Professional Documents
Culture Documents
INTRODUCTION
In general, alcohol means colorless volatile inflammable liquid especially
intoxicant in wire, beer, spirits etc. and as a solvent, fuel etc. Depending on the
interest of the person involved, for alcohols are many things to many people. To
most non technical people, "alcohol" in the broad sense is used to describe any
intoxicating beverage; thus, a heavy or habitual drinker is called "alcoholic" the case
is some what different in the industrial manufacturing fields which produce finished
goods, intermediates, or raw materials, alcohols play a key role as important
organic solvents and rank second only to water in terms of their almost universal
application. Hence to these people alcohols mean solvents.
Take a spoonful of medicine; feel the smoothness of the lacquer on the pine
pralines in the play room ; look at the tyres of your car, smell the window cleaner
spray, make use of a hair spray, deodorant stick, or are antiperspiral; carry your
water proof cloth covered books to school etc. Alcohols play their solvent role in all
these personal events. Alcohols can be regarded as hydroxyl derivatives of
hydrocarbons, one the basis of several types of classification, di-hydric. There are
various types of alcohol belonging to the homologues series of alcohols, of like
methanol, ethanol, propanol etc. teach member in the series have its own specific
property and most active member of the series is "Ethanol".
Here the fig. Below shows the chemicals from ethanol.
Acetaldehyde
Diethyl Ether
Ethylene
Mixed ether
Alkylated
Aeromatics Ethanol
Butadiene Ethoxides
Esters
C.O.E.& T.,Akola 1
Manufacturing of Ethyl Alcohol from Fruit Waste
Now, in this project we have made an attempt to prey prepare the alcohol
from waste fruits and for it we have chosen Sapota (Hindi Name:Chiku ). (Botanical
Name : Acharas Sapota, Mallinkara Acaras. Sopota the sweetest fruit second to
banana, is chiefly grown in moist coastal tracts of peninsular India, but in recent
years it has spread in the zones of plateau and also sub-mountains tracts of North
India. In India, the main centers of its cultivation are the coastal tract and
Maharashtra, coastal areas of Andhra Pradesh, Tamil Nadu, Karnataka, Saurashtra
and submountain and sumountain areas of H.P. and Bengal. In Maharashtra it is
grown over the areas of too hectares mainly concentrated in Thana, Pune,
Ahmednagar and Aurangabad districts. More than 70% of the area is in Thana
district. In India, it is mainly grown for fruits, but in outer countries the milky latex
from the bank of the "tree" , yields an important commercial product, which fours the
base for manufacture of chewing gums.
TREE CHARACTERS :
One of the definitions of alcohol refer to the occurrence or preparation of
alcohol by known methods such as fermentation of carbohydrates, or synthesis by
hydration of ethylene.
Alcoholic fermentation " a process in which certain kinds of sugar (glucose)
are converted in to alcohols and carbon dioxide by the action of various yields,
moulds of Bacteria on carbohydrate materials. Some of which do not themselves
undergo fermentation but can be hydrolysed in to fermentation substances. ( as in
the production alcohol and alcoholic beverages.)
HISTORY :
The knowledge of fermentation goes back about 6000 years, long before any
written records of history. Archeological studies of relics from due old tombs of
Egypt have uncovered vessels that contained residues of starch and yeasts. During
these ancient times, man originated alcohol which was accepted and celebrated
among puritive and civilized people for thousands of years. All the accident
references discuss alcohol in the form of beverage. But distillation was not known
in Europe until the twelfth a thirteenth century, A.D. Gradually, the concept of
C.O.E.& T.,Akola 2
Manufacturing of Ethyl Alcohol from Fruit Waste
distillation came into the mind of the people workers over the put of alcohol for
India.
In India, the concept of fermentation was commercialized in 1900 to 1910
after the discovery of Louis Pastern and the process came in to use before 1930 to
about 1948 saw the development of indirect Hydration process to manufacture
Ethanol synthetically.
OBJECTIVE :
Growth in potable alcohol industries in liked with the demand for the
consumption of the people and the chemical products in industries in which alcohol
plays an impatant role.
Fruits ripe within 4-5 days, the unripe fruits can be stored at 50% 52 F for
five weeks while ripe fruits can be stored at 320 to 350F.
Yield up to 10 years – 750 fruits/ha.
Field up to 5 years – 1000 – 1500 fruits/ha.
After 15 years, yield was – 2000 – 2500 fruits or 18 – 20 tons /ha.
Especially, in Maharashtra, Sapota was grown in area of 3900ha and the
production was obtained 10,920.
HANDLING AND STORAGE :
Unripe Sapota is kept into the large capacity containers and the containers
are packed with the straw. So, that the surface of the two fruits could not touch with
each other. It should be stored away from all ignition sources and also from high
and low temp. The temp is kept moderate ( depending upon the atmosphere
conditions of the place ).
Under these conditions, the unripe Sapota gets ripen and ready to eat.
All the sources for ethanol production
The three types of sources of ethanol production –
1) SACCHARINE ( Sugar containing ) materials in which the carbohydrate ( the
actual substance from which the alcohol is made ) is present in the form of simple,
directly fermentable six and twelve carbon sugar cane, sugar beets, fruit ( Fresh or
dried ), citrus molasses, cane sorghum why and skim milk.
C.O.E.& T.,Akola 3
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 4
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 5
Manufacturing of Ethyl Alcohol from Fruit Waste
banks, sandy loans sea, red lateritic soils of high rainfall area and well drained
medium black soils are suitable for its cultivation. Chiku will not thrife well on ill
drained soils, soils having hard pan below, loamy soils very deep and stickly soils,
soils containing high per cent of lime are not suitable. The pH range should be 5.5
to 7.5.
Propagation:- Chiku is commercially propagated by vegetative methods like are
layering or inarch grafting, Inarch grafts are prepared on the root stock seedlings of
Rayans(Khirni) or chiku itself. In India, Khirni is very commonly used as root stock
for chiku. The gooti is shallow rooted the majority of roots concentrating in upper
30-40 cms. Of soils while roots of graft go as deep as 90 cms so gooti can thrive
well in both light and deep soils while grafts are suitable for planting only in soils
having 1 m depth, gooti is reported to hear sweeter and mellower pulp, Grafts on
Khirni bear havily than on layers.
Planting:- In drier part planting is done on the onset of monsoon where as in heavy
rainfall areas it is planted after the heavy showers are over. Before planting the
land should be ploughed harrowed and brought to a fine tilth. The pits of size 1 x 1
x 1 m. are opened at a distance of 10 x 10 m. or 12 x 12 m. The pits should be
filled in with 2 kg phosphate, FYM and good soil. After planting the plant should be
supported with bamboo.
Varieties:- There are three main varieties grown in Maharashtra.
1. Kalipatti:- Leaves are dark green, leading variety of the state level shaped fruits,
or excedant spreading branches. The quality is best, pulp is very sweet, mellowing,
yields heavily. It contains one-two seeds, does well in climate of Konkan.
2. Pillipatti:- Next best variety of the State. It is also called as 'Chatri' due to
peculiar habit of growth in whorls, leaves lighter green, fruits are oval and round
small fruits. It is less sweet as compared to Kalipatti. Does best in humid climate.
3.Cricket ball :- Fruits large sized, round variety having granular flesh of market
sweetness grown away from the see coast in drier areas. Bears heavily as
compared to above two varieties.
Manuring:- When the plants are one year old it should receive about 5 kg of FYM
and about 150 gm of nitrogen. The doses should be increased with the
C.O.E.& T.,Akola 6
Manufacturing of Ethyl Alcohol from Fruit Waste
advancement in age. At the age of 7th years it starts bearing fruits. There are two
main seasons Oct-Nov. and Jan-Feb, so far each flowering the tree should receive
50 kg FYM + 1 kg N, 0.5 kg P 2O5 and 0.5 kg of K2O. In drier areas the flowering will
be mostly at beginning of monsoon, so manuring should be done in the month of
May. In case of Chiku there is not bahar treatment (i.e. with holding of water
practices are followed ). However, immediately after harvest orchard hygienic
practices are followed.
Training and Pruning:- Naturally chiku trees assumes a very attractive shape. It is
an ever green tree and requires hardly and pruning, training is done by allowing the
plant to grow upto and height of 1 m above which 3-4 well spaced branches are
allowed to arise.
Harvesting and Yield:- Fruits are ready for harvest in about 4 months i.e. Oct-Nov.
flowering fruits matures by Jan-Feb. or flower matures fruits by April-May.
Harvesting is done when fruits is fully developed matured fruit are not allowed to
ripe on the fruit. At maturity it develop deep chocolate color. If you take a streak on
the fruit immature fruit shown a green below while matured fruit shows yellow colour
below the skin.
Fruits ripe within 4-5 days. The unripe fruits can be stored at 50 0-520F for
five weeks while ripe fruits can be stored at 320-350F.
Yield up to 10 years - 750 fruits/ha.
Yield 15 years - 1000 – 1500 fruits/ha.
After 15 years yield - 2000-2500 fruits or 18-20 tons/ha.
