CHAPTER 1

INTRODUCTION

Ethanol

The word alcohol derives from Arabic al-kuhul, which denotes a fine powder of antimony produced by distilling antimony and used as all eye makeup. Alcohol originally referred to any fine powder, but medieval alchemists later applied the term to the refined products of distillation, and this led to the current usage Ethanol is a clear liquid alcohol that is made by the fermentation of different biological materials. This alcohol is known to have many uses, but one in particular is becoming more popular. Ethanol, the most widely used biofuel, is made in a process similar to brewing beer. The ethanol in the end is blended with gasoline to improve vehicle performance and reduce air Pollution.

Sources of Ethanol

Ethanol is a liquid alcohol that is manufactured by the fermentation of a wide variety of biological materials. These materials include grains such as wheat, barley, corn, wood, and sugar cane. In Canada, agricultural crops particularly grains- are likely to be used because they have both high productivity and high levels of carbohydrates needed for ethanol manufacture. Ethanol is best produced from lower value grains such as barley, corn and feed wheat. Higher value ‘bread’ wheat would remain in sample supply for export sales, when Canada begins major ethanol manufacturing. Also, poor quality (weather damaged, immature) grains which are less suitable for either human or livestock use are excellent for Ethanol production. Corn and starch based crops are the most common medium used in ethanol production. This indicates that once ethanol is in high demand, the prices of these crops will increase. for this reason other alternatives are being studied. Among these is use of domestic cellulosic biomass feedstock such as herbaceous and woody plants, agricultural and forestry residues, and a large portion of municipal solid waste and industrial waste streams. Temeco Enterprises, a pulp and paper producer in Quebec started in 1991 produce ethanol from forest waste. As the technology and economics improve for ethanol production from these materials, they would be expected to become an increasingly important base for ethanol production in Canada. However, excessive amount of crop residue should not be removed farmland so that they can continue to build soil organic-matter levels.(1)

Merits of Sweet Sorghum as feedstock for bio-ethanol production

Unlike grain sorghum, Sweet sorghum or "Sorgo” or"kadwal" stalks are taller and juicier and have high sugar content, similar to sugarcane. Conventionally, some sweet sorghum varieties are grown for syrup production, while others are grown for

forage. The stem juice of sweet sorghum is rich in fermentable sugar and is useful for alcohol production.

1. Can be uniformly grown in warm sunny weather.

2. The crop is a known to farmers.

3. Harvesting & cultivation practices are easier and are identical to sugar cane.

4. Sweet sorghum requires less water and fertilizers compared to sugarcane.

5. Crop cycle is short- 3.5 to 4 months usually, two cycles are possible from same piece of land annually, provided irrigation is possible.

6. Sweet Sorghum, on crushing to extract juice, gives bagasse as co-product which can be a principal source of energy for operation of' distillery in the form of boiler fuel.

This practically makes alcohol production free of energy cost and improves possibility of operation in remote areas.(2)

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 in Temperatures. 'Global warming' is a term used to describe tile 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 Iow-lying coastal areas. The Earth's climate is all-ready Adjusting to past greenhouse gas emissions, and the average global temperature is expected to rise by 1c to 35c by the year 2100 ('this increase in average temperature is larger than that which has been experienced over the last 10,000 years). By 2100, the Earth's average sea level is predicted to raise by approximately 50 cm. these phenomena could have serious repercussions on the natural and physical environment, as well as on human health. With the threat of global warming & energy crises in today's environment the need for clean, "green" fuels is quickly becoming a necessity. The US Environmental Protection Agency considers ozone to be the most widespread air pollution problem. To combat this problem, ethanol is widely used in reformulated gasoline to help urban cities meet public health standards for ozone. Because it's produced from renewable resources, ethanol is the only transportation fuel that reduces greenhouse gas emissions from cars. Fossil fuels release carbon trapped in the soil into the air, where it reacts with oxygen to form carbon dioxide, a greenhouse gas that traps the earth's heat, contributing to global warming. (3)

Ethanol is made from agricultural crops, which "breathe" carbon dioxide and give off oxygen. This maintains the balance of carbon dioxide in the atmosphere 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 El0 reduces greenhouse gases by 2 4-2.9% and fossil energy use by 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. (3)

Energy Value

Many have wondered whether ethanol makes sense, from an energy use perspective. In fact, each liter of ethanol contains at least 2-4 times as much energy as is required for inputs for crop production (fuel, machinery, fertilizers, etc), and ethanol manufacture Although petroleum-derived energy is used in the manufacture and transportation of inputs, this is more than offset by the solar energy captured through photosynthesis. This positive energy balance is predicted to improve by up to 25%, as more ever efficient crop and ethanol production becomes common over the next decade. (4)

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 the possible health consequences of using ethanol for this purpose. The scientific literature contains virtually no reports of injury to humans from inhaled ethanol. The apparent lack of harm may be attributable to rapid metabolism of ethanol and the difficulty in significantly raising blood ethanol concentration by inhalation exposure, which keep internal doses extremely low except in unusual situations, such as heavy exercise in the presence of concentrated vapors (4)

A report written by Sarah P, Armstrong concludes the following: It is highly unlikely that exposure to airborne ethanol associated with gasoline use could produce toxic effects The reasons for this are (a) the tiny doses that might be received, which might not be observable in light of endogenous levels of ethanol in blood, (b) the body's rapid elimination of ethanol, and (c) the relatively large doses of ethanol and high blood levels of ethanol associated with toxic effects in people No data in the scientific literature support the hypothesis that chronic exposure

non-irritating levels of ethanol in air could cause significant elevation of blood ethanol concentrations’(unless exposed individuals are exercising at the time), or that a risk of cancer or birth defects would be created. A recent survey of the literature regarding the inhalation toxicity of ethanol by the Swedish Institute for Environmental Medicine reached similar conclusions, namely that ‘a high blood concentration of ethanol is needed for the development of adverse effects “and "ethanol at Low air concentrations should not constitute a risk for the general population’. Emission impact of ethanol at positive finding regarding ethanol’s environmental benefits.(5)

Demand of alcohol

Alcohol has assumed very important place in the country’s economy. It has potentially as fuel in the form of power alcohol for blending with petrol. Fermentation alcohol has great demand in various countries. The synthetic alcohol produced by these countries from Naphtha of petroleum crude is not useful for beverages. (6)

There are about 322 distilleries in the country (1998-1999) with total installed capacity of 2711 million lit per annum. It is however, disheartening to note that inspire of' such abundant licensed and installed capacity and notwithstanding the fact that there is a great demand for alcohol, both for chemical industries and potable purpose, alcohol production in the country has being lagging behind and is varying only around 1300 million liter the target of alcohol demand as projected in the perspective plan for chemical industry, department of' chemical and petrochemical is 2400 million lit pet' annual by year (2000). (6)

