example, more than 50% reduction
in yield was noted in penicillin fermentation was a bronze valve was in a feed line. There are
three ways of temperature control:
a) Cooling coils
b) External heat exchanger
c)Irrigation
For larger tanks because heat transfer area of a jacket is inadequate for cooling from sterilization
temperature to operating temperature in a reasonable time. So jackets may be inadequate for
fermentation. The problems of foam production are encountered.
a) By scrubbing carbon dioxide
b) By adding antifoam agents

Design Calculations for fermenter:


Mass to be handled per day in fermenter = 197,571.5168kg/day
If we use one fermenter it has very big dimensions; so reduce the fermenter 4 times.
Instead of using single fermenter we use 4 fermenter to handle the some mass.
Mass handled per hour = 8232.15
Mass to be handled in 6 hours = 32928.59
Density of fluid = 1145 kg/m3
Volume of the fluid (Vf) = (32928.59/1145)
= 28.76 m3
Free space in the fermenter = 30%
Total volume of the fermenter = 1.30 Vf
VT = 1.3 x 28.76
= 37.394 m3
L = 2D
VT = Area x Length

38
Area = (π/4) (Di)2
Di = inside diameter of fermenter
VT = (π/4) (Di)2 x (2Di)
37.394 = (π/2) (Di)3
Di = 2.87 m
L = 2 x Di
= 2 x 6.119
= 5.75 m
The volume occupied by the ellipsoidal head and bottom = VZ

VZ = 2 (π/6) (Di) 2 x H
H = 0.5 m
VZ = (π/3) (2.87) 2 x 0.5
= 4.33 m3

Volume occupied by the cylinder = VC


VC = VT – VZ
= 37.39 – 4.33
= 33.09m3

VC
1
Height of the cylinder, l = π *
( Di) 2
4

33.09
1
l= π *
(2.87)2
4

l =5.11 m

Pressure of liquid head = ρgh

h = liquid head, cylindrical

V
1
h== π * , and
( Di) 2
4
v =Vt – Volume of ellipsoidal bottom
= Vt – Vz
= 37.394 – (4.33/2)
= 35.22 m3

39
35.22
1
h= π *
(2.87)2
4

= 5.44m

Maximum height of ellipsoidal shape = H = 0.5m


Actual head = h’ = h + H
= 5.44+ 0.5
= 5.94 m
So, pressure due to liquid head = ρgh’
= 1145 x 9.8 x (5.94/1000)
= 61.6KN/m2
Maximum allowable pressure = P = 1.33 (101.3 + 61.6)
= 216.66 KN/m2
Material of construction = Carbon Steel
Let Thickness of cylindrical shell = tm = 0.015, including Corrosion allowance

Actual volume of cylindrical shell = Vs


Vs = (π/4) {(O.D)2 – (I.D) 2} x l

O.D = Outer diameter


I.D = Inside diameter
O.D = I.D + (2xtm)

= 2.87 + 2 x 0.015
= 2.9
Vs = (π/4) {(2.9) 2 – (2.87) 2} x 5.44

= 2.846 m3
Volume of the material used for ellipsoidal at the top = Vt
Vt = (π/6) {(2.9)2 x 0.507 – (2.87)2} x 0.5
Vt = 0.0205 m3
Volume of flat bottom = Vb = (π/4) (O.D)2 x tm
Vb = (π/4) (2.9) 2 x 0.0205
Vb = 0.166 m3
Total volume = 2.846 m3
Volume of the material used for ellipsoidal at the top = Vt
Vt = (π/6) {(6.1446)2 x 0.507 – (6.119)2} x 0.5
Vt = 0.2205 m3
Volume of flat bottom = Vb = (π/4) (O.D) 2 x tm
Vb = (π/4) (2.97) 2 x 0.0128
Vb = 0.379 m3

Specifications:
Inner diameter of the fermenter = 2.87 m
Outer diameter of the fermenter = 2.9 m

40
Total height of the fermenter = 5.44 + 0.5
= 5.94 m
Total volume of the material used = 0.2205m3
Total weight of the fermenter = 23144.23 kg
No of fermenter used = 4

HEAT EXCHANGERS:
Heat transfer equipment is defined by the function it fulfills in a process.
There are many types of heat exchangers.
1. Double Type Heat Exchangers: (Hairpin type)
These are used for small duty and usually fit in a process line. The principal
disadvantage to the use of double pipe heat exchanger lies in the small
amount of heat transfer surface contained in a single hair pin. So large
number of hair pin are used for larger heat transfer. There are 14 points
where leakage may occur. So for large heat transfer shell and tube heat
exchanger are used.
2. Shell and Tube Heat Exchangers:
These types of heat exchangers consist of a shell containing large number of
tubes. Hot and cold fluid passes through them.