Highly susceptible to water logging and very densative to stagnation. It
however tolerates considerable drought. The plant can tolerate extremes but the
yield goes down as shadding of flowers occurs above 390C. Fair distribution or
rains with mild summer helps in increasing the set. Ramphal cannot withstand
severe summers or cold as that of sustard apple.
C.O.E.& T.,Akola 7
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 8
Manufacturing of Ethyl Alcohol from Fruit Waste
Pear 12 grams 45
Pineapple 12 grams 50
Plum 6 grams 25
Prunes 2.2 grams 9
Raisins 1.4 grams 5
Raspberries each 0.2 grams 1.1
Rhubarb 0.8 grams 8
Satsumas 8.5 grams 35
Strawberries (1 average) 0.6 grams 2.7
Sultanas 1.4 grams 5
Tangerine 6 grams 26
Values for carbohydrates in fruit may vary between different sized pieces!
C.O.E.& T.,Akola 9
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 10
Manufacturing of Ethyl Alcohol from Fruit Waste
ethyl benzene
Concentrated sulfuric acid may from ethyl hydrogen sulfate if added slowly to
ethanol :
CH3 CH2OH + H2SO4 CH3 CH2 H2SO4 + H2O
Ester Formation. Both inorganic and organic acids will form esters with
ethanol :
CH3 CH2OH + HNO3 CH3 CH2 NO3 + H2O
ethyl nitrate
C.O.E.& T.,Akola 11
Manufacturing of Ethyl Alcohol from Fruit Waste
The process of ester interchange is used to prepare ethyl esters from natural
fats and oils :
CH2OOCR CH2OH
| |
2CH3 CH2OH + CH2OOCR CH2OH + 3 RCOOCH2CH3
| | ethyl esters
CH2OOCR CH2OH
glycerol
Vinyl ethyl ether or diethyl acetal are formed by the addition of ethanol to
acetylene, the final product being dependent on whether an alkaline or acid catalyst
is used :
NaOC2H5
CH3 CH2OH + CH ≡CH CH3 CH2OCH2 =CH2
Vinyl ethyl ether
acid
CH3 CH2OH + CH3 CH2OCH ≡CH2 CH3 CH(OCH2CH3)2
catalyst diethyl acetal
C.O.E.& T.,Akola 12
Manufacturing of Ethyl Alcohol from Fruit Waste
Sodium and aluminum ethoxide are valuable agents in the field of organic
synthesis.
C.O.E.& T.,Akola 13
Manufacturing of Ethyl Alcohol from Fruit Waste
FERMENTATION
Eight hundred million people do not have enough food to eat. If we include those
not free from hunger the figure rises to 1.2 billion people. This is one fifth of the
World's population. A further two billion people are deficient in one or more micro-
nutrients (Anon, 1996). In the seventies, food security was viewed mainly in terms
of food supply at the global and national levels. Since then there has been a major
shift in understanding of food security with more emphasis on access to food rather
than purely on production. The Food and Agriculture Organisation of the United
Nations (FAO), amongst other influential organisations, has recognised that the
problem of food security cannot be tackled in isolation. Moreover that it is an
integral component of other development issues. FAO highlights the fact that the
world food insecurity problem is a result of undemocratic and inequitable distribution
of and access to resources rather than a problem of global food production (Anon,
1995), (Anon, 1996).
C.O.E.& T.,Akola 14
Manufacturing of Ethyl Alcohol from Fruit Waste
of raw materials that can be used to produce edible food products and removing
anti- nutritional factors to make food safe to eat.
Food preservation
The production of fermented fruit and vegetable products provides income and
employment to millions of people around the world.
Food processing is probably the most important source of income and employment
in Africa, Asia and Latin America. The Food and Agriculture Organisation of the
United Nations has stated that value added through marketing and processing raw
products can be much greater than the value of primary production (Anon, 1995).
For instance in sub-Saharan Africa more than 60% of the workforce is employed in
the small scale food processing sector, and between one third and two thirds of
value added manufacturing is based on agricultural raw materials (World Bank,
C.O.E.& T.,Akola 15
Manufacturing of Ethyl Alcohol from Fruit Waste
1989), (Conroy et al, 1995). This is particularly important as agriculture and the
formal sector are unable to absorb the growing labour force in many countries.
Fermented foods are popular throughout the world and the production of fermented
food products is important in many countries in providing income and employment.
In Africa, fermented cassava products (like Gari and Fufu) are a major component
of the diet of more than 800 million people and in some parts of Africa it constitutes
over 50% of the diet (Oyewole, 1992). In Asia the preparation of fermented foods is
a widespread tradition. Kimchi (a fermented cabbage product) is the major food
product of Korea. Soy sauce (a fermented legume product) is economically
important from Indonesia to Japan. Over a billion litres are produced each year in
Japan alone. Over 2000 million litres are produced each year in Korea and over 150
million litres in Taiwan. Miso (a fermented legume product) is also very important in
Asia with over 560,000 tons produced a year in Japan alone (Anon, 1982). In Latin
America, fermented cereal products, alcoholic drinks and fermented milk products
are three of the most important sectors of the economy.
Improving nutrition
The optimum health and nutrition of individuals is dependent upon a regular supply
of food and a balanced diet. When diets are sub-optimal, the individual's capacity
for work and achievements are greatly reduced. The most vulnerable groups are
women, children and weaning infants. Availability of food, dietary restrictions and
taboos, misconceptions, limited time available for feeding or eating compound to
create a group of individuals who are nutritionally disadvantaged. Approximately
30% of women consume less than their daily requirements of energy and at least
40% of women world-wide suffer from iron-deficiency anaemia. Fermentation can
enhance the nutritional value of a food product though increased vitamin levels and
improved digestibility.
Vitamins
C.O.E.& T.,Akola 16
Manufacturing of Ethyl Alcohol from Fruit Waste
Digestibility
C.O.E.& T.,Akola 17
Manufacturing of Ethyl Alcohol from Fruit Waste
consistency of these gruels, combined with the small capacity of the infants
stomach, means that it is physically impossible for the child to consume adequate
energy to meet its high demands. By acidifying the porridge through lactic acid
fermentation, starch is hydrolysed into shorter chains of glucose and dextrose,
which reduce the viscosity of the porridge and increase its energy density. Thus the
child is more able to meet its energy requirements.
Medicinal benefits
There are many traditional beliefs about the medicinal properties of fermented food
products. The Fur ethnic group in Sudan strongly believe that the consumption of
fermented foods protects them from disease (Dirar, 1992). Koumiss (a fermented
milk product in Russia) has been used to treat tuberculosis. Pulque (a fermented
fruit sap) is felt to have medicinal properties in Mexico.
C.O.E.& T.,Akola 18
Manufacturing of Ethyl Alcohol from Fruit Waste
in Tanzania has shown that children fed with fermented gruels had a 33% lower
incidence of diarrhoea than those fed unfermented gruels, owing to the inhibition of
pathogenic bacteria by lactic acid forming bacteria (Svanberg, 1992).
Fermentation can improve the flavour and appearance of food. One important area
is the creation of meat-like flavour. Over the years, Sudanese women have
developed products to replace meat in their diets. These include "kawal", fermented
wild legume leaves, "sigda" (fermented sesame press-cake) and "furundu"
(fermented red sorrel seeds). The strong flavours of fermented food products can
enhance a dull diet. Fermented vegetables such as pickles, gundruk and sauerkraut
are used as condiments to enhance the overall flavour of the meal. A small amount
of pickle can make a bland starchy diet (like dahl and rice in Asia) much more
appealing (Battcock, 1992).
Numerous fermented foods are consumed around the world. Each nation has its
own types of fermented food, representing the staple diet and the raw ingredients
available in that particular place. Although the products are well know to the
individual, they may not be associated with fermentation. Indeed, it is likely that the
methods of producing many of the worlds fermented foods are unknown and came
about by chance. Some of the more obvious fermented fruit and vegetable products
are the alcoholic beverages - beers and wines. However, several more fermented
fruit and vegetable products arise from lactic acid fermentation and are extremely
important in meeting the nutritional requirements of a large proportion of the worlds
population. Table 2.1 contains examples of fermented fruit and vegetable products
from around the world.
C.O.E.& T.,Akola 19
Manufacturing of Ethyl Alcohol from Fruit Waste
• Bacteria
• Yeasts
• Moulds
1 Bacteria
Several bacterial families are present in foods, the majority of which are concerned
with food spoilage. As a result, the important role of bacteria in the fermentation of
foods is often overlooked. The most important bacteria in desirable food
fermentations are the lactobacillaceae which have the ability to produce lactic acid
from carbohydrates. Other important bacteria, especially in the fermentation of fruits
and vegetables, are the acetic acid producing acetobacter species.
2 Yeasts
Yeasts and yeast-like fungi are widely distributed in nature. They are present in
orchards and vineyards, in the air, the soil and in the intestinal tract of animals. Like
bacteria and moulds, yeasts can have beneficial and non-beneficial effects in foods.
The most beneficial yeasts in terms of desirable food fermentation are from the
Saccharomyces family, especially S. cerevisiae. Yeasts are unicellular organisms
that reproduce asexually by budding. In general, yeasts are larger than most
bacteria. Yeasts play an important role in the food industry as they produce
enzymes that favour desirable chemical reactions such as the leavening of bread
and the production of alcohol and invert sugar.