Now Indian government has been realized the importance of alcohol as fuel. As India is agricultural country and has got large source of biomass which can be used for production of alcohol and just now Indian government has passed the bill of 5% blending of ethanol with petrol"(7)

Importance of ethanol in biofuel

One method to reduce air pollution is to oxygenated fuel for vehicle MTBE), (MethylTert-btyl elher) is a member of a ,group of chemicals commonly known as fuel oxygenates. It is a fuel additive to raise the octane number. But it is vary soluble in water and it is a possible human carcinogenic. Thereby, it should be, substituted for other oxygenated substances to increase the octane number of the fuel. Presently, ethanol as an oxygen us biomass fuel is considered as a predominant alternative to MTBE for its biodegradable, low toxicity, persistence and regenerative characteristic. The United States gasoline supply is an ethanol blend and the importance of ethanol use is expected to increase as more health issues are related to air quality. Ethanol may be produced from many high energy crops such as sweet sorghum corn, wheat, barley, sugar-cane, sugar beet, Cassava, sweet potato etc.like most biofuel crops, sweet sorghum has the potential to reduce carbon emissions. (7)

Sweet sorghum has the following characteristics

It is an efficient converter of solar energy, as it requires low inputs and yet, a high carbohydrate producer.

As a drought-tolerant crop with multiple uses. It has a concentration of sugar, which normally varies between 12 - 21%,

directly fermentable. It can be cultivated in temperature, subtropical and tropical climates. All components of the plant have economic value - the grain from sweet

sorghum can be used as food or feed, the leaves for forage, the stalk for fuel, the fiber both as mulch or animal feed and with second-generation technologies even for fuel.

Its bagasse, after sugar extraction, has a higher biological value than the bagasse from sugarcane, when used as feed for animals.

Its growing period is shorter (3 - 5 months) than that of sugarcane (10 - 12 months), and fuel quantity of' water required is 1/3 of' sugarcane

In tropical irrigated areas sweet sorghum can be harvested twice, each year and its production can be completely mechanized.

It has some tolerance to salinity. It can produce large quantities of both readily fermentable carbohydrate and

fiber per unit land area. (8)

Therefore, based on the above characteristics, it seems that seems that sweet sorghum is the most suitable plant for biofuel production than other crops under hot and dry climatic conditions in addition, possible rise of' bagasse as a byproduct of sweet sorghum include: burning to provide heat energy paper or fiber board manufacturing, silage for animal feed or fiber for ethanol production. However, since sweet sorghum is a relatively early stage of its Development, continued research was needed to obtain better genetic material and match local agro-economic conditions. The challenge is to harvest tile crop separate it into juice and fiber and utilize each constituent for year-round production of ethanol. Sweet sorghum juice is assumed to be converted to ethanol at 87 % theoretical, or 54.4 L per 100kg fresh stalk yield Potential ethanol yield from the fiber is more difficult to predict. The emerging enzymatic hydrolysis technology has not been proven on a commercial scale. One ton of corn grain produces 387 L of 182 proof alcohol while the same amount of sorghum grain produces 372 L Sorghum is used extensively for alcohol production, where it is significantly lower in price than corn or wheat. The commercial technology required ferment sweet sorghum biomass into alcohol has been reported in china. One ton of sweet sorghum stalks has the potential to yield 74 L of 200- proof alcohol Therefore, it seems that because ethanol can be produced from both stalk and grain of sweet sorghum, so it is tile most suitable crop for ethanol production using for biofuel comparing to other crops such as corn or sugarcane. (8)

Sweet sorghum juice content

Glucose Fructose sucrose content, starch and total sugar content, Amino acid content Protein content by nitrogen, total Phosphorus content, mineral element content.

This is the new bleed (R.S.S.V.9) cultured by Dr. Narkhede from rahuri krishi vidyapeeth especially for production of ethanol This method gives equal yield of ethanol as from molasses route and it is experimentally found that cost of ethanol by sweet sorghum method is nearly same as by molasses, however cost of ethanol by sweet sorghum method on commercial scale could be less than that by molasses method. (9)

Juice conversion to ethanol

The production of ethanol from the sweet juice is a well-understood process it has long been used in Brazil with sweet sugar as a raw material the fermentation process envisaged is a continuous cascade using a train of fomenters and buffer tank The alcohol concentration rises from 6 – 7%(vol.) In the last one fermentation temperature is kept between 33oC and 35oC. The growth of yeast is controlled by oxygen supply to the first and second fermented. Phosphorous (in the form of phosphoric acid) and nitrogen are also needed for yeast growth. Yeast cream is separated by centrifuges rate holding tanks, and clarified beer from the separators is fed into the fermentation buffer tank. Ethanol is then recovered.

This is accomplished into two columns, namely a distillation column and rectification column coupled with vapor-phase molecular sieves in which a mixer of nearly azeotropic water and ethanol is purified to pure ethanol. The ethanol yield is 87L per ton of the sweet juice process.

Project objective

Three main reasons led us to convert sorghum biomass into ethanol.

India has to face the significant problem of oil lacking. This energy resource is very expensive and increases too much the cost of all industrials transformations. Ethanol should be an alternative fuel or an additive.

An industrial outlet of this crop should open a new field for this culture and encourage agriculturists. By this way agriculture economy should be improved. The environmental point of view has to be considered. India is

Concerned by pollution future industrial developments have to take care with this Problem. In fact ethanol is less pollutant than petroleum.

CHAPTER 2

LITERATURE SURVEY

Sheorain V, Banka R, and Chavan M. Ethanol Production from Sorghum [1]

Sorghum (Sorghum bicolor L.Moench) is one of the main course cereal crops of India. India is second largest producer of sorghum in the world with production of about 10–11 million t from a total area of 12 million ha. This crop is ideally suited for semi-arid agro climatic regions of the country and, it gives reasonably good yield with minimal requirement of irrigation and fertilizers (Maiti 1996). On the other hand, cereals such as wheat (Triticum aestivum L.) and rice (Oryza sativa L.) cannot withstand the harsh semi-arid climates. These crops also require fair amount of water and other inputs such as fertilizers and pesticides. Therefore, sorghum is one of the few cereals, which can be grown in semi-arid regions. However, demand for sorghum for human consumption is decreasing with enhanced socioeconomic status of population in general and easy availability of preferred cereals in sufficient quantities at affordable prices. Since sorghum must be cultivated in the semi-arid regions for fodder to feed the large cattle population of the country, industrial applications for this grain are needed so that sorghum cultivation becomes economically viable for marginal farmers.