Design Calculations for Heat Exchanger:


Heat to be removed from hot stream of the beer still = 485,864.081 kcal/hr
Or 485,864.081 x 3.97 = 1,928,880.4 BTU/hr

Δt 2− Δt 1 95−61.7
LMTD = = =77.15
lnΔt 2/ Δt 1 ln 95 /61.7

T 1 – T 2 120 – 86.7
R= = =3.14
t 2−t 1 35.62−25

t 2−t 1 35.62−25
S= = =0.11
T 1 – t 1 120 – 25

Ft = 0.76

For 1 shell pass, 2 tubes pass


t = 0.76 x 77.15

41
= 58.9 °F
Assume UD = 150 BTU/hr-ft2 °F

Area required = ?
Q = UDA x Δt

Q
A=
U D Δt

1,928,880.4
A=
150 x 77.15

A= 166.7 ft2

3
We employ. Inch O.D, 16 BWG tubes, 16ft long wherever possible, because the slops may tend
4
to deposit residue, a combined dirt factor of 0.004 and square pitch will be used.

Area per foot of tube = alt = 0.1963 ft2

A
No. of tubes required = Nt =
al t N t

166.7
=Nt =
0.1963 x 16

= 53.1

Assume 1 shell pass, 4 tube passes . inch O.D, 1 inch square pitch, 194 tubes
in 17.25 inch I.D shell

Corrected UD

A = 53.1 x 0.1963 x 16
= 166.67ft2

1,928,880.4
UD =
77.15 x 166.67

=150.21 BTU/hr-ft2 °F

SHELL SIDE

Flow area = As
Assume baffle space, B = 4 inch
I .DxC xB
As =
144 P T

42
13.25 x 0.25 x 4
=
144 x 1

= 0.92 ft2

Mass Velocity
W
Gs=
as

W = 41677.08 kg/hr (or) 95440.51 lb/hr

Gs = (95440.51/0.092)
= 1037396.84 lb/ hr-ft2

NRe(s) = {(Ds Gs)/μ}


μ = 0.87712, De = 0.0792 ft
NRe(s) = {(0.0792 x 1037396.84)/0.87712}
= 93672
JH = 185

k = 0.353 BTU/hr-ft2 °F
ϕs = 1
Cp = 1 BTU/lb °F
ho = JH (k/De) (Cpμ/k)1/3 ϕs
= 185 x (0.353/0.0792) (1 x 0.8712/0.353)1/3 x 1
= 1114

TUBE SIDE:

Flow area = at = 0.302 ft2 (from Kern)

N t x(flowarea /tube)
Total flow area =
144 x No . of tubes

194 x 0.302
=
144 x 4

=0.1017 ft2

Mass Velocity = Gt = W/at


Mass flow rate of mash = W = 52096.35 kg/hr
= 119591.52 lb/hr
Gt = 119591.52 / 0.1017
= 1175924.48 lb/ hr-ft2

NRe(t) = {(Ds Gs)/μ}

43
At ta = 114.8 °F
μ = 0.662 x 2.42
= 1.602 lb/hr ft (Kern, fig. 14)

D = 0.62/12
= 0.0517 ft (Kern)

NRe(t) = {(0.0517 x 1175924.48)/1.602}


= 37949

L/D = 16/ 0.0517 = 309.47

JH = 115
At t = 114.8 °F
k = 0.339 BTU/hr-ft2 °F
ϕt = 1
Cp = 0.97 BTU/lb °F
hi = JH (k/D) (Cpμ/k)1/3 ϕt
= 115 x (0.339/0.0517) (0.97 x 1.602/0.339)1/3 x1
= 1253
hio = hi x (I.D/O.D)
= 1253 x (0.62/0.75)
= 1036
Clean overall coefficient, Uc
h io x h o
Uc =
h io+h o

1036 x 1114
Uc =
1036+1114

Uc = 536.79 BTU/hr-ft2 °F

Design overall coefficient, UD

UD = Q/AΔt = 5617299.81/ (61.32 x 609.31)


= 151

Dirt Factor , Rd

U C – U D 536.79−151
Rd = = =0.00475
U C x U D 536.79 x 151

Pressure Drop Calculations:

Shell Side
NRe(s) = 93672

44
f = 0.0015 (Kern)