Indian sub-continent
Acar, Achar, Tandal achar, Garam nimboo achar Pickled fruit and vegetables
C.O.E.& T.,Akola 20
Manufacturing of Ethyl Alcohol from Fruit Waste
Asinan, Burong mangga, Dalok, Jeruk, Kiam-chai, Pickled fruit and vegetables
Kiam-cheyi, Kong-chai, Naw-mai-dong, Pak-siam-
dong, Paw-tsay, Phak-dong, Phonlami-dong,
Sajur asin, Sambal tempo-jak, Santol, Si-sek-chai,
Sunki, Tang-chai, Tempoyak, Vanilla,
East Asia
Africa
Lamoun makbouss, Mauoloh, Msir, Mslalla, Olive Pickled fruit and vegetables
C.O.E.& T.,Akola 21
Manufacturing of Ethyl Alcohol from Fruit Waste
seeds
Americas
Cucumber pickles, Dill pickles, Olives, Sauerkraut, Pickled fruit and vegetables
Middle East
Moulds
Moulds are also important organisms in the food industry, both as spoilers and
preservers of foods. Certain moulds produce undesirable toxins and contribute to
the spoilage of foods. The Aspergillus species are often responsible for undesirable
changes in foods. These moulds are frequently found in foods and can tolerate high
C.O.E.& T.,Akola 22
Manufacturing of Ethyl Alcohol from Fruit Waste
Enzymes
The changes that occur during fermentation of foods are the result of enzymic
activity. Enzymes are complex proteins produced by living cells to carry out specific
biochemical reactions. They are known as catalysts since their role is to initiate and
control reactions, rather than being used in a reaction. Because they are
proteinaceous in nature, they are sensitive to fluctuations in temperature, pH,
moisture content, ionic strength and concentrations of substrate and inhibitors. Each
enzyme has requirements at which it will operate most efficiently. Extremes of
temperature and pH will denature the protein and destroy enzyme activity. Because
they are so sensitive, enzymic reactions can easily be controlled by slight
C.O.E.& T.,Akola 23
Manufacturing of Ethyl Alcohol from Fruit Waste
Nearly all food fermentations are the result of more than one micro-organism, either
working together or in a sequence. For example, vinegar production is a joint effort
between yeast and acetic acid forming bacteria. The yeast convert sugars to
alcohol, which is the substrate required by the acetobacter to produce acetic acid.
Bacteria from different species and the various micro-organisms - yeast and moulds
-all have their own preferences for growing conditions, which are set within narrow
limits. There are very few pure culture fermentations. An organism that initiates
fermentation will grow there until it’s by-products inhibit further growth and activity.
During this initial growth period, other organisms develop which are ready to take
over when the conditions become intolerable for the former ones.
In general, growth will be initiated by bacteria, followed by yeasts and then moulds.
There are definite reasons for this type of sequence. The smaller micro-organisms
are the ones that multiply and take up nutrients from the surrounding area most
rapidly. Bacteria are the smallest of micro-organisms, followed by yeasts and
moulds. The smaller bacteria, such as Leuconostoc and Streptococcus grow and
ferment more rapidly than their close relations and are therefore often the first
species to colonise a substrate (Mountney and Gould, 1988).
C.O.E.& T.,Akola 24
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 25
Manufacturing of Ethyl Alcohol from Fruit Waste
Yeasts Tolerate
acid, 40%
sugar
aw > =0.85
C.O.E.& T.,Akola 26
Manufacturing of Ethyl Alcohol from Fruit Waste
Desirable fermentation
It is essential with any fermentation to ensure that only the desired bacteria, yeasts
or moulds start to multiply and grow on the substrate. This has the effect of
suppressing other micro-organisms which may be either pathogenic and cause food
poisoning or will generally spoil the fermentation process, resulting in an end-
product which is neither expected or desired. An everyday example used to
illustrate this point is the differences in spoilage between pasteurised and
unpasteurised milk. Unpasteurised milk will spoil naturally to produce a sour tasting
product which can be used in baking to improve the texture of certain breads.
Pasteurised milk, however, spoils (non-desirable fermentation) to produce an
unpleasant product which has to be disposed of. The reason for this difference is
that pasteurisation (despite being a very important process to destroy pathogenic
micro-organisms) changes the micro-organism environment and if pasteurised milk
is kept unrefrigerated for some time, undesirable micro-organisms start to grow and
multiply before the desirable ones. In the case of unpasteurised milk, the non-
pathogenic lactic acid bacteria start to grow and multiply at a greater rate that any
pathogenic bacteria. Not only do the larger numbers of lactic acid bacteria compete
C.O.E.& T.,Akola 27
Manufacturing of Ethyl Alcohol from Fruit Waste
more successfully for the available nutrients, but as they grow they produce lactic
acid which increases the acidity of the substrate and further suppresses the bacteria
which cannot tolerate an acid environment.
The principles of microbial action are identical both in the use of micro-organisms in
food preservation, such as through desirable fermentations, and also as agents of
destruction via food spoilage. The type of organisms present and the environmental
conditions will determine the nature of the reaction and the ultimate products. By
manipulating the external reaction conditions, microbial reactions can be controlled
to produce desirable results. There are several means of altering the reaction
environment to encourage the growth of desirable organisms. These are discussed
below.
There are six major factors that influence the growth and activity of micro-organisms
in foods. These are moisture, oxygen concentration, temperature, nutrients, pH and
inhibitors (Mountney and Gould, 1988). The food supply available to the micro-
organisms depends on the composition of the food on which they grow. All micro-
organisms differ in their ability to metabolise proteins, carbohydrates and fats.
Obviously, by manipulating any of these six factors, the activity of micro-organisms
within foods can be controlled.
Moisture
C.O.E.& T.,Akola 28
Manufacturing of Ethyl Alcohol from Fruit Waste
Water is essential for the growth and metabolism of all cells. If it is reduced or
removed, cellular activity is decreased. For example, the removal of water from cells
by drying or the change in state of water (from liquid to solid) affected by freezing,
reduces the availability of water to cells (including microbial cells) for metabolic
activity. The form in which water exists within the food is important as far as
microbial activity is concerned. There are two types of water - free and bound.
Bound water is present within the tissue and is vital to all the physiological
processes within the cell. Free water exists in and around the tissues and can be
removed from cells without seriously interfering with the vital processes. Free water
is essential for the survival and activity of micro-organisms. Therefore, by removing
free water, the level of microbial activity can be controlled. The amount of water
available for micro-organisms is referred to as the water activity (aw). Pure water
has a water activity of 1.0. Bacteria require more water than yeasts, which require
more water than moulds to carry out their metabolic activities. Almost all microbial
activity is inhibited below aw of 0.6. Most fungi are inhibited below aw of 0.7, most
yeasts are inhibited below aw of 0.8 and most bacteria below aw 0.9. Naturally, there
are exceptions to these guidelines and several species of micro-organism can exist
outside the stated range. See table for further information on water activity and
microbial action. The water activity of foods can be changed by altering the amount
of free water available. There are several ways to achieve this – drying to remove
water; freezing to change the state of water from liquid to solid; increasing or
decreasing the concentration of solutes by adding salt or sugar or other hydrophylic
compounds (salt and sugar are the two common additives used for food
preservation). Addition of salt or sugar to a food will bind free water and so
decrease the aw. Alternatively, decreasing the concentration will increase the
amount of free water and in turn the aw. Manipulation of the aw in this manner can be
used to encourage the growth of favourable micro-organisms and discourage the
growth of spoilage ones.
C.O.E.& T.,Akola 29
Manufacturing of Ethyl Alcohol from Fruit Waste
Aw Phenomenon Examples
0.90 Lower limit for bacterial growth. Foods with 55% sucrose, 12% salt.
Salmonella, Vibrio
Intermediate-moisture foods (aw =
parahaemolyticus, Clostridium
0.90-0.55)
botulinum, Lactobacillus and some
yeasts and fungi inhibited
0.85 Many yeasts inhibited Foods with 65% sucrose, 15% salt
0.60 Lower limt for growth of osmophilic Dried fruits (15-20% water)
or xerophilic yeasts and fungi
C.O.E.& T.,Akola 30
Manufacturing of Ethyl Alcohol from Fruit Waste
Oxidation-Reduction potential
Oxygen is essential to carry out metabolic activities that support all forms of life.
Free atmospheric oxygen is utilised by some groups of micro-organisms, while
others are able to metabolise the oxygen which is bound to other compounds such
as carbohydrates. This bound oxygen is in a reduced form.
Micro-organisms can be broadly classified into two groups - aerobic and anaerobic.
Aerobes grow in the presence of atmospheric oxygen while anaerobes grow in the
absence of atmospheric oxygen. In the middle of these two extremes are the
facultative anaerobes which can adapt to the prevailing conditions and grow in
either the absence or presence of atmospheric oxygen. Microaerophilic organisms
grow in the presence of reduced amounts of atmospheric oxygen. Thus, controlling
the availability of free oxygen is one means of controlling microbial activity within a
food. In aerobic fermentations, the amount of oxygen present is one of the limiting
factors. It determines the type and amount of biological product obtained, the
amount of substrate consumed and the energy released from the reaction.