African Journal of Biotechnology

Ethanol production from Sorghum bicolor using both separate and simultaneous saccharification and fermentation in batch and fed batch systems [2]

The objective of this work was to find the best combination of different experimental conditions during pre-treatment, enzymatic saccharification, detoxification of inhibitors and fermentation of Sorghum bicolor straw for ethanol production. The optimization of pre-treatment using different concentrations of dilute sulfuric acid, various temperatures and residence times was achieved at 121°C, 1% acid concentration, 60 min residence time and enzyme saccharification using cellulose (celluclast 1.5 L) and _-glycosidase (Novozyme 188) at 50°C and pH 4.8 for 48 h. Different surfactants were used in order to increase the monomeric sugar during enzymatic hydrolysis and it has been observed that the addition of these surfactants contributed significantly in cellulosic conversion but no effect was shown on hemicelluloses hydrolysis. Ferment ability of hydrolyzed was tested using Saccharomyces cerevisiae Ethanol Red TM and it was observed that simultaneous saccharification and fermentation (SSF) with both batch and fed batch resulted in better ethanol yield as compared to separate hydrolysis and fermentation (SHF). Detoxification of furan during SHF facilitated reduction in fermentation time from 96 to 48 h. 98.5% theoretical yield was achieved in SHF with detoxification experiment attaining an ethanol concentration and yield of 23.01 gL-1 and 0.115 gg-1 DM respectively. During the SSF batch and fed batch fermentation, the maximum yields of ethanol per gram of dry matter were 0.1257 and 0.1332 g respectively.

S.C. May,R.A. Stenzel, M.C. Weekes J. Yu. Industrial Utilization of Sorghum in India [3]

This study is based upon fieldwork undertaken in mid-1998 in the context of the project 'Sorghum in India: Technical, policy, economic, and social factors affecting improved utilization', which was funded by the Department for International Development (DFID) and jointly undertaken by ICRISAT, NRCS, and NR1. The main industries using sorghum in India are the animal feed sector, alcohol distilleries, and starch industries. Only rainy-season sorghum is used for industrial purposes. Post rainy-sorghum is a highly valued food grain, and thus too expensive to be used as industrial raw material. This study formed part of the project 'Sorghum in India: Technical, policy, economic, and social factors affecting improved utilization', which was DFID-funded and jointly undertaken by ICRISAT, NRCS, and NRI. Apart from production, human consumption, marketing, and policy issues, industrial utilization was identified as one of the key areas to be studied in determining the potential of sorghum in the semi-arid regions of India. Given the limited prospects of human consumption of rainy-season sorghum, the study concentrated on documenting the current status of the crop as an industrial raw material, and projecting future trends. There have been few such studies in the past, partly due to lack of reliable data. The purpose of this paper is to document facts based on extensive surveys and discussions with industries concerned, rather than to advocate the use of sorghum.

SAT ejournal | ejournal.icrisat.org. Effect of decorticating sorghum on ethanol production and composition of DDGS[4]

The use of a renewable biomass that contains considerable amounts of starch and cellulose could provide a sugar platform for the production of numerous byproducts. Pretreatment technologies have been developed to increase the bioconversion rate for both starch and cellulosic-based biomass. This study investigated the effect of decortications as a pretreatment method on ethanol production from sorghum as well as its impact on quality of distiller’s dry grains with soluble (DDGS). Eight sorghum hybrids with 0, 10, and 20% of their outer layers removed were used as raw materials for ethanol production. The decorticated samples were fermented to ethanol using Saccharomyces cerevisiae. Removal of germ and fiber prior to fermentation allowed for a higher starch loading for ethanol fermentation and resulted in increased ethanol production. Ethanol yields increased as the percentage of decortications increased. The decortication process resulted in DDGS with higher protein content and lower fiber content, which may improve the feed quality.

D.Y. Corredor, Sweet sorghum R&D at the Nimbkar Agricultural Research Institute (NARI) [5]

The research work on sweet sorghum carried out at the Nimbkar Agricultural Research Institute (NARI) since 1970s has been summarized. American lines were crossed with a local Indian fodder/grain variety to produce varieties with a juicy stalk and good quality grain. Further breeding was carried out to produce varieties and hybrids giving high yield of good quality grain while retaining the characteristic of juicy stalks high in sugar. Complete development of indigenous technology for fermentation of sweet sorghum juice, solar distillation of ethanol and finally its use as a cooking and lighting fuel in new and improved stoves and lanterns was carried out. The technology of producing jaggery (unrefined sugar) and syrup from sweet sorghum was also developed. Consumer response to these products was assessed by marketing them in limited quantities. A completely automated multifuel gasification system capable of producing thermal output between 120-500 kW was developed for direct heat applications such as those in jaggery and syrup making units. Sweet sorghum bagasse was also tested in an existing paper mill to assess its suitability for paper manufacture. Areas of possible research for better exploitation of sweet sorghum have been suggested.

A. K. Rajvanshi and N. Nimbkar. Ethanol Production from Sweet Sorghum Syrup for Utilization as Automotive Fuel in India [6]

Ethanol demand is increasing drastically in the present time due to its blending in automotive fuels, which is desirable for getting clean exhaust and fuel sufficiency. The higher cost of cultivation of sugarcane/-beets, highly sensitive molasses rates, and ultimately instabilities in the price of ethanol have created grounds to search for an alternative source for ethanol production. Sweet sorghum has shown potential as a raw material for fuel-grade ethanol production due to its rapid growth rate and early maturity, greater water use efficiency, limited fertilizer requirement, high total value, and wide adoptability. Ethanol-producing companies, research institutions, and governments can coordinate with farmers to strategically develop value-added utilization of sweet sorghum. Fuel-grade ethanol production from sweet sorghum syrup can significantly reduce India’s dependence on foreign oil and also minimize the environmental threat caused by fossil fuels.

CHAPTER 3

PROPERTIES OF ETHANOL

PHYSICAL PROPERTIES

Ethyl alcohol under ordinary conditions is a volatile, flammable, clear, colorless liquid. Its odor is pleasant, familiar, and characteristic, as is its taste when suitably diluted with water. The most amazing property of ethanol is the volume shrinkage that occurs when it is mixed with water, or the volume expansion that occurs when it is mixed with gasoline. One volume of ethanol plus one volume of water results in only 1.92 volumes of mixture.

The physical and chemical properties of ethyl alcohol are primarily dependent upon the hydroxyl group. This group imparts polarity to the molecule and gives rise to intermolecular hydrogen bonding. These two properties account for the differences between the physical behavior of lower molecular weight alcohols and that of hydrocarbons of equivalent weight. Infrared spectrographic studies (5) have shown that, in the liquid state, hydrogen bonds are formed by the attraction of the hydroxyl hydrogen of one molecule and the hydroxyl oxygen of a second molecule. This bonding makes liquid alcohol behave as though it were largely demonized.