No of crosses N + 1 = 12 L/B
= 12 x (16/4) = 48
DS = 13.25/12 = 1.104 ft

fGs 2 DS(N +1)


ΔPS =
5.22 x 1010 D e S ϕ s

0.0015(1037396.84)2 x 1.104 x 48
ΔPS =
5.22 x 10 10 x 0.0792 x 1 x 1

ΔPS = 9.5 psi

Tube Side
NRe(t) = 37949.62
f = 0.00019 ft2/in2 (Kern, (7) fig. 26)
S=1

f Gt 2 L n
ΔPt =
5.22 x 1010 D S ϕ t

0.00019 x(1175924.48)2 x 16 x 4
ΔPt =
5.22 x 1010 x 0.05 x 1 x 1

ΔPt = 6.442 psi

Specifications:

Shell Side Tube Side


I.D = 13.25 in No of tubes = 194
Baffle Space = 4 in Length of tube = 16 ft
Passes = 1 Pitch = 1 in.sq
Passes = 4

CONDENSER:
They are used to convert vapor to liquid phase and recover latent heat only

DESIGN CALCULATIONS FOR CONDENSER - 1


Heat provided by condenser = latent heat lost by vapors’

45
= mλ

=(100,000*260)kcal/day

=26,000,000 kcal/day

=1,083,333.333 kcal/hr.

Water Requirement

Assuming water is available at 25℃

Q = mCpΔt

1,083,333.333 kcal/hr. = m(1)(78-25)

m= 20,440.25 kg/hr.

Q = UD A ΔT
Q
A=
∆tU D

1,083,333.33
A=
53∗100
= 204.4 ft2
BWG = 10
Length of each tube = 16 ft
3
Outer diameter of the tube = D = inch
4
PT = Pitch = 1 inch square
Surface area per linear foot for the above specification
at = 0.1963 ft2/ linear ft

Calculation for the No of tubes


area
No of tubes =
length∗at
=204.4/(16*0.1963)
=67.2 or 68
Actual no of plates = 54
Shell inside diameter = 25 inch (Perry C. hb)
A’ = Actual heat transfer area = Nl x length of tube x at
A’ = 54 x 16 x 0.1963
A’ = 169.6ft2
Q
Corrected value of UD =
A’∆T

46
1,083,333.33
=
169.25∗81.64

= 120.5 BTU/ hr-ft2 °F

Baffle spacing = B = 12 inch


Baffle spacing < shell I.D
Baffle spacing > 1/5 of shell I.D
C’ = clearance between tubes = 0.25 inch

SPECIFICATIONS:

Shell and tube type Heat Exchangers


One shell side pass and two tube side pass
Fluid passing in shell side = Cold
Fluid passing in tube side = Hot
A’ = Actual heat transfer area = 204.4 ft2
L = Length of the tube = 16ft
O.D = Outer diameter of the tube = 3/4 inch
D1 = Inside diameter of tube = 0.625 inch
I.D = Inside diameter of the shell = 25 inch
N1 = No of tubes = 54
B = Baffle spacing = 12 inch
C’ = Clearance between tubes = 0.25 inch

DESIGN CALCULATIONS FOR DISTIILATION COLUMN

Basis: 1 hour operation


Feed = 10% ethanol
Total amount of feed = 8232,15 kg

Mass of ethanol = 0.1 x 8232.15


= 823.21kg
Mass of water = 0.9 x 8232.1
= 7408,9kg
Total mass = 52096.34 kg
Mole = Mass / Molecular Weight
Moles of ethanol = 823.21/46 = 18.89

47
Moles of water = 7408.9/18
= 411.6
Total moles = 430,5
Mole fraction of ethanol = 18.89/430.5
= 0.04

Mole fraction of water = 411.6 /430.5

= 0.96
Average molecular weight of feed = Total mass /Total moles
= 8232,15 kg/430.5

= 19.12 kg/kg-mol
Moles of feed = F = 8232,15 /19.12
= 430.59kg-moles
Mole fraction of FM in feed = Xf

Moles of ethanol 18.89


Xf = = =
Moles of feed 430.59

Product = 60% Ethanol


Total amount of product = 10185.62 kg
Mass of ethanol = 0.6 x 10185.62 =6111.4 kg
Mass of water = 0.4 x 10185.62 =4074.23 kg
Total Mass = 11155.62 kg