Moulds do not grow well in anaerobic conditions, therefore they are not important in
terms of food spoilage or beneficial fermentation, in conditions of low oxygen
availability.
Temperature
Temperature affects the growth and activity of all living cells. At high temperatures,
organisms are destroyed, while at low temperatures, their rate of activity is
decreased or suspended. Micro-organisms can be classified into three distinct
categories according to their temperature preference (see table2.4).
C.O.E.& T.,Akola 31
Manufacturing of Ethyl Alcohol from Fruit Waste
Nutritional requirements
The majority of organisms are dependent on nutrients for both energy and growth.
Organisms vary in their specificity towards different substrates and usually only
colonise foods which contain the substrates they require. Sources of energy vary
from simple sugars to complex carbohydrates and proteins. The energy
requirements of micro-organisms are very high. Limiting the amount of substrate
available can check their growth.
The optimum pH for most micro-organisms is near the neutral point (pH 7.0).
Certain bacteria are acid tolerant and will survive at reduced pH levels. Notable
C.O.E.& T.,Akola 32
Manufacturing of Ethyl Alcohol from Fruit Waste
Inhibitors
Many chemical compounds can inhibit the growth and activity of micro-organisms.
They do so by preventing metabolism, denaturation of the protein or by causing
physical damage to the cell. The production of substrates as part of the metabolic
reaction also acts to inhibit microbial action.
Controlled fermentation
C.O.E.& T.,Akola 33
Manufacturing of Ethyl Alcohol from Fruit Waste
It is highly probable that the first controlled food fermentations came into existence
through trial and error and a need to preserve foods for consumption later in the
season. It is possible that the initial attempts at preservation involved the addition of
salt or seawater. During the removal of the salt prior to consumption, the foods
would pass through stages favourable to acid fermentation. Although the process
worked, it is likely that the causative agents were unknown. Today, there are
numerous examples of controlled fermentation for the preservation and processing
of foods. However, only a few of these have been studied in any detail - these
include sauerkraut, pickles, kimchi, beer, wine and vinegar production. Although the
general principles and processes for many of the fermented fruit and vegetable
products are the same -relying mainly on lactic acid and acetic acid forming
bacteria, yeasts and moulds, the reactions have not been quantified for each
product. The reactions are usually very complex and involve a series of micro-
organisms, either working together or in succession to achieve the final product.
Some yeasts are chromogenic and produce a variety of pigments, including green,
yellow and black. Others are capable of synthesising essential B group vitamins.
C.O.E.& T.,Akola 34
Manufacturing of Ethyl Alcohol from Fruit Waste
Although there is a large diversity of yeasts and yeast-like fungi, (about 500
species), only a few are commonly associated with the production of fermented
foods. They are all either ascomycetous yeasts or members of the genus Candida.
Varieties of the Saccharomyces cervisiae genus are the most common yeasts in
fermented foods and beverages based on fruit and vegetables. All strains of this
genus ferment glucose and many ferment other plant derived carbohydrates such
as sucrose, maltose and raffinose. In the tropics, Saccharomyces pombe is the
dominant yeast in the production of traditional fermented beverages, especially
those derived from maize and millet (Adams and Moss, 1995).
Most yeasts require an abundance of oxygen for growth, therefore by controlling the
supply of oxygen, their growth can be checked. In addition to oxygen, they require a
basic substrate such as sugar. Some yeasts can ferment sugars to alcohol and
carbon dioxide in the absence of air but require oxygen for growth. They produce
ethyl alcohol and carbon dioxide from simple sugars such as glucose and fructose.
CH O
6 12 6 2C H OH
2 5 + 2CO 2
In conditions of excess oxygen (and in the presence of acetobacter) the alcohol can
be oxidised to form acetic acid. This is undesirable if the end product is a fruit
alcohol, but is a technique employed for the production of fruit vinegars (see later
section on mixed fermentations).
Yeasts are active in a very broad temperature range - from 0 to 500 C, with an
optimum temperature range of 200 to 300 C.
The optimum pH for most micro-organisms is near the neutral point (pH 7.0).
Moulds and yeasts are usually acid tolerant and are therefore associated with the
spoilage of acidic foods. Yeasts can grow in a pH range of 4 to 4.5 and moulds can
grow from pH 2 to 8.5, but favour an acid pH (Mountney and Gould, 1988).
C.O.E.& T.,Akola 35
Manufacturing of Ethyl Alcohol from Fruit Waste
Yeasts are fairly tolerant of high concentrations of sugar and grow well in solutions
containing 40% sugar. At concentrations higher than this, only a certain group of
yeasts – the osmophilic type – can survive. There are only a few yeasts that can
tolerate sugar concentrations of 65-70% and these grow very slowly in these
conditions (Board, 1983). Some yeasts – for example the Debaromyces - can
tolerate high salt concentrations. Another group which can tolerate high salt
concentrations and low water activity is Zygosaccharomyces rouxii, which is
associated with fermentations in which salting is an integral part of the process.
C.O.E.& T.,Akola 36
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 37
Manufacturing of Ethyl Alcohol from Fruit Waste
the microbiological phase of wine making is over. Thereafter, the quality and stability
of the wine depend very largely on preventing further microbial activity, both during
the "aging" in wooden casks and after bottling (Stanier et al, 1972).
At all stages during its manufacture, fruit juice alcohol is subject to spoilage by
undesirable microorganisms. Pasteur, whose descriptions of the organisms
responsible and recommendations for overcoming them are still valid today, first
scientifically explored the problem of the "diseases" of wines. The most serious
aerobic spoilage processes are brought about by film-forming yeasts and acetic
acid bacteria, both of which grow at the expense of the alcohol, converting it to
acetic acid or to carbon dioxide and water. The chief danger from these organisms
arises when access of air is not carefully regulated during aging. Much more serious
are the diseases caused by fermentative bacteria, particularly rod-shaped lactic acid
bacteria, which utilise any residual sugar and impart a mousy taste to the wine.
Such wines are known as turned wines. Since oxygen is unnecessary for the growth
of lactic acid bacteria, wine spoilage of this kind can occur even after bottling. These
risks of spoilage can be minimised by pasteurisation after bottling.
Fermentation pathways
The initial steps are identical to those of respiration. For example, for
carbohydrate fermentation, the pathway begins with glycolysis. In EM glycolytic
pathway, there are generated two pyruvate molecules, two reduced coenzyme
NADH molecules, and two ATP molecules for each molecule of glucose. The
remainder of the fermentation pathway is concerned with reoxidising the coenzyme.
In fermentation, reoxidation of NADH to NAD+ depends on the reduction of
pyruvate molecules formed during glycolysis. Different microorganisms have
developed different pathways for utilising the pyruvate for reoxidising the reduced
coenzyme with different terminal sequences of the various fermentation pathways
resulting in the formation of various end products (Fig). The different fermentation
pathways are named for the characteristic end products that are formed. The most
common ones are as follows :
C.O.E.& T.,Akola 38
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 39
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 40
Manufacturing of Ethyl Alcohol from Fruit Waste
Formation by
= Accumulation
biochemical
So, for the case of the biomass:
reaction
dx
R xV = µVX = V (1)
dT
where µ is the specific growth rate, V is the volume of the vessel and X is the
instantaneous concentration of the biomass. If Y is the overall yield coefficient for
the formation of biomass and the limiting substrate concentration is 5, then the
equivalent expression for substrate is:
dS
RS V = V (2)
dT
where Rs is the rate of conversion of substrate per unit volume of the reactor.
Equation 5.116 makes no assumptions regarding the uniformity of the yield
coefficient Yx/s, but if that can be taken to be constant then equation may be used to
relate equations (1) and (2). This condition is met when µ is large in comparison
with m so that, dispensing with the subscript, the differential form of equation can be
written:
dS dX
Y =− (3)
dt dt
which gives:
YRs = - µ X (4)
Equation 2 thus becomes:
C.O.E.& T.,Akola 41
Manufacturing of Ethyl Alcohol from Fruit Waste
1 dS
− µX = (5)
Y dt
The yield coefficient may also be expressed in its integral form as:
X − X0
Y= (6)
S0 − S
which can be re-arranged:
X − X0
S = S0 − (6)
Y
If the growth follows the Monod kinetic model, then equation may be substituted into
equation 1 to give:
dX µ SX
= m (7)
dt Ks + S
The condition of the fermentation after any time / would then be given by:
X
K s + S dX t
∫ µ m S X =∫0 dt
X0
(8)
K S Y + S 0Y + X 0 Y ( S 0 − S ) K SY S
ln1 + − ln = t (10)
µ m ( YS 0 + X 0 ) X0 µ m ( X 0 + YS 0 ) S 0
These rather unwieldy equations can be used to generate a graph showing the
changes in biomass and substrate concentrations during the course of a batch
fermentation (fig). Their main disadvantage is that they are not explicit in X and S so
that a trial and error technique has to be used to determine their values at a
particular value of t.