This behavior is analogous to that of water, which, however, is more strongly bonded and appears to exist in liquid clusters of more than two molecules. The association of ethyl alcohol is confined to the liquid state; in the vapor state it is nonnumeric.

Its properties can be listed as follows:

Name Ethyl alcohol

Formula CH3CH2OH

CAS NO 64175

Formula weight 46.07

Color Colorless liquid.

Density of 100% ethanol at 200C 0.78934 g/ml

Melting point -114.10C

Flash point 210C

Boiling point 78.40C

Ignition Temp. 3720C

Enthalpy H 298 278.98 KJ/gmol

Gibbs free energy G 298 -174.138 KJ/gmol

Antoins constant A=18.9119

B=-3803.99

C=-41.68

CHEMICAL PROPERTIES

Ethanol is classified as a primary alcohol, meaning that the carbon its hydroxyl group attaches to has at least two hydrogen atoms attached to it as well. Many ethanol reactions occur at its hydroxyl group.

Ester formation

In the presence of acid catalysts, ethanol reacts with carboxylic acids to produce ethyl esters and water:

RCOOH + HOCH2CH3 → RCOOCH2CH3 + H2O

This reaction, which is conducted on large scale industrially, requires the removal of the water from the reaction mixture as it is formed. Esters react in the presence of an acid or base to give back the alcohol and carboxylic acid. This reaction is known as saponification because it is used in the preparation of soap. Ethanol can also form esters with inorganic acids. Diethyl sulfate and triethyl phosphate are prepared by treating ethanol with sulfur trioxide and phosphorus pentoxide respectively. Diethyl sulfate is a useful ethylating agent in organic synthesis. Ethyl nitrite, prepared from the reaction of ethanol with sodium nitrite and sulfuric acid, was formerly a widely used diuretic.

Dehydration

Strong acid desiccants cause the dehydration of ethanol to form diethyl ether and other byproducts. If the Temperature of the ethanol being dehydrated exceeds around 160 °C, ethylene will be the main product. Millions of kilograms of diethyl ether are produced annually using sulfuric acid catalyst.

2 CH3CH2OH → CH3CH2OCH2CH3 + H2O (on 120 °C)

Combustion

Complete combustion of ethanol forms carbon dioxide and water:

C2H5OH + 3 O2 → 2 CO2 + 3 H2O(l)

(ΔHc = −1371 kJ/mol) specific heat = 2.44 kJ/(Kg·K)

Acid-base chemistry

Ethanol is a neutral molecule and the pH of a solution of ethanol in water is nearly 7.00. Ethanol can be quantitatively converted to its conjugate base, the ethoxide ion (CH3CH2O−), by reaction with an alkali metal such as sodium:

2 CH3CH2OH + 2 Na → 2 CH3CH2ONa + H2

Or a very strong base such as sodium hydride:

CH3CH2OH + NaOH → CH3CH2ONa + H2

The acidity of water and ethanol are nearly the same, as indicated by their of 15.7 and 16 respectively. Thus, sodium ethoxide and sodium hydroxide exist in an equilbrium that is closely balanced:

CH3CH2OH + NaOH CH3CH2ONa + H2O

Halogenation

Ethanol is not used industrially as a precursor to ethyl halides, but the reactions are illustrative. Ethanol reacts with hydrogen halides to produce ethyl halides such as ethyl chloride and ethyl bromide via an sn2 reaction:

CH3CH2OH + HCl → CH3CH2Cl + H2O

These reactions require a catalyst such as zinc chloride. HBr requires refluxing with a sulfuric acid catalyst. Ethyl halides can, in principle, also be produced by treating ethanol with more specialized halogen ting agents, such as thionyl chloride or phosphorus tribromide.

CH3CH2OH + SOCl2 → CH3CH2Cl + SO2 + HCl

Upon treatment with halogens in the presence of base, ethanol gives the corresponding halo form (CHX3, where X = Cl, Br, I). This conversion is called the halo form reaction. An intermediate in the reaction with chlorine is the aldehydes called chloral:

4 Cl2 + CH3CH2OH → CCl3CHO + 5 HCl

Oxidation

Ethanol can be oxidized to acetaldehyde and further oxidized to acetic acid, depending on the reagents and conditions. This oxidation is of no importance industrially, but in the human body, these oxidation reactions are catalyzed by the enzyme liver alcohol dehydrogenises. The oxidation product of ethanol, acetic acid, is a nutrient for humans, being a precursor to acetyl CoA, where the acetyl group can be spent as energy or used for biosyntheses.

CHAPTER 4ETHANOL AS A FUEL

Here is a lot of confusion surrounding the production of and trade in ethanol. This is hardly surprising given that there are a variety of feed-stocks from which it can be produced, a number of production processes and very different uses for this commodity. While these obstacles, to more transparency in the ethanol market may be termed technical, there are economic ones as well. In many countries one or two companies control the production of ethyl alcohol. As publicly available figures in sensitive areas could provide foreign rivals with a competitive edge, governments often allow statistical data on trade and production to be suppressed but there is yet another economic reason for the notorious unreliability of data on alcohol. Usually, beverage alcohol is heavy taxed which provides an incentive to smuggle or produce it illicitly, which can have a significant impact on the overall supply picture. Some basic concepts.

There is semantic confusion with regard to the term ethanol. Very often the term is used as a synonym for alcoholic beverages. This is misleading, even though ethanol may be used as a raw material for the production of spirits. In order to avoid misunderstandings we would like to define ethanol as a clear, colorless,' flammable oxygenated hydrocarbon, with the chemical formula C2 H5 OH. Even though the definition is fairly straightforward, there are various categories for describing a particular type of ethyl alcohol that are not mutually exclusive:

By feedstock. By composition. By end use.

The feedstock and therefore the processes by which ethanol can be produced are diverse. Synthetic alcohol may be derived from crude oil or gas and coal. Agricultural alcohol may be distilled from grains, molasses, fruit, sugar cane juice, cellulose and numerous other sources. Both products fermentation and synthetic alcohol are chemically identical. Synthetic alcohol is concentrated in the hands of a couple of mostly multinational companies such as Sasol with operations in South Africa and Germany, SADAF of Saudi Arabia, a 50:50 joint venture between Shell of the UK and Netherlands and the Saudi Arabian Basic Industries Corporation, and BP of the UK as well as Equistar in the US However, on a global scale synthetic feedstock plays a minor role. In 2003, less than 5% of overall output was accounted for by synthetic feedstock. More than 95% came from agricultural crops and given the strong interest in fuel ethanol production worldwide this share can be expected to grow in the future. Another distinction that is of importance in the field of ethanol is the one between anhydrous and hydrous alcohol. Anhydrous alcohol is free of water and at least 99% pure.