6111.4
Moles of ethanol = =132.86
46

4074.23
Moles of water= =226.35
18

Total no. of moles = 359.21


Mole fraction of ethanol = 0.36
Mole fraction of water = 0.64

Total mass
Average molecular weight of the product =
Total moles

=10185.62/359.21`

= 28.35 kg/kg mol

10185.62
Moles of product = D =
28.35

48
= 359.21 kg moles

Bottom:
Total amount of bottom = 97,571.51kg

Mole fraction of ethanol in bottoms = 0.00


Mole fraction of water in bottoms = 1.00
Average molecular weight of bottoms = 18 kg / kg of mole
97571.51
Moles of bottom =
18
= 54420.6 kg moles

Mole fraction of Fm in bottoms = XW = 0.00


No of theoretical plates = 2
Considering efficiency of sieve column = 50%
2
Then actual no of plates =
0.5
=4
For washing purposes extra no. of plates = 2
Total no of plates = 4 + 2 = 6
Flow rate of feed = G = 52096.354 kg/hr

54420.6
=G=
3600∗0.4536

G= 33.33 lbm/sec

Density of the liquid = L = 60.126 lbm/ ft3


Density of vapor = G = 0.06 lbm/ ft3

Let the tray spacing = 24 inch

Liquid seal = 0.05 inch (From peters, page 656))


The Max. Allowable super facial vapor velocity can be calculated as
Vm = Kv {(ρ L – ρ G)/ ρ G} ½ ,where Kv= 0.3
Vm = 0.3 {(60.126 – 0.06)/ 0.06} 1/2
= 9.49 ft/sec

flow rate of feed


Area of the column = Vm∗Density of vapor

97.12
= 9.49∗0.06 = 170.7ft2

Diameter = d = {(4 x Area /π)} 1/2


= 14.57 ft
49
Height = H = {Tray spacing x no of trays} + allowance
H = {2 x 6} + 2
H = 14 ft

SPECIFICATIONS
Diameter of the column = 8.44 ft

Height of the column = 14 ft

No of trays = 6

4.2 Materials of Construction:


Any Engineering design, particularly for a chemical process plant, is only useful when it can be
translated into reality by using available materials of construction combined with the appropriate
techniques of fabrication can play a vital role in the success or failure of a new chemical plant.
Corrosion in Brewery Industry:
Breweries are unique in many aspects in the food-processing industry. The product and its
production as well as cleaning procedure, storage, and bottling, all use great quantities of water.
They require a large amount of tank age and extensive hot water facilities. Furthermore, the
product is an acidic liquid that is aggressive to low carbon steel. This is further complicated that
the presence of irons ions in the product drastically affects its shelf life. Wet, damp, and high-

50
humidity conditions all contribute to plant corrosion and premature equipment failure if not
properly treated. The factors make the typical brewery a challenge to the corrosion engineer. A
brewery materials engineer must be familiar with the materials of constructions for all of this
equipment and must also be aware of diverse corrosion control techniques involving coatings,
metals, cathodic protection, plastics and even the use of inhibitors.
Corrosion Control Methods:
As in any other industry, there are always several ways to solve a given material problem in the
brewery. The task of the materials (corrosion) engineer is to sort out the available choices and to
arrive at the most cost-effective solution to the problem. Traditionally, brew masters, who at one
time exercised, employed set conditions for plant equipment, such as wood with wax linings
( tanks with slotted or perforated false bottoms used for filtering clear liquid from the grain
mash) for fermentation and storage, copper for kettles and lanter tubes, and low carbon steel for
pasteurization.
Here, for our case corrosion is controlled by coating the equipment’s with paints.
Important Material Available
Material of construction may be divided in to two general classifications of metals and non
metals. Pure metals and metallic alloys are included under the first classification.
1. Iron and Steel:
Although many materials have greater corrosion resistance than iron and steel cost aspects favor
the use of iron and steel. As a result they are often used as a material of construction when it is
known that some corrosion will occur. If this is done the presence of iron salts and discoloration
in the product can be expected and periodic replacement of the equipment should be anticipated.
In general, cost of iron and carbon steel exhibit about the some corrosion resistance. They are not
suitable for use with dilute acids, but can be used with many strong acids, since a protective
coating composed of corrosion products forms on the metal surface.