C.O.E.& T.,Akola 42
Manufacturing of Ethyl Alcohol from Fruit Waste
Fig. The time couse of a batch fermentation as predicted by equations 9 and 10. The parameters
used in the calculation were : KS= 0.015 g/l, µm=0.35 h-1, Y = 0.5, X0 = 0.1 g/l, S0= 2 g/l
It is worth noting that the curves obtained in Fig. show an inflexion towards
the final stages of the fermentation, whereas the broken line showing the values of
X generated by equation shows no such characteristic and predicts that the growth
would proceed to give an infinite value of X.
C.O.E.& T.,Akola 43
Manufacturing of Ethyl Alcohol from Fruit Waste
Quantitative requirements
(a) Basis : 1 ton of 100% alcohol (1.26 kiloliters) and 90%
yield from total sugar
Molasses (50-55% total sugar) 5.6 tons
Sulfuric acid (600 Be) 27 kg
Ammonium sulfate 2.5 kg
Coal 0.7-1.5 tons
Process water 12 tons
Cooling water 50 tons
Electricity 35 KWH
By-products : CO2 0.76 ton
Fusel oil (higher mol. wt. Alcohols )
Residual cattle feed or fertilizer 0.20 – 0.60 ton
(b) Plant capacities : 10-100 tons/day of ethyl alcohol
Process description
Molasses is diluted to a 10-15% sugar concentration and adjusted to a pH of
4-5 to support yeast growth which furnishes invertase and zymase catalytic
enzymes. Nutrients such as ammonium and magnesium sulfate or phosphate is
added when lacking in the molasses. This diluted mixture called mash is run into
large wooden or steel fermentation tanks.
Yeast solution, grown by inoculating sterile mash, is added and fermentation
ensues with evolution of heat which is removed via cooling coils. The temperature
is kept at 20-300C over a 30-70 hr period, rising near the end of 350C. Carbon
C.O.E.& T.,Akola 44
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 45
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 46
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 47
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 48
Manufacturing of Ethyl Alcohol from Fruit Waste
The acidity of the sulfite waste liquor can be sufficiently reduced by stripping
alone to make further treatment unnecessary, but for best economy it usually proves
desirable to add lime. The lime is added as a 10% water slurry injected into the
sulfite waste liquor at a point just ahead of the coolers. The equipment consists of
an outside lime-storage bin, two agitated lime-slurry tanks, and the necessary
pump. A pH controller regulates the amount of lime addition. The sulfite waste
liquor is adjusted to a pH of 4.5 for fermentation. The quantity of lime average
about 3 lb.of lime per 1000 gal.of sulfite waste liquor treated.
After lime addition, the liquor is cooled to a temperature of 32 0C. Cooling is
accomplished by two-stage flash evaporation under high vacuum, as this method
has the advantage of concentrating the liquor at the same time that it is being
cooled and also of eliminating additional amounts of sulfur dioxide. Concentration is
in the order of 12% which results in proportional reduction of costs during the
subsequent steps of processing.
The essential feature of this process is that after fermentation, the fermented
work is run through a centrifugal separator to remove the yeast. This yeast is then
re-used in a following fermentation in the operating cycle. The basis of this process
is that when yeast is present in a suitable medium containing sugar, the course of
the resulting fermentation tends to divide into two stages. In the first stage, the
yeast cells multiply, using sugar for food, until they become crowded. During this
stage there is maximum growth of yeast and minimum production of alcohol. In the
second stage, the yeast reduces its rate of budding, or division, and continues to
feed on the remaining sugar present. During this stage there is minimum growth of
yeast and maximum production of alcohol. The purpose of re-using the yeast is to
establish at once in each new fermentation the same high concentration of yeast
cells that was present at the end of the previous fermentation. In this way the
fermentation is limited to the second stage and the alcohol yield, therefore, is
improved.
Under any given set of conditions there is a fairly narrow concentration range
of yeast cells per unit volume above which the rate of yeast growth diminishes every
rapidly. Operation throughout the entire fermenting cycle at yeast concentration in
C.O.E.& T.,Akola 49
Manufacturing of Ethyl Alcohol from Fruit Waste
excess of such critical value offers important advantages in the case of waste sulfite
liquor. Since large volumes of fermenting liquor are involved, profile yeast growths
must ensue before the critical concentration is reached if the initial inoculum is
small. This yeast growth is obtained at the expense of sugar, which would
otherwise produce alcohol. At the same time, because waste sulfite liquor is, at
best, a dilute sugar solution, the sugar required for yeast growth represents a
greater proportion of the total than in the case of more concentrated sugar solutions
from molasses or grain. The advantages of the yeast re-use process in increasing
alcohol yields are, therefore, much greater in the case of waste sulfite liquor than in
application to the more conventional raw materials.
Fermentation is carried out in eight interconnected fomenter of 90,000 gal
capacity each. To the liquor being pumped from storage is injected measured
proportionate amounts of urea and yeast. The liquor enters the first fomenter,
overflows into the second and so on through to the last fomenter whereupon
fermentation is complete. From 70 to 80% of the fermentable sugars are fermented
in the first two fomenters and about 95% of the fermentable sugars are converted to
alcohol in the complete cycle. Fermentation time has been varied between 12 and
20 hours. This short fermentation time, principally due to the elimination of the
yeast-multiplication stage, can also be attributed partly to the adequate mixing
provided in the fermenters, which keeps the yeast cells in suspension and partly to
the fact that the yeast is acclimatized through re-use.
Control of fermentation consists of regular measurement of the sugar
concentration of the liquor entering and leaving the fermented and the alcohol
content of the fermented liquor. The yeast is examined daily under the microscope
for viability and cell count.
C.O.E.& T.,Akola 50
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 51
Manufacturing of Ethyl Alcohol from Fruit Waste
Salient Features
Quality of yeast creature
The flocculating yeast culture must having fermentation efficiency of over
90%. Fermentation temp.
The performance of yeast towards alcohol production depends on
temperature. The efficiency is highest at and below 32°C and hence maintaining
section temp, is very important.
The salt content of diluted molasses should be such that the osmotic
pressure generated will not destroy the yeast functioning. Apart from this, the
problem of salting out on dissolved inorganics is also reduced by reducing the salts.
The typical detrimental problem is that almost all other continuous
fermentation lies in the fact that any effect to separate yeast from salt (precipitated)
C.O.E.& T.,Akola 52
Manufacturing of Ethyl Alcohol from Fruit Waste
for recycle of yeast is not successful. Salt recycle along with yeast should not be
avoided.
In the process, the yeast is denser than the precipitating salt and hence the
salt and yeast separation is easy and complete.
C.O.E.& T.,Akola 53
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 54
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 55
Manufacturing of Ethyl Alcohol from Fruit Waste
Flow diagram for the manufacture of ethyl alcohol by esterification and hydrolysis
C.O.E.& T.,Akola 56
Manufacturing of Ethyl Alcohol from Fruit Waste
The mixed esters (ethyl hydrogen sulfate and diethyl sulfate) in the absorbate
are hydrolyzed with 1-2 volumes of water. The equivalent practice in the USSR is to
hydrolyze with 0.8 volume of water per volume of absorbate. In the United States a
residence time of 1.5-2 hr at 700 C hydrolyzes the sulfates to ethyl alcohol and dilute
sulfuric acid.
The hydrolysis mixture contains ethyl alcohol, ethyl ether, sulfuric acid and
water. Diethyl ether tends to form as the main by-product of the reaction between
ethanol and diethyl sulfate :
CH3 CH2 OH + (CH3 CH2 )2 SO4 CH3 CH2 OSO3 H + CH3CH2OCH2 CH2
C.O.E.& T.,Akola 57
Manufacturing of Ethyl Alcohol from Fruit Waste
SELECTION OF PROCESS
a) PROCESS SELECTION :
As seen previously the different processes used in ethanol manufacture are
basically of two types only synthetically from petroleum or by fermentation of sugar
i.e. biochemical process.
Considering the economics, the cost of ethanol from petroleum derivatives is
favorable even today ( outside India ) as the 86 prices in the U.S. candidate (8)
Alcohol from ethylene 0.3706$/Kg. And that from fermentation of molasses
0.4012$/Kg. Indian alcohol without tax costs Rs.3/ht., which at the present dollar
rate works out about 0.15$/Kg.
b) Why synthetic Ethanol is not favorable ?
C.O.E.& T.,Akola 58
Manufacturing of Ethyl Alcohol from Fruit Waste
However, the cost of petroleum to India is very high. One reason for this is
that most of petroleum has to be imported for which costly foreign exchange is
needed. Also, the to the recent gulf wars the prices of crude have zone up. Thus
the synthetic ethanol manufacture is not favorable.
c) Why Synthetic Ethanol is not suitable ?
Almost 30% of the alcohol consumed in India is for potable purpose. That
alcohol desired from petroleum does not provide the special properties required
from liquor making. As a result fermentation alcohol is the best option from India's
point of view.
d) Why Sapota is suitable for alcohol production in India.