This ethanol may be used in fuel blends. Hydrous alcohol on the other hand contains some water and usually has a purity of 96%. In Brazil, this ethanol is being used as a 100% gasoline substitute in cars with dedicated engines. The distinction between anhydrous and hydrous alcohol is of relevance not only in the fuel sector but may be regarded as the basic quality distinction in the ethanol market. The final distinction that is necessary in order to understand the dynamics of the world

ethanol market is by end-use. Certainly the oldest form of use of alcohol is that of a beverage. The most important market for ethanol as an industrial application is solvent. Solvents are primarily utilized in the production of paints and coatings, pharmaceuticals, adhesives inks and other products. Ethanol represents one of the most important oxygenated solvents in this category. Production and consumption is concentrated in the industrialized countries in Northern America, Europe and Asia. It is the only market where synthetic ethanol producers hold a significant market share. The last usage category is fuel alcohol. As mentioned before, fuel alcohol is either used in blends, for example in gasohol or diesohol, or in its pure form. However, at present Brazil is the only country that uses ethanol as a 100% substitute for gasoline.

The history of ethanol as a fuel dates back to the early days of the automobile. However, cheap petrol quickly replaced ethanol, as the fuel of choice and it was not until the early 1980s, when the Brazilian government launched the Proalcool program, that ethanol made a come back to the market place. It may be estimated that fuel ethanol accounts for roughly 70% of world ethyl alcohol production in 2003. As can be seen from Chart 1, this share is forecast to rise to over 80% by the end of the decade. However, this projection only holds if the sometimes-ambitious fuel ethanol programs which have been proposed in the

CHART 1 : ETHANOL PRODUCTION BY TYPE

Chart 1 shows, that the industrial alcohol market is the smallest of the three. Moreover, it is showing a rather modest rate of growth, which is similar to the increase in Gross Domestic Product, Demand for distilled spirits in most developed

countries is stagnating or even declining, due to increased health awareness. This is unlikely to change in the future.

Ethyl alcohol as an automotive fuel can be used in two ways: First it replaces gasoline outright in dedicated internal combustion engines and secondly it is an effective "octane booster" when mixed with gasoline in blends of 5 to 30%. In this case no engine modifications are required. These blends achieve the same octane boosting or anti-knock effect as petroleum derived aromatics like benzene or metallic additives like lead. Ethanol easily blends with gasoline but not with diesel. If the diesohol blend is to obtain more than 3% ethanol special emulsifiers are needed. if we look at the bio-fuel programs that are already in existence, there are three key success factors that must be considered: first, the abundance and cheapness of feedstock used for their production together with The technology involved and last, but not least, A supportive political framework.

The feedstock issue

Let's look at the feedstock's issue fuel first. According to our 2003 survey, around 61% of world ethanol production is being produced from sugar crops, be it sugar beet, sugar cane or molasses, while the remainder is being produced from grains and here maize or corn is the dominating feedstock. Feedstock’s crucially determine the profitability of fuel ethanol production. There are various ways to look at the issue

CHART 2) the theoretical per ha ethanol yields of the three major feedstock’s currently in use are plotted.

CHART 3

If we look at the gross feedstock costs per .qallon of fuel ethanol produced, it is sugar cane grown in the Centre/South of Brazil, which clearly leaves the rest of the competition behind (Chart 3).

We may arrive at a first conclusion concerning the role of feedstock’s in biofuel production the raw material accounts for around 70 to 80% of the overall costs of fuel ethanol. Therefore, their relative abundance plays a crucial role in getting the fuel alcohol industry started in a particular country.

Political support

Critics often ask why bio4uels must be supported by the state. If fuel ethanol is such a great product, so they say, then it surely will gain market share without any government help. This argument is very much dependent on the assumption that the energy markets that we look at work perfectly. In the energy market, and in fact, in almost any market, these conditions are insufficiently meet and, therefore, an active policy approach may be justified.

There is growing consensus that fuel ethanol may serve a multitude of goals that are socially desirable. At the same time, as a fuel, it is invariably more expensive to produce than for example gasoline. Or looked at it from another angle, ethanol faces

an unfavorable opportunity cost structure. The opportunity costs for ethanol production from, for example sugar crops like cane or beet, is the return otherwise achievable if these feedstock’s were used to produce sugar. So, if policy makers decide that ethanol is a desirable, good, they have to find ways to bridge the gap between the cost of ethanol and that of gasoline and they have to make ethanol production more attractive as compared to the manufacture of, say, sugar.

There are various ways to achieve that It may be useful to distinguish between the various stages in the production and marketing process where subsidization may occur. For this end one can distinguish between input subsidies and output subsidies. Under the former category, one may summarize measures like feedstock price support (which results in prices below the going market rate) capital cost support (in the form of cheap loans and debt cancellations) and income tax concessions. On the output side most widely employed forms of support are excise tax concessions which make the product cheaper than would have been the case otherwise, so-called captive or mandated markets which ensure sufficient demand for the product, price guarantees and direct price support measures.

Comparison Of Ethanol with other Potential Fuel

Above chart clearly indicate

merits of ethanol compared to other oxygenates like methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME).

Demand for ethanol as fuel has been increasing since ages, in-spite of presence of other oxygenates. This can better be understood by seeing examples of USA, Basically early years USA also used both MTBE and fuel ethanol

The various tax incentives have certainly helped the ethanol industry in the US to get off the ground. However, the real boost came with the introduction of mandated or captive markets in the early 1990s. The Clean Air Act mandated the use of cleaner burning fuels in the dirtiest US cities. In order to achieve that, the legislation enforces the addition of oxygen to gasoline. For long time petrol derived MTBE has been oxygenate of choice but this is likely to change now and this explains the amazing growth in recent years. Starting in January 2004, US states banned MTBE from its ~uel pool. This opened the way for ethanol.

CHAPTER 5

DEMAND OF ETHANOL AS FUEL IN INDIA

India's transport sector is growing rapidly and presently accounts for over half of the country's oil consurnption whilst the country has to import a large part of its oil needs. Hastening interest in an ethanol program was the country's sugar glut (part of which the industry is now exporting to the world market) and burgeoning supplies of molasses. The sugar industry lobbied the government to embrace a bio-ethanol programmed for several years. The industry emphasized that producing fuel ethanol would absorb the sugar surplus and help the country's distillery sector, which is presently burdened with huge overcapacity, and also allow value adding to by-products, particularly molasses.