2. Stainless Steel:
There are more than 100 different types of stainless steels. The main reason for the existence of
stainless steels in their resistance to corrosion. Chromium is the main alloying element, and the
steel should contain at least 11%. Chromium is a reactive element but it and its alloys passivity
and exhibit excellent resistance to many environments. A large number of steels are available. So
stainless steel contains chromium, nickel, iron, and also containing small amount of other
essentials properties. They have excellent corrosion resistance and heat-resistance properties.
Most of the brewery equipment currently being installed is fabricated from type 304 stainless
steel.
3. Nickel and its Alloy:
Nickel exhibits high corrosion resistance to most alkalies. Nickel – clad steel is used extensively
for equipment in the production of caustic soda and alkalies. The strength and hardness of nickel
is almost as great as carbon steel. In general, oxidizing conditions promote the corrosion of
nickel, and reducing conditions retard it. Monel, an alloy of nickel containing 67% nickel and
30% copper is often used in food industry. This alloy is stronger than nickel and has better
corrosion resistance properties than either nickel or copper.
4. Copper:
It has been the traditional metal in breweries for centuries, but with advent of new alkaline
cleaner, some corrosion problem has occurred. Copper and Copper base alloys are use in the

51
formation of heat exchanger tubing, piping, fittings, etc. Although corrosion rates are
comparatively small. However, the corrosion rate of 100° C, the corrosion rate of copper is
comparatively small. However, the corrosion of 100° C is about 5 times that which takes place at
room temperature.
5. Aluminum:
The lightness and relative ease of fabrication of Aluminum and its alloys are factors favoring the
use of these materials. Aluminum resists attacks by acid because a surface film of inert hydrated
aluminum oxide is formed. This film adheres to the surface and offers good protection unless
materials which can remove the oxides, such as hydrogen acids or alkalies are present.
6. Lead:
Pure lead has creep fatigue resistance, but its physical properties can be improved by the addition
of small amount of silver, copper, antimony, tellurium. Lead- Clad equipment is in common use
in many chemical plants. Lead shows good resistance to phosphoric acid and sulfuric acid but it
is susceptible to attack by acetic acid and nitric acid.
7. Hastelloy:
The beneficial effects of nickel, chromium and molybdenum are combined in hastelloy C to give
an expensive but highly corrosion-resistance material. A typical analysis of this shows 56%
nickel,17 % molybdenum, 16% chromium,5% iron, and 4% tungsten with manganese, silicon,
carbon, phosphorus, and sulfur making up the balance. Hastelloy C is used where structural
strength and good corrosion resistance are necessary under conditions of high temperature. The
material an be machined and is easily fabricated.
8. Coatings:
Breweries are large consumer of quality coatings, not only for tankage but also for structural
steel, flooring and other working areas. The coating used range from high heat silicones for
stacks to special super resistant grouts for floor pavers.
9. Floor materials:
Considerable glazed tile is used in breweries and special epoxies with good adhesion to very
smooth surfaces have employed to coat glazed ceramic tile in order to prevent crazing
(cracking). Bacterial contamination deep in the pores of the concrete is a common occurrence. If
floors are not properly sealed, corrosion of concrete rebar’s and structural steel can result, with
eventual cracking and spalling of concrete.
10. Plastics:
For corrosion control point of view, plastics materials are very useful; therefore they found
application in breweries, water treatment tanks, Acid storage, roofing and gutters are application
for plastics that are common to most industrial activity. Fiberglass and polyvineyl chloride are
among the plastics that have been employed. Small polypropylene tanks for yeast culture and
other specialty service have some record of use.

Recommended Materials of Construction:

Properties of Stainless Steel-304:


1) Have combination of desirable mechanical properties corrosion resistance with
ease of fabrication for industrial application.
2) They are shock resistant.
3) Strength about 750 MN/m2.
4) Yield strength about 270 MN/m2.

52
5) Elongation varies between 30-75% depending upon carbon constant.
Reason for Reason for the Selection of S.S.304
These steel have the best high temperature strength and resistance to scaling of the S.S.
the corrosion resistance of the stainless steel is usually better than that of ferritic steels.
Cost
Stain less steel alloys 304………………..2.15-3.50 US $/day
Stain less steel alloys 316………………..3.0-4.4 US$/day
Stain less steel alloys 440………………..6.2 US$/ day
Stain less steel alloys 440a……………….4.4-52 US$/ day
Yield Strength
Yield strength of SS 304 is 860 which is again 2nd highest in steel family.
Tensile strength
Tensile strength of SS 304 is 860 which is again 2nd highest in steels.
Elongation
Irrespective of the 2nd of being 2nd highest in steel, we still prefer SS 304 because of its highest
% elongation which is 10-40%. Industrial alcohol when pure shows no corrosive action up to its
boiling point temperature, but under certain conditions in the presence of air and in aqueous
solution it can and does give trouble. Therefore, special material of construction used in the
production and handling of ethyl alcohol.
At temperature up to its boiling point (78.3°C) pure ethyl alcohol is probably less corrosive
toward iron, steel and copper than any other common liquid. It also has little or no action on tin
and lead. However, in the presence of air and its aqueous solution its couple effects can be set up
between two or more of the above metals. Corrosion may occur at the elevated temperature,
especially with iron and lead. Although many materials have greater corrosion resistance than
carbon steel, cost aspects favor the use of carbon steel. As a result they are often used as material
of construction when it is known that some corrosion will. All the major equipment’s of
“industrial alcohol plant” is recommended to be manufactured by carbon steel; some
equipment’s where concentrated H2SO4 and dilute acid used stainless steel 304 or 316 are used
otherwise lining of corrosion resistance material can be used.