Also India produces large quantity of sugar ( 11 mt in 1989-90). Now 3 Kgs
of sugar produced also produce one kg of sapota such large quantity of sapota
would be wasted of not used. Then, it is suitable for alcohol production such me
Sapota is having high carbohydrate content, cheaply having high carbohydrate
content, cheaply available, can be easily fermented. It is the cheapest product
compared to other fruits having much better yield. The present price of tax paid
alcohol is Rs.5.60/lit, which at present price of dollar works out to be 18/lit, which is
quite competitive internationally.
India has got large production of fruits. Most of the fruits having high sugar
and carbohydrate content is exported from India. The fruits having high
carbohydrate content are Banana, Mango, Jackfruit, Grapes, Orange Sapota etc.
and a variety of fruits are available inthenantent. But we have chosen the Sapota
for our project because of the following reasons –
1. It is easily perishable.
2. It is having high carbohydrate and sugar content.
3. It can be fermented easily.
4. It is cheaply available in the market.
5. Its storage cost is cheap.
C.O.E.& T.,Akola 59
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 60
Manufacturing of Ethyl Alcohol from Fruit Waste
2. Dilution and Sterilization :- As seen before Sapota contains about 50% sugar
and also that nearest cannot sustain in sugar concentration of about 15-20 %
depending upon strain quality. As such dilution of the Sapota to between 10-15 %
Sugar is done.
Also, nearest cannot complete with other micro organizers such as bacteria,
which are even present. Thus, the Sapota must be sterilized by heating to about
700C. Both these procedures can be simultaneous achieved in a continuous dilutes
in which water are fed so that detection and sterilization is done.
Culture Development :- Yeast strains are usually proprietary and energy distillery
maintains a culture of its own that's suitable to the molasses and environment found
there. This culture must be grown to a size useful for industrial scale production.
This involves many difficulties such as control over temperature, pH, nutrient level,
sterile and ascetics conditions.
Single strain of yeast from the laboratory refrigerator is first grown in small
flask and the size doubled energy eight hours until 20ht stage. Then the operation
shifts from the laboratory to plant shed where it is grown up to the 200 lit. size and
then used for fermentation, in the pre-fomenters at about 5-10% w/w of the diluted
Sapota. At each stage, sterilized diluted Sapota is used. Nutrients such as ammonia
sulphate, urea, diammonium phosphate are added and also sulphuric acid.
C.O.E.& T.,Akola 61
Manufacturing of Ethyl Alcohol from Fruit Waste
Pre-fermenter Stage :- The diluted Sapota & developed yeast culture are fed to
the fomenter tanks, which are provided with heating coils and air sparkers. The
idea here is not to produce alcohol but to allow the yeast to grow to a high
concentration i.e. the part of life cycle of yeast involving the exponential growth
stage is completed here. Oxygen is required in this stage and to air sparing is
required this also helps in agitation. The exothermic reactions are aided by cooling
water calculated through the cells. Generally, 2-4 pre fomenters are used and
residence time is between 6-8 hours.
Fermenters :- The work from the prefer mentors is prepared to the fomenters.
These are not provided with air spanners since here only the anaerobic stage of the
life cycle of yeast is to be allowed since alcohol is produced only during this stage.
The sugar is converted according to the following equation.
C6H12O6 2 C2H5OH + 2CO2 + 130KJ
It is observe that a lot of heat is generated during the reaction and hence
inter cooling is required. The froth is pumped through a plate type exchanger and
maintained at around 30-320c. At high temperature, not only is the alcohol
productivity low but also the amount of alcohol cost as a result of evaporation and is
entrained along with carbon dioxide formed is high.
Hence the maintenance of low temp. is must. The fomenters have closed
heads and the carbon dioxide formed is easily collected. It is bubbled through a tank
of water so that any alcohol entranced is it is recovered the gas may then be
compressed and stored. These are usually between? 4-8 fomenters and residence
time 28-32 hours.
Separation and Recovery of alcohol - : The resulting solution from the fomenters is
known as wash. This wash contains between 8-10% alcohol, unfermented sugar,
ash from the Sapota and water. The costtrest of all and the price determining stage
of the process is the recovery of the alcohol from the wash not only in high purity
but also economically.
C.O.E.& T.,Akola 62
Manufacturing of Ethyl Alcohol from Fruit Waste
Distillation of Ethanol
Whatever method of preparation is used, the ethanol is initially obtained in
admixture with water. The ethanol is then extracted from this solution by simple or
steam distillation.
Although the boiling of ethanol, 78.3°C, is significantly lower than the boiling
point of water, 100°C, these material cannot be separated completely by distillation.
Instead, an azeotropic mixture (i.e. a mixture of 95% ethanol and 5% water) is
obtained, and the boiling point of the azeotrope is 78.15°C. In the distillation, the
most volatile material (i.e. the material that the has the lowest boiling point) is the
first material to distill from the boiling point. If flask, and this material is the
azeotrope of 95% ethanol which has the lowest boiling point. If an efficient
fractionating column is used, there is obtained first 95% alcohol, then a small
intermediate fraction of lower concentration and then water. But no matter how
efficient the fractionating column used, 95% alcohol cannot be further concentrated
by distillation.
The separation of mixture by simple distillation occurs because the vapour
has a different composition from the liquid from which it distills (i.e. the vapour is
richer in the more volatile component). We cannot separate 95% alcohol into its
components by distillation, because here the vapour has exactly the same
composition as the liquid, towards distillation, then 95% alcohol behaves exactly like
a pure compound.
A liquid mixture that has the peculiar property of giving a vapour of the same
composition is called an azeotrope (i.e. constant - boiling mixture). Since it contains
two components 95% alcohol, have boiling points lower than those of their
components, and are known as minimum - boiling mixtures. Azeotrope having
boiling points higher than those of their components are known as maximum boiling
mixtures.
C.O.E.& T.,Akola 63
Manufacturing of Ethyl Alcohol from Fruit Waste
Confirmative Test
C.O.E.& T.,Akola 64
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 65
Manufacturing of Ethyl Alcohol from Fruit Waste
PLANT LAYOUT
Sapota
C.O.E.& T.,Akola 66
Manufacturing of Ethyl Alcohol from Fruit Waste
PROCESS
LAYOUT
RESULTS OF EXPERIMENTATION
C.O.E.& T.,Akola 67
Manufacturing of Ethyl Alcohol from Fruit Waste
MATERIAL BALANCE
C.O.E.& T.,Akola 68
Manufacturing of Ethyl Alcohol from Fruit Waste
184
= × 220kg = 118.36kg
342
118.36
= = 150.77 wt
0.785
1000
1 lit of ethonal = = 6.632 kg of Sapota.
150.77
= 6632 Kg/day
C.O.E.& T.,Akola 69
Manufacturing of Ethyl Alcohol from Fruit Waste
= 26528 Kg/day
= 1459.04 Kg Glucose/day.
16.56 Kg of ethanol.
1459.04 × 16.56
∴ethanol produced =
180
= 134.23
= 0.055
Balance on Fermenter
3) Nutrients present =
HCL ( 31 % ) = 5 Kg / day
C.O.E.& T.,Akola 70
Manufacturing of Ethyl Alcohol from Fruit Waste
2) CO2 gas
5) Un converted sugar.
6) Waste water.
18
= × 26528 = 2652. Kg / day
180
= 17243.2 + 1.05
= 17244.95 Kg / day
C.O.E.& T.,Akola 71
Manufacturing of Ethyl Alcohol from Fruit Waste
3) Biomass produced :- Material balance over the fermanter with respect to yeast
mass is –
[ Change within the vessel ] = [ increase due to feed ] + [ increase due to growth ] –
Dx x − xo
it can be given as = K = 0.5
Ds So − s
For ethanol system value of K is 0.5 value taken from book wasteless chemical
So = 1459.04 Kg sugar
2.91
Moles of Glucose converted =
2
1459.04
initial moles of glucose =
180
= 8.105 K. moles
S = 119.79 Kg / day
C.O.E.& T.,Akola 72
Manufacturing of Ethyl Alcohol from Fruit Waste
X − Xo
Now = 0.5
So − S
X − .5
= 0.5
1459.04 − 119.79
X = 670.125 Kg of cells.
= 0.5 × 670.125
= 335.0625 Kg water
∴We obtain
C.O.E.& T.,Akola 73
Manufacturing of Ethyl Alcohol from Fruit Waste
= 17400.2 Kg / day
134.23
% of ethanol in spent wash = × 100 = 17
17400.2
= 17400.2 Kg / day
F Xc = D × d + R Xf ………………………. (2)
XD = .18
= 1000 × 0.9720
= 972 Kg
972
Kg of water in distillation = × 100 − 972
18
= 4428 Kg.
Equation 2 gives
C.O.E.& T.,Akola 74
Manufacturing of Ethyl Alcohol from Fruit Waste
R Xr = 1986.034
= 12000.2 Kg
R = 12000.2 Kg
1986.034
Xr = × 100 = 16.55%
12000.2
XF = 0.17 % = 0.0017
Xd = 18 % ( deried ) = 0.18
Xw = 16.55 % = 0.1655
C.O.E.& T.,Akola 75
Manufacturing of Ethyl Alcohol from Fruit Waste
ENERGY BALANCE
C.O.E.& T.,Akola 76
Manufacturing of Ethyl Alcohol from Fruit Waste
EXAMPLES
Problems on y-x data prediction (binary azeotrope)
(1) The azeotrope of ethanol (1) - benzene (2) system has a composition of 44.8%
mole % ethanol with a boiling point of 68.2°C at 760 mm Hg. At 68.2°C the vapour
pressure of pure benzene is 517 mm Hg and that of ethanol is 506 mm Hg.