India's Minister for Petroleum and Natural Gas gave his approval in December 2001 to a proposal to launch pilot projects to test the feasibility of blending ethanol with gasoline. Mid-March 2002 the government decided to allow the sale of E 5 across the country. On 13 September 2002, India's government rnandated that refine states and four federally ruled areas would have to sell E-5 by law from 1 April 2004. In response India's sugar producers reportedly planned to build 20 ethanol plants before the end of the year in addition to 10 plants already constructed. Most of the plants were being constructed in Uttar-Pradesh, Maharashtra and Tamil Nadu, the key sugar producing states and will chiefly use cane sugar molasses as a feedstock.

Estimated annual ethanol needs for a E-5 blend is 0.37 bln litres. A 10% blend increases the need to 0.72bln litres. This is against installed annual production capacity of 2.7bln litres/year and annual consumption of 1.5bin litres. These figures have to be treated with some caution. The chemical industry, fearing higher ethanol prices as a result of the fuel alcohol programmed, usually estimates the surplus to be much lower or even non-existent.

The sugar industry, on the other hand, estimates capacity at 3.2bln litres inflating the surplus. The success of ethanol in India will depend to a significant degree on pricing The sugar industry originally claimed that it could provide ethanol at 19 Rupee per litre ($0.38/litre), which is at a lower cost than the product it would substitute, MTBE. which costs 24-26 rupees per litre ($0.49-0.53/litre). The oil industry however is seeking parity between ethanol and the price of gasoline on an ex-refinery or import basis. In April 2002 the government announced Rs0.75 excise duty exemption. Implementation of the excise duty for ethanol which, however, was delayed however until February 2003, because the chemical industry opposed it, fearing higher prices and shortages of alcohol.

ANHYDROUS ETHANOL POTENTIAL FOR GASOLINE BLENDING

The statistics published by the Ministry of Petroleum the potential is as follows: For 5% Blend in Gasoline

Requirement on all India Basis - 600 million ltrs. per annum Requirement in 8 States - 300 million ltrs. per annumRequirement in UP & Maharashtra - 40 & 70 million ltrs. per annum

This statistics show a direct potential. Due to govt. promoting ethanol to mix in petrol there is drastic demand for ethanol, which could overcome the existing unutilized capacity and thus creating an excess demand. However, pricing appears to becoming a stumbling block and in June 2003 India's Petroleum Ministry announced that it would appoint a Tariff Commission to fix an appropriate price for ethanol sourced from sugar mills. Ethanol pricing in India is also complicated by differences in excise duty and sales tax across states and the central government is trying to rationalize ethanol sales tax across the country. More significantly perhaps, there are still substantial differences in the profitability of potable alcohol as against fuel alcohol and in several states. Consequently, insufficient fuel alcohol is being produced to meet demand. Other states have yet to set up sufficient production capacity. Analysts expect that there is a deficit of around 150 mln litres under the current geographic base to the fuel ethanol program; a deficit that will grow once the mandated blending requirement is extended to all states in India. Consequently, there may be a short-term market for imported Brazilian ethanol. As the use of fuel ethanol has just started it's export has not yet began but it has a great scope The Centre's Gasohol Program' of blending 5% ethanol in petrol has given an assured scope for ethanol industry in the country. The Centre's Kisan-friendly imitative has definitely been a boost to the venture. Following statistics could show how there is definite market potential for such industry.

PETROL CONSUMPTION

10000000 KILO Liters

500000 KILO Liters - 5% ALCOHOL required

500000000 Ltrs.

Demand all over Country 5000 Lac liters

Existing Production 1840 Lac liters

Total demand 2460 Lac liters

Demand in Maharashtra 700 Lac liters

Source: The information is taken from document published by Govt. of India Ministry of Petroleum and Natural Gas.

   

In parts of 4 states of Andhra Pradesh, Maharashtra, Punjab, Uttar Pradesh & Goa 5% of ethanol blended petrol has already been started and till 30 th June 2003, it will be fully covered. Gujarat, Haryana, Karnataka, Tamilnadu and the Union Territories of Chandigarh, Dadra & Nagar Haveli Daman and Div and Pondicherry are also covered till end of July 2003.

 The entire country will be covered in 2nd Phase and ethanol content to be increased to 10% in 3rd Phase. Most important R & D Studies are successful of blending ethanol with Diesel, which itself is a very significant point in developing ethanol. All this significance shows a definite assured market for the industry leading the project to most viable and safe for financial assistance.

IMPORT EXPORT DATA

India ranks 2 nd in world for production of ethanol (Hydrous usually <95% pure) India is leading exporter of hydrous ethanol worldwide. It exports hydrous ethanol to countries like Sri-lanka ,Yemen, Iraq, Iran, etc. In India, blending of anhydrous just started 2 yrs back (April 2004). Presently its (anhydrous ethanol’s) demand as a fuel basically for blending purpose is increasing. So as to satisfy this increasing demand within country, India has not yet started exporting anhydrous ethanol (i.e.100% pure).

India Minister for petroleum and natural gas gave his approval in December 2001 to a proposal to launch a pilot project to test the feasibility of blending ethanol with gasoline. Mid-march 2002 the government decided to allow the sale of E-5 across the country. On 13 September 2002, India’s government mandated that nine states and four federally ruled areas would have to sale E-5 by law from 1 April 2004. As Indian govt. gave for blending of ethanol around 2004, so India has not yet started to import.

CHAPTER 6

MANUFACTURING PROCESSES

Industrial ethyl alcohol can be produced synthetically from ethylene, as a by-product of certain industrial operations, or by the fermentation of sugar, starch, or cellulose. Fermentation processes accounted for 83% of total production in the U.S., Western Europe and Japan in 1997. By 2001 fermentation increased to 90%. The first synthesis of ethanol from ethylene occurred in 1828 in Michael Faraday’s laboratory in Cambridge. There are two main processes for the synthesis of ethyl alcohol from ethylene.

The earliest to be developed (in 1930 by Union Carbide Corp.) was the indirect hydration process, variously called the strong sulfuric acid–ethylene process, the ethyl sulfate process, the esterification–hydrolysis process, or the sulfation–hydrolysis process. This process is still in use in Russia. The other synthesis process, designed to eliminate the use of sulfuric acid and which, since the early 1970s, has completely supplanted the old sulfuric acid process in the United States, is the direct hydration process. This process, the catalytic vapor-phase hydration of ethylene, is now practiced in the U.S. only by Dow Chemical; Texas City, Texas, Dow imports crude industrial ethanol, CIE, from Saudi Arabia in a tolling arrangement with shell chemicals, and refines it to industrial grade.

Other synthetic methods have been investigated but have not become commercial. These include, for example, the hydration of ethylene in the presence of dilute acids (weak sulfuric acid process); the conversion of acetylene to acetaldehyde, followed by hydrogenation of the aldehydes to ethyl alcohol; and the Fischer-Tropsch hydrocarbon synthesis. Synthetic fuels research has resulted in a whole new look at processes to make lower molecular weight alcohols from synthesis gas.