Chapter 5
ESTIMATION OF EQUIPMENT COST
1. CO2 Scrubber

Inner diameter = 40.57 in

Height = 1.11 m

53
Volume of the scrubber = 0.311 m3 =

Purchased cost of scrubber = $ 2000

Cost index of 1990 = 924

Present Cost index = 1917.5

2000∗1917.5
Present Total cost =
924

= $ 4150.4

2. Fermenter
Inside diameter = 2.87 m
Height = 5.94 m
Total capacity = 153.71 m3
Cost of fermenter = $ 75000
Cost index of 1990 = 924
Present Cost index = 1917.5

75000∗1917.15
Present Total cost =
924

= 155641.23

3. Heat Exchanger
Heat transfer area for carbon steel = 609.31 ft2
The Purchase cost in 1990 = $8000 (for the above H.E)
Calculated heat transfer area =166.6
Present Cost index = 1917.5

8000∗1917.5
Present Cost of H.E =
924

= $ 16,601.7
166.6 0.6
Present Cost =$ 16,601.7( ¿
609.31

54
= $7,625.26

4. Condenser
Heat transfer area = 1237.47 ft2
Purchased cost = $ 18500
Calculated heat transfer area =204.4
Present Purchased cost =18500*1917.5
924
= $ 30270.725
204.4 0.6
Present cost =$ 30270.725( )
1237.47
= $ 10,275.21

5. Distillation Column
Diameter of the column = 8.44 ft
Height o column = 14 ft
Total purchased cost = 22000 x 14 = $ 308,000
$ 308,000∗1917.5
Present Purchased cost =
924

=$639,166.7

6. Storage Tank
Inside diameter = 3.813 m
Total Height = 5.723 m
Capacity = 65.32 m3 = 17253.8 gallon
Purchased cost in 1990 = $ 30000
30000∗1511.9
Purchased cost in 2009 =
924

= $ 49087.66

Equipment Construction of material Total cost($)

Milling Cast iron 72,000

55
Carbon steel 155,641.23
Fermenter
7,625.26
Carbon steel
Heat exchanger
Carbon steel 639,166.7
Distillation column
Carbon steel 10,275.21
Condenser
Cast iron 146,000
Evaporator
Carbon steel 12480
Centrifuge
Carbon steel 4150.4
CO2 scrubber
Carbon steel 49087.66
Storage tank
Carbon steel 124680
Dryer
total 1,221,106.46

Total purchased equipment cost = 1,221,106.46

COST ESTIMATES
Purchased equipment (Delivered), E $ 1,221,106.46
Purchased equipment installation, 47% E $ 573,920.04
Instrumentation and control (Installed), 18% E $ 219,799.163
Piping (Installed), 66% E $ 805,930.26
Electrical Installed, 11% E $ 134,321.71
Buildings (Including services), 18% E $ 573,920.04
Yard Improvement, 10% E $ 122,110.646
Services facilities installed, 70% E $ 854,774.52
Land, 6% E $ 73,266.44

Total Direct Plant cost, D $ 4,579,149.28

Engineering and Supervision, 33% E $ 402,965.13


Construction Expenses, 41% E $ 500,653.65

Total Direct and Indirect Plant cost, (D + I) $ 5,482,768.1

Contractor’s Fees, 21% E $ 256,432.336


Contingency, 42% E $ 512,864.7

56
Fixed Capital Investment $ 6,252,065.1

Working Capital, 86% E $ 1,050,151.556

Total Capital Investment $ 7,302,216.65

TOTAL PRODUCT COST (TPC)

Variable Cost

1. Raw material
Corn = $ 12055.32 (@ $40/ton)
Chemicals = 0.25 TPC
2. Operating Labor (10 – 20%TPC) = 0.15 TPC
3. Direct Supervision (10 – 25% of Operating labor) = 0.02625 TPC
4. Utilities (10 – 20% TPC) = 0.15 TPC
5. Maintenance And Repair (2 – 10% FCI)
= 0.06 x $ 6,252,065.1
=$ 375,123.91