Calculate the Van Laar constants for the system and evaluate the activity
coefficients for a solution containing 10, 20, 70 and 90% (mole) of ethanol. Prepare
the plot of log γ1 – x1 and log γ2 – x2.
Ans. A = 0.870 B = 0.577
for 10% solution γ1= 4.19 γ2 = 1.026
(2) At atmospheric pressure ethyl acetate and ethanol form an azeotrope containing
53.9% (mole) of the former component with a boiling point of 71.8°C. Evaluate (a)
the values of the constants in the Van Laar equation and (b) the azeotropic
composition at 56.3°C if the Van Laar constants remain unchanged. The vapour
pressures in mm Hg of the pure liquids are as follows
71.8°C 56.3°C
ethanol 587 298
ethyl acetate 636 360
Problem on VLE
(1) The isobaric y-x data for the system ethanol (1) n-heptane (2) at 760 mm Hg pr
are as follows
x1 y1 rc
0.023 0.330 85.0
0.181 0.580 73.3
0.310 0.605 71.6
0.406 0.625 71.4
0.610 0.648 71.4
0.821 0.700 71.5
0.910 0.760 72.5
0.970 0.881 75.4
C.O.E.& T.,Akola 77
Manufacturing of Ethyl Alcohol from Fruit Waste
The temp, dependence of wilson's and R-K constants established from other
sources is given below. The model constants of R-K and wilson equations are
temperature sensitive for some systems.
Wilsons constants
Λ12 = 0.0366 + 0.000253 t + 0.0000143 t2
Λ21 = 0.1720 + 0.0006516 t (where t °C)
R-K consts
B = 0.8525 + 0.00095 t
C = -0.1185-0 - 00025 t ( t °C)
Evaluate the activity coefficient values at x, = 0.023 and x, = 0.610 by the wilson
and R-K equations by (i) by taking the average value of the constants between the
min & max temperatures, and (ii) taking into account their temperature dependence.
(3) The azeotrope of ethanol (1) 78.4°C b.pt. - benzene (2) 80.5°C b. pt, system has
a composition of 44.8 mole % ethanol with a boiling point of 68.24°C at 760mm Hg
pressure. At 68.24°C the v.p. of pure benzene is 507 mm Hg and that of ethanol is
516 mm Hg calculate the Van Laar constants for the system and the predict the y-x
data for this system for the entire molefraction range giving an increment of 0.1
molefraction in the x1 values Van Laar consts
A = 0.830, B = 0.575
The v.p. values for the two components are given below
ethanol
temperature °C V.p mm Hg
19.0°C 40 mm
26 60
35 100
48.4 200
63.5 400
78.4 760
C.O.E.& T.,Akola 78
Manufacturing of Ethyl Alcohol from Fruit Waste
B
The Antoine eqn. is log10 p = A −
C + t 0C
Illustration
CO Cp = 6.60 + 0.00120 T
H2 Cp = 6.62 + 0.00081 T
C2 H5 OH Cp = 3.58 + 0.04985 T - 16.99x10-6 T2
H2O Cp = 8.22 + 0.00015 T + 1.34X10-6 T2
From these data the difference terms are obtained
∆α = 3.58 + 8.22 - 2 (6.60) - 4 (6.62) = - 27.88
400
C.O.E.& T.,Akola 79
Manufacturing of Ethyl Alcohol from Fruit Waste
300
200
y'
100
0
0.001 0.002 0.003 0.004 0.005
1
T
Similarly
∆β = 0.04436 and ∆γ = -15.65x10-6
By plotting y' as defined below versus 1/T, the values of ∆H00 and I may be
determined graphically.
∆β ∆γ 2 ∆H 00
R ln K a − ∆α ln T - T− T = y' = 1 −
2 6 T
From the line on the graph, the slope is 55,400 cal/gm mole and is equal
to -∆H00. The intercept 65.0 and is equal to I. The equation for ∆G° is then
∆G° = - RT In Ka = -55400 + 27.88T lnT- 0.02218 T2 +2.61 x106T3 - 65.0 T
Illustration
C.O.E.& T.,Akola 80
Manufacturing of Ethyl Alcohol from Fruit Waste
Express the heat of reaction as a function of temperature for the reaction shown in
the above illustration. Calculate the heat of reaction as a function of pressure at
200°C and from 1 atm to 20 atm.
Solution
Referring to the above illustration, the values for the heat capacity constant
differences were as follows
∆α = - 27.88 ∆β = 0.04436 ∆γ = -15.65 x 106
By using heats of formation we may get an improved value of -∆H00. The heats of
formation are
Component -∆H0298 cal/gm mole
CO -26416
H2 0
C2H5OH - 56,625
H2O - 58,798
For the reaction
Cal
-∆H0298 = -61,591
gm mole of C 2 H 5 OH
By the equation
1 1
∆H 0 = ∆H 00 + ∆αT + ∆βT 2 + ∆γT 3 + ...
2 2
∆H00 = - 55,386
The equation for the heat of reaction as a function of temperature would be
∆H0 = - 55,386 – 27.88 T + 0.02218 T2 – 5.217 x 10-6 T3
C.O.E.& T.,Akola 81
Manufacturing of Ethyl Alcohol from Fruit Waste
COST ESTIMATION
Cost Estimation for 15,000Lpd rectified spirit plant at (A.P. D. R.C., P.K.V Akola)
1. Liquification section 20,00,000 (20 Lacs)
2.Saccharification section 20,00,000 ( 20 Lacs)
3. Weighing and fermentation and storage tank 1,10,00,00 ( 110 Lacs)
4. Instrumentation 5,00,000 ( 5 Lac )
5. Electrical 25,00,000 ( 25 lacs)
6. Utilization for fermentation plant 18,00,000 ( 18 lacs)
7. Distillation plant to produce rectified spirit/extra ± 65,00,000 (65 lacs )
neutral Alcohol for 10,000 L PD
8. Zero effluent discharge process
to get protein cattle feed 2,50,00,000 ( 25 lacs)
9. Inter connection pipelines,
valve and instrumentation 10,00,000 ( 10 lacs )
10. Reaction and commissioning 5,00,000 ( 5 lacs )
11. Building 75,00,000 ( 75 lacs )
12. Boiler for 11,000 1/day plant 40,00,000 (40 lacs )
-------------------------
6,43,00,000 (6.43 Crore )
The total price of equipment for 15,000 LPD Rectified spirit plant is Rs 6.43 crore.
(Rupees six crores forty three lacs only ). The above price is based on present
prevailing price of deonedized copper sheets and copper tubes ex-manufacturing
works at Rs 175/ per kg. For shut and tubes respectively.
C.O.E.& T.,Akola 82
Manufacturing of Ethyl Alcohol from Fruit Waste
Basis :-
No of working days = 300/ year
Glucose content in Sapota = 220 gm/Kg
Alcohol yield from Sapota = 150-170 lit lt
Fermantation efficiency = 92 – 95 %
Plant capacity = 15 KL / day
Consumption Rate Total cost /
year
Raw material Per day Per year Rs.
Waste Sapota 47 t 14100 4000 /t 564.00
Enzymes
-1 45 Kg 13.50 t 465 / kg 62.775
AMG 22.5 Kg 6.75 t 825 / kg 55.6875
Steam 52.5t 15750 t 1190 / t 187.425
Electricity 2400Kw 7.2 lack kw 7.5 / Kw 54.00
Water
Process water 300 m3 90000 m3 2.50 / m3 2.25
Cooling water 250m3 75000 m3 2.50 /m3 1.875
Acid 75 Kg 22500 Kg 4 / Kg 0.90
Antifoam 15 Kg 4500 Kg 20 / Kg 0.90
agent
CaCO3 25 Kg 7500 Kg 5 / Kg 0.375
Yeast Only during start up
Total variable cost = 930.1875
Less credit for spent Sapota
14100 t 3000 / t = 423.00
Net variable cost = 507.1875
Natural produced = 45 lacs liters.
Variable cost of alcohol / lit of alcohol = Rs.11.27 / lit
Basis:-
C.O.E.& T.,Akola 83
Manufacturing of Ethyl Alcohol from Fruit Waste
Fermentation efficiency = 92 – 95 %
DISCUSSION
Chiku is called as Sapota. It is mostly grown in moist coastal tracts of
paninsular India, but in recent years it is seen that, it can be grown in zones of the
Deccan plateau and also in sub mountain traces of north India. Fruits are ready for
harvest in about 4 months i.e. oct-Nov, flowering fruits natures by Jan- Feb or
flowering natures fruits by April –May. Harvesting is done when the fruit is fully
malined. The sapota can be easily stored. It is that type of fruit which is easily
penshable , cheap in cost, having high sugar and carbohydrate content. It can be
fermented easily so its operating cost is very low.