Ethylene hydration

Ethanol for use as an industrial feedstock or solvent (sometimes referred to as synthetic ethanol) is often made from petrochemical feed stocks, primarily by the acid-catalyzed hydration of ethylene, represented by the chemical equation

C2H4(g) + H2O(g) → CH3CH2OH(l).

The catalyst is most commonly phosphoric acid, adsorbed onto a porous support such as silica gel or earth. This catalyst was first used for large-scale ethanol production by the Shell Oil Company in 1947. The reaction is carried out with an excess of high pressure steam at 300 °C. In the U.S., this process was used on an industrial scale by Union Carbide Corporation and others; but now only Lyondell Bissell uses it commercially.

In an older process, first practiced on the industrial scale in 1930 by Union Carbide,[21] but now almost entirely obsolete, ethylene was hydrated indirectly by reacting it with concentrated sulfuric acid to produce ethyl sulfate, which was hydrolyzed to yield ethanol and regenerate the sulfuric acid:

C2H4 + H2SO4 → CH3CH2SO4H

CH3CH2SO4H + H2O → CH3CH2OH + H2SO4

Fermentation

Fermentation one of the oldest chemical processes known, it is used to make a variety of products, including fuel, foods, flavorings, beverages, pharmaceuticals, and chemicals. Most of the fermentation ethanol is made from corn even though before World War II molasses was the chief feedstock. Ethanol can be made from a variety of agricultural products such as other grains, sugar cane and beets, fruit, whey, and sulfite waste liquor. Studies are underway to ferment garbage to ethanol. Generally, most of the agricultural products mentioned command higher prices as foods, and others, eg, potatoes, are uneconomical because of their low ethanol yield and high transportation cost. The use of fermentation ethanol in the industrial market depends on the availability and cost of the carbohydrate relative to the availability and cost of ethylene, and the economics and government policies relating to the fuel ethanol market.

Ethanol can be derived by fermentation processes from any material that contains sugar or compounds that can be converted to sugar. The many and varied raw materials used in the manufacture of ethanol via fermentation are conveniently classified under three types of agricultural raw materials: sugar, starches, and cellulose materials. Sugars (from sugar cane, sugar beets, molasses, or fruit) can be converted to ethanol directly. Starches (from grains, potatoes, or root crops) must first be hydrolyzed to fermentable sugars by the action of enzymes from malt or molds. Cellulose (from wood, agricultural residues, or waste sulfite liquor from Pulp and paper mills) must likewise be converted to sugars, generally by the action of mineral acids.

Once simple sugars are formed, enzymes from yeast can readily ferment them to ethanol. Because fermentation ethanol has been thoroughly and repeatedly discussed in the literature, the coverage here is illustrative rather than comprehensive, with special emphasis on the potential raw materials for ethanol production of the future

Sugar

Prior to the late 1970s, the most widely used sugar for ethanol fermentation was blackstrap molasses which contains about 35–40 wt % sucrose, 15–20 wt % invert sugars such as glucose and fructose, and 28–35 wt % of no sugar solids. Blackstrap (derived from Java and the Dutch word stoop, meaning syrup) is

collected as a by-product of cane sugar manufacture. The molasses is diluted to a mash containing10 − 20 wt % sugar.

After the pH of the mash is adjusted to about 4–5 with mineral acid, it is inoculated with the yeast, and the fermentation is carried out no aseptically at 20–32◦C for about 1–3 d. The fermented beer, which typically contains 6 − 10 wt % ethanol, is then sent to the product recovery and purification section of the plant. The direct fermentation of sugar cane juice, sugar beet juice, beet molasses (a by-product in the production of beet sugar), fresh and dried fruits, cane sorghum, whey, and skim milk had been considered as a means of obtaining ethanol, but none of these raw materials could compete economically with molasses. Although the manufacture of ethanol from the sugar-containing waste products of the fruit industry appears to be a highly desirable operation, particularly as a means of reducing stream pollution in the vicinity of canning plants, such production is costly because of the need to remove most of the water (as much as 97%) contained in the waste product. The results of the sugar-crop research on agronomics and fuels conversion undertaken by Battelle’s Columbus Laboratories lists several merits of sugar cane as a candidate energy resource. Sugar cane, a renewable raw material, is renowned for its agricultural productivity, and its juice is directly fermentable to ethanol. On the other hand, sugar cane products are valuable in food and feed applications and their conversion to chemicals and energy can be considered an underutilization of their potential value. In 1975, Brazil embarked upon the ambitious pro Alcohol program for fermentation ethanol manufacture from sugar cane to reduce the country’s dependence on foreign oil, and to modernize and make more competitive Brazil’s sugar mills in a lagging international sugar market.

Gasohol’s have been used in Brazil since the early 1930s. The number of alcohol distilleries grew to over 500 while the number of big sugar plantations grew to over 1000. Brazil is currently the world’s largest producer of fermentation alcohol. The subject of fermentation alcohol has always been of considerable interest to several tropical countries, but until the oil crisis of 1973, other than Brazil, only India appeared to appreciate the importance of fermentation alcohol as a strategic material in its economy. Ethanol prices in India have been maintained at an extremely low level by processing cane molasses, which has been a waste product of negligible value.

Starch

In the United States, all potable alcohol, most fermentation industrial alcohol, and most fuel alcohol is currently made principally from grains; corn is the principal feedstock for fuel alcohol. Fermentation of starch from grain is somewhat more complex than fermentation of sugars because starch must first be converted to sugar and then to ethanol. This process was known to the ancient Egyptians and Mesopotamians who brewed beer almost 5000 years ago. The simplified equations for the conversion of starch to ethanol are

C6H10O5 + H2 enzyme C6H12O6 yeast 2 C2H5OH + 2 CO2

Starch is converted enzymatic ally to glucose either by diastase presents in sprouting grain or by fungal amylase. The resulting dextrose is fermented to ethanol with the aid of yeast, producing CO2 as a co product. Other byproducts depend on the type of process. The basic process steps for converting corn into ethanol are degermination, milling, and separation of starch bearing endosperm from hulls, slurring–liquefaction, and hydrolysis of starch to sugar, fermentation, distillation, and dehydration. The hydrolysis or saccharification is usually carried out with an amylase enzyme and the fermentation is usually by the yeast Saccharomyces cerevisiae.

Corn can be prepared for fermentation by three different processes: whole-grain grinding, dry milling, and wet milling. The fermentation process has been considerably refined and has led to an efficient process. The two main processes are dry milling and wet milling. The main difference is in the treatment of the grain. For dry milling, the entire corn or starchy grain is ground into flour (meal), and processed without separating out the components. The meal is slurried to form mush. Enzymes are added to convert starch to dextrose. Ammonia is added for pH control and as a nutrient for yeast. The mash is processed in a high temperature cooker to reduce bacteria levels ahead of fermentation. The mash is cooled and then transferred to the fermenters where yeast is added and conversion of sugar to ethanol and carbon dioxide begins.