Fixed Cost
1. Depreciation (10% FCI)
= 0.1 x 6,252,065.1
= $ 625,206.51
2. Local Tax (1 -4% FCI)
= 0.025 x 6,252,065.1
= $ 156,301.627
3. Insurance (0.5 -1 % FCI)
= 0.0075 x 6,252,065.1
= $ 46,890.49

TPC = Variable cost + Fixed Cost


= 0.62625 TPC + 828,398.62
= $ 2,216,451.17

Production cost = Annual production cost


Annual production rate

$ 2,216,451.17
=
100∗300

57
= 173.88/ton

Selling Price = $ 324.705/ton (recent pr. = 0.987/gallon)

PAYBACK PERIOD
Profit/yr = Selling price – TPC
= (324.705–173.88) x 100
= $ 15082.5x 300
= $ 4,524,750

Depreciation/yr = V – Vs
n

$ 6,252,065.1
= assuming 10yrs shelf life.
10

= $ 625,206.51

Payout Period = Fixed capital investment


(Profit/yr)+(depreciation/yr)

$ 6,252,065.1
=
4,524,750+625,206.51

= 1.2 years

Chapter 6

Environmental impacts of ethanol


58
Production
 Negative impacts of ethanol production from corn

Some of the economic and energy contributions of the by-products mentioned earlier are negated
by the environmental pollution costs associated with ethanol production. In addition, corn
production uses more herbicides and insecticides than any other crop produced in the thereby
causing more water pollution than any other. Further, corn production uses more nitrogen
fertilizer than produced and therefore is a major contributor to ground water and river water
pollution. In some Western irrigated corn acreage, ground water is being mined 25% faster than
the natural recharge of its aquifer. All these factors suggest that the environmental system in
which corn is being produced is being rapidly degraded. Further, it substantiates the conclusion
that the corn production system is not environmentally sustainable for the future, unless major
changes are made in the cultivation of this major food/feed crop. Major air and water pollution
problems also are associated with the production of ethanol in the chemical plan. Another
pollution problem is the large amounts of waste water that each plant produces, for each gallon
of ethanol produced using corn, about 12 gallons of waste water are produced. This waste water
has a biological oxygen demand (BOD) of 18,000 to 37,000 mg/liter depending of the type of
plant. Ethanol contributes to air pollution problems when burned in automobiles. The
consumption of the fossil fuels release significant quantities of pollutants to the atmosphere.
Furthermore, carbon dioxide emissions released from burning these fossil fuels contribute to
global warming. Overall, if air pollution problems were controlled and included in the
production costs, then ethanol production costs in terms of energy and economics would be
significantly increase.

Ethanol and the Environment

Increasing industrial activity and population growth has resulted in a rising concentration of
'greenhouse gases' in the atmosphere that contribute to the 'Greenhouse Effect'. These gases
include carbon dioxide, methane, and nitrous oxide. The term 'Greenhouse Effect' refers to the
Earth's trapping of the sun's incoming solar radiation, causing warming of the Earth's
atmosphere. This offsets the Earth's natural climatic equilibrium, and results in a net increase in
global temperatures. 'Global Warming' is a term used to describe the increasing average global
temperature. The term 'Climate Change' refers to a wide range of changes in weather patterns
that result from global warming. A substantial increase in the Earth's average temperature could
result in a change in agricultural patterns and melting of polar ice caps, raising sea levels and
causing flooding of low-lying coastal areas. These phenomena could have serious repercussions
on the natural and physical environment, as well as on human health.

To combat these problems, ethanol is widely used in reformulated gasoline’s to help urban cities
meet public health standards.

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Environmental Benefits of Fuel Ethanol

1, Carbon Dioxide

Carbon dioxide from the burning of fossil fuels is the largest single source of greenhouse gases
from human activities, representing about half of all greenhouse gas emissions. Use of 10%
ethanol-blended fuels results in a 6-10% CO2 reduction and higher levels of ethanol can further
reduce the net quantity of CO2 emitted into the atmosphere. More CO2 is absorbed by crop
growth than is released by manufacturing and using ethanol. The carbon dioxide produced during
ethanol production and gasoline combustion is extracted from the atmosphere by plants for
starch and sugar formation during photosynthesis. It is assimilated by the crop in its roots, stalks
and leaves, which usually return to the soil to maintain organic matter, or to the grain, the portion
currently used to produce ethanol. Only about 40 percent or less of the organic matter is actually
removed from farm fields for ethanol production. The rest is returned to the soil as organic
matter, increasing fertility and reducing soil erosion.With modern conservation farming
practices, this soil organic-matter will build up, representing a net removal of carbon dioxide
from the atmosphere. An increase of only 1% in the soil organic matter level means an
atmospheric reduction of over 40 tons of CO2 per hectare of farmland. Ethanol uses in gasoline
has tremendous potential for a net reduction in atmospheric carbon dioxide levels.