C.O.E.& T.,Akola 84
Manufacturing of Ethyl Alcohol from Fruit Waste
Total municipal solid waste of Akola district is 150 mt/day. The organic waste
content in total waste is 29 %. Out of total organic waste 50 % will be available for
the alcohol Production ( 37.5 mt/day). Since by the fermentation process we are
able to produce ethyl alcohol at the cost of 11.27 Rs/lit it will be feasible to develop
such plant in Akola.
Ethyl alcohol is an important feed stock for the manufacturer of various
chemicals. These chemicals are primarily the basic carbon based products like
acetic acid, butanol, butadiene, Acetic an hydride etc. Ethylene, Ethylene oxide are
also produced from Petrochemical route. However this requires plants of huge
scales and thus requires substantially high investments. The drug industry also
uses alcohol as a raw material for production of insulin, Antibiotics tonics and
several other essential bulk drugs and formulations.
The areas for future research and development activities are briefly listed
below :
To increase the substrate utilization ability of excellent ethanol producers like yeast
and 2 mobiles.
To enhance alcohol tolerance of yeast.
To increase the ethanol production ability of bacteria capable of utilizing cellulose,
hemicellulose, pentoses etc.
Practical exploitation of the superior capabilities of Z mobiles. This anaerobic
bacterium is a better producer of ethanol than yeast as it has a relatively slower
growth rate coupled with higher sugar conversion rate. Immobalized Z. mobilis
could be used to achieve high rate of ethanol production. Z mobilis production rates
can be as high as 60/9/11 hr as compared to only 309/1/hr for yeast.
Efficient and cost effective process of continuous recovery of ethanol needs to be
developed. Such a process would keep ethanol concentration in the bioreactor
growth to low levels and would avoid product inhibition of yeast cells.
More efficient and cheaper methods of ethanol recovery need to be developed to
reduce the cost of recovery. Some possible approaches may be reverse osmosis,
Selective absorption using solid absorbants and use of super critical CO2 to
selectively extract ethanol. The major upcoming user segments are cosmetics and
C.O.E.& T.,Akola 85
Manufacturing of Ethyl Alcohol from Fruit Waste
premium potable liquor. These segments require extra neutral alcohol (ENA) or
grain alcohol. Extra neutral alcohol is obtained from sugar molasses after it has
been re-distilled 3 to 4 times. Even after triple distillation, the alcohol has traces of
sulphur odour, as the base material has traces of sulphur. Fuel ethanol or
anhydrous alcohol is produced by dehydration of rectified spirit. Ethanol used as
part of the fuel by blending with petrol, for a motor vehicle is called fuel ethanol.
India produce 1.3 billion lit. of ethanol in world production of lit. over 35 billion litres.
Ethanol – General Demand.
The total Ethanol production in India was in order of 1200 million lit. for the
year 1993-94 of this 48% or 570 million lit. accounted for industrial sector 42% or
504 million lit. or potable sector, 3.5 % or 4.2 million lit. for other end use and 2.5%
or 3 million lit for exports. The percentage of growth rate observed between 15 to
20 % per annum.
C.O.E.& T.,Akola 86
Manufacturing of Ethyl Alcohol from Fruit Waste
MARKET POTENTIAL
Alcohol finds its use in diverse applications ranging from potable liquor of life saving
drugs to paints and perfumery to renewable source of energy.
Future Demands
Fuel/motor spirit 68%
Industrial/Solvents 21%
Beverages 11%
Ethanol possibilities
As potable hard drinks.
As an extraction agent in the synthesis of medicine as a solvent and as
dilluant in liquors and paints.
As an industrial raw material for valve added down stream.
As disinfectant for cleaning.
As an add mix in fuels.
As an oxygenate reducing exhaust emission
As anti-freezing agent in colder climate.
As octane booster
SAFETY
General Safety Rules Followed In Chemical Process Plant Operation :
All process plant injuries even if they are minor has to be reported to the concerned
higher authority and medical data bank system.
'Strike any where' matches are prohibited on the process plant area.
Firearms, ammunition, explosives are prohibited within the process plant area.
Intoxicants or the persons under the influence of intoxicants are prohibited in the
process plant area.
Smoking is permitted in designated areas only, Matches, lighters are not permitted
in the areas marked strictly prohibited'.
All employees must follow the rules for any area they enter. This is strictly
necessary when they are exposed to hazardous area.
C.O.E.& T.,Akola 87
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 88
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 89
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 90
Manufacturing of Ethyl Alcohol from Fruit Waste
operating personnel must have the authority to stop construction work in evern of a
production hazard or the violation of standard safety rules. The project engineer
should visit the work site at least once during each working day to observe whether
the work is accomplished on schedule and safely. If extra hazardous work is to be
carried out, he should be personally present to guide and direct these efforts.
Personal Safety:
In a process plant operation personal safety has high importance. It can be
achieved by i) hazard removal, ii) hazard control, iii) personal protection.
Personal safety can be achieved by thorough training and effective
supervision, training should be aimed at providing the ability to use the process
equipment and perform its function and motivate to do the operation property and
safety. Many of the problems arise due to some training insufficiency. It is also
necessary to have continuous supervision so that any procedure is not violated and
malpractices are stopped. Supervision helps to enforce strict discipline. Human
factors need to be considered to design the work place. It helps to reduce the
accidents. Human factors should be considered from the beginning of the project.
Proper allocation of functions between man and machine can help for accident
prevention.
Human factors are mainly considered in terms of human errors. Human error,
to a large extent is a function of the work situation and can be reduced by good
design of the work situation. Some errors can be attributed to individuals and there
can be variations in error rates between individuals. From management point of
view human errors have to be considered in the areas of.
i) equipment design, ii) working methods, iii) motivation, iv) stress/tension
In environmental conditions proper illumination, fresh air, temperature
conditions and noise I are important parameters. However, it is wrong to say that all
the stresses are harmful. There is generally an optimum stress level for any
individual in any particular work assignment.
Common kind of stresses can be due to:
C.O.E.& T.,Akola 91
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 92
Manufacturing of Ethyl Alcohol from Fruit Waste
Through ventilation should be provided at the floor as well as at the ceiling level to
remove accumualted vapours. .
Solvents should not be stored along with chemicals with which they are likely
to react violently, in confined spaces, solvent vapours can cause oxygen deficiency.
In flammable liquid storage area, electrical fittings should be flame proof and
vapour proof type.
8. Used as the starting material for the production of formaldehyde and antifreeze
in autonecatine cooling systems.
9. Used as a nersotile compound used as a solvent for fats, oils, varnishes and
lacquers and plastic fibre such as cellulose nitrate.
10. Used as a fuel.
11. It is approved as denaturant for industries and chemical intermediate for the
manufacture of many organic compounds including dyes, esters, plastics etc.
12. Used for the extraction of aromatic portions from petroleum.
13. Used as solvent to recover tars from ignite deposits; for removing acid impurities
from vegetable oils, denaxing guns, extracting organic salts, purifying harmones
and steroids etc.
14. Used as cleaner of steel, metal and plastic surfaces; as a component in glass
cleaners and special dry cleaners; as a reducing agent in copper clearing brass
annealing and soldering fluxes.
15. Formation of gas hydrates & ice in natural gas pipelines is inherited by this
alcohol.
CONCLUSION
Ethyl /Alcohol is widely used in chemical industries. Growth in potable
alcohol industries is likely to be increase with the demand and consumption of the
people and the chemical products in industries in which alcohol plays an important
role. In this project we have selected Sapota as raw material for the Ethyl Alcohol
production, as it contains high carbohydrate percentage and is widely grown in
Maharashtra State.
From the experiments it was found that Ethyl alcohol can be obtained
conveniently with simple fermentation process. Economically the project is feasible
as the cost required for the overall project is less and the product price is
considerably less than the market price. Hence the production of Ethyl alcohol from
fruit waste like Sapota, is feasible in region like Maharashtra.
C.O.E.& T.,Akola 94
Manufacturing of Ethyl Alcohol from Fruit Waste
REFERENCES
1. Ullman's Encydopedia of Industrial Chemistry Vol : A1 ( Fifth edition )
2. Encyclopedia of Chemical technology Vol.1.
3. ALCOHOLS : By John. A. Monick.
4. Outlines of Chemical Technology : By G. RAO & Dryden.
5. Agro Product Development Research Center. : Dr.P.D.K.V.Akola
6. Stoichiometry IIIrd Edition By : B. I. Bhatt.
7. Handbook of Chemical Engineering. 5th Edition J. H. Perrys.
8. Plant Design & Economics for Chemical Engg.
3rd Edition By : Max. 5 Peters & Klaus Timmerhaus.
9. Handbook of Horticulture Vol. 12
10. Introduction of Bio technology : By R. A. Singh.
11. Pollution Control In Process Industries. : By : S. P. Mahajan.
12. Project Report on " Production of 15 KL Per Day
C.O.E.& T.,Akola 95
Manufacturing of Ethyl Alcohol from Fruit Waste
APPENDIX
C.O.E.& T.,Akola 96
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 97
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 98
Manufacturing of Ethyl Alcohol from Fruit Waste
C.O.E.& T.,Akola 99
Manufacturing of Ethyl Alcohol from Fruit Waste
INDEX