The process takes about 40–50 hours. The mash is agitated and kept cool to facilitate yeast activity. The fermentation product is agitated and is kept cool. The ethanol is separated out. Ethanol is concentrated to 190 proofs by distillation and then dehydrated to 200 proofs by a molecular sieve system. Ethanol is treated with a denaturant to render it undrinkable, and thus, is not subject to beverage tax. A by-product produced by centrifugation of coarse grain and soluble material is Condensed Distiller’s Syrup. This is used for livestock feed. In wet milling, the grain is soaked or steeped in water and sulfurous acid for 24–48 hours to separate it into components. After steeping, the corn slurry goes through grinders to separate corn germ and fiber components. Corn oil is extracted. The steepage liquor is concentrated by evaporation. Gluten is separated outland used in livestock feed.

The remaining liquid is fermented to ethanol or dried to corn starch or corn syrup. The fermentation is the same as for the dry milling process. The fuel alcohol program has spawned a tremendous amount of research aimed at improving the cost and efficiency of the corn process. Three promising technologies for lowering operating costs are substituting yeast with high temperature bacteria such as Zymomonous mobilis; using a permeable membrane to separate dissolved solids and some of the water before distillation; and immobilizing the yeasts and enzymes in the wet-mill process to provide continuous processes with higher productivities.

Cellulosic Materials

Over 900 × 106 metric tons of carbohydrate-containing cellulosicwastes are generated annually. The technology for converting this material into ethanol is available, but the stoichiometry of the process is disadvantageous. Even if each step

in the process of the conversion of cellulose to ethanol proceeded with 100% yields, almost two-thirds of the mass would disappear during the sequence, most of it as carbon dioxide in the fermentation of glucose to ethanol. This amount of carbon dioxide leads to a disposal problem rather than to a raw material credit.

Starch and cellulose are both polymers of glucose, but cellulose is much more difficult to hydrolyze to the sugar. Its structure is more crystalline which protects the internal bonds from hydrolysis, and cellulose in plants is protected by lignin, a polyphenolic material that forms a seal around the cellulose for further protection against hydrolysis. Cellulosic wastes also contain substantial amounts of hemicellulose, which is a polymer of pentoses. The aqueous mineral acids used to hydrolyze the cellulose to glucose destroy much of the sugars, particularly the pentoses, in the process. Nevertheless, a 1978 study claimed that forests could theoretically provide 50% of the oil and gas used by U.S. utilities, replacing 20% of annual fossil fuel consumption. None of this has taken place, but research has continued. A process utilizing low temperature hydrolysis to separate cellulose from paper has been licensed, with plans to construct a plant in Germany. The process uses electrodialysis rather than diffusion dialysis to recover hydrochloric acid for reuse. Other new ways of reducing the cost of converting cellulosic wastes from wood, newspapers, and municipal garbage into glucose include the use of less corrosive acids and reduced hydrolysis time. One way of making cellulose wastes more susceptible to hydrolysis is by subjecting them to a short burst of high energy electron beam radiation. Hydropulping of cellulose feedstocks followed by a 10 μs burst from a 3 × 106−eV electron-beam accelerator is claimed to reduce the time of hydrolysis by dilute acid from hours to seconds. An alternative to acid hydrolysis is the use of enzymes. Although they avoid the corrosion problems and loss of fuel product associated with acid hydrolysis, enzymes have their own drawbacks Enzymatic hydrolysis slows as the glucose product accumulates in a reaction vessel. This end-product inhibition eventually halts the hydrolysis unless some way is found to draw off the glucose as it is formed.

In mid-1978, Gulf Oil researchers described the simultaneous enzymatic hydrolysis of cellulose and fermentation of the resulting glucose to ethanol, removing glucose as it is formed and overcoming the problem of product inhibition of hydrolysis. Mutated strains of the common soil mold Trichoderma viride can process 15 times as much cellulose as natural strains. The results have been encouraging; in some cases, cellulose from sawdust, bark, and effluent streams from the pulp and paper industries have produced ethanol in yields approaching 100% of the theoretical value. A sequential hydrolysis process has been proposed, in which the hemicelluloses is hydrolyzed to pentose by aqueous sulfuric acid and then separated for fermentation. The remaining ligno-cellulose is then pretreated with the solvent cad oxen (5–7% cadmium oxide in 28% aqueous ethylenediamine) which break the lignin seal to allow enzyme-catalyzed hydrolysis to glucose. Pentose fermentation to ethanol is more difficult and this process allows the two sugars to be fermented separately. Research is underway on genetically engineered bacteria for cellulose conversion. A novel pretreatment for municipal solid waste consists of soaking the waste in high pressure liquid ammonia. An instant pressure release opens up the fiber structure so that enzymes can more easily penetrate and digest the cellulose. A 25% increase in the amount of waste digested to sugar is claimed. Steam explosion has been reported as an effective pretreatment for the enzymatic hydrolysis of wood and agricultural residues.

REFINIG OF ETHANOL

Till now we have discussed about manufacture of Ethanol (85-95% pure), now we shall see about refining. As discussed previously, available technologies for dehydration of rectified spirit can be classified in to three broad headings.

Azeotropic distillation Molecular Sieve Technology Per-vaporization technique

They are as follows

AZEO'I'ROPIC DISTILLATION

Distillation as ethyl alcohol forms a constant boiling mixture with water at this concentration and is known as azeotropic. Therefore, special process for removal of water is required for manufacture of absolute alcohol. in order to extract water from alcohol it is necessary to use some dehydrate, which is capable of separating, water from alcohol. Simple dehydrate is unslacked lime, Industrial alcohol is taken in a reactor and quick lime is added to that and the mixture is left over night for complete reaction. it is then distilled in fractionating column to get absolute alcohol. Water' is retained by quick lime. This process is used for small-scale production of absolute alcohol by batch process.

MOLECULAR SIEVE DERHYDRATION

The rectified spirit from the rectifier is superheated with steam in feed super-heater. Super-heated rectified spirit from feed super-heater is passed to one of the pair of molecular sieve beds for several minutes. On a timed basis, the flow of superheated rectified spirit vapors is switched to the alternate bed of the pair. A portion of the anhydrous ethanol vapors leaving the fresh adsorption bed is used to regenerate the loaded bed.

A moderate vacuum is applied by vacuum pump operating after condensation of the regenerated ethanol water mixture. This condensate is transferred from recycle drum to the Rectified Column in the hydrous distillation plant Via Recycle pump. The net make of anhydrous Absolute alcohol draw is condensed