2. Carbon Monoxide

Carbon monoxide, formed by the incomplete combustion of fuels, is produced most readily from
petroleum fuels, which contain no oxygen in their molecular structure. Because ethanol and other
“oxygenated” compounds contain oxygen, their combustion in automobile engines is more
complete. The result is a substantial reduction in carbon monoxide emissions.

3. Nitrous Oxide (N2O)

Agricultural grain production for ethanol may generate a slight increase in nitrous oxide (N2O)
emissions resulting from heavy fertilizer use. However, research and advances in agricultural
technology in grain production are resulting in a reduction of these emissions, often to levels
below other common crops.

4.Other Octane Additives

Because of its high octane rating, adding ethanol to gasoline can permit the reduction or removal
of aromatic hydrocarbons (such as benzene), and other hazardous high-octane additives
commonly used to replace tetra-ethyl lead.

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5.Ozone

Because of its effect in reducing hydrocarbons and carbon monoxide in exhaust (that causes
respiratory problems), adding ethanol to gasoline results in an overall reduction in exhaust
ozone-forming potential.

Adding of ethanol to gasoline does create slightly greater amounts of aldehydes during fuel
combustion. Yet the resulting concentrations are extremely small and are effectively reduced by
the three-way catalytic converters in the exhaust systems of all recent-model cars. The Royal
Society of Canada termed the possibility of negative health effects caused by aldehyde emissions
with the use of ethanol blended gasoline as being “remote.” Increased use of renewable fuels like
ethanol, will help counter the pollution and global warming effects of burning gasoline. Under
current conditions, use of ethanol blended fuels as E85 can reduce the net emissions of
greenhouse gases by as much as 30-36% and can further contribute by decreasing fossil energy
use by 42-48%. Ethanol blended fuel as E10 reduces greenhouse gases by 2.4-2.9% and fossil
energy use by 3.3-3.9%. The E10 blend reductions are lower because a smaller fraction of the
blend is ethanol. With improved technologies and use of ethanol made from cellulose, these
reductions in emissions will increase.

Environmental behavior

Recent reviews of the environmental behavior of gasoline oxygenates generally note that ethanol
is not likely to accumulate or persist for long in the environment. For example, the Interagency
Assessment of Oxygenated Fuels observes that ethanol is expected to be rapidly degraded in
groundwater and is not expected to persist beyond source areas. Ethanol in surface water is also
expected to undergo rapid biodegradation, as long as it is not present in concentrations directly
toxic to microorganisms.

Health Effects

Ethanol, the active ingredient of alcoholic beverages, has been part of the human diet — and the
human environment — for thousands of years. It is produced by fermentation by fungi and other
microorganisms, and is found at low levels in the blood and breath of persons who do not drink
alcohol. Ethanol is widely ingested in alcoholic beverages, usually with only mild effects.
However, at sufficiently high doses, ethanol can cause toxic effects in humans, both short-term
(such as inebriation) and long-term (such as cirrhosis of the liver). If ethanol becomes a common
fuel additive, there may be opportunities for exposure by inhalation: ethanol vapors might be
inhaled at gasoline stations or in automobiles, for example. Thus, concern has been raised about

61
the possible health consequences of using ethanol for this purpose. The scientific literature
contains virtually no reports of injury to humans from inhaled ethanol.

REFERENCES

1. www. Wikepedia.com

2. James Bemiller and Roy Whistler, Starch Chemistry and Technology,3 rd edition, 2009

3. J.M Coulson and J.F Richardson, ‘’Chemical Engineering Vol 1,2,6 #rd Edition
press, NewYork 1988

4. Groggins P.H, ‘’Unit Process in Organic Synthesis’’ 5th Edition Mc Graw HIll
Company, NewYork

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5.Kern D.Q, ‘’ Process Heat Transfer Mc Graw Hill Book Company, 1980

6. browonell, Llyod E; ‘’Process Equipment Design’’ Edwing H. Young, 1959, John


Willey and Sons, NewYork Chapman and Hall limited,London.

7. Ethyl Alcohol Production Technique, Noyes Development Corp., Pearl River, N.Y.,
1964.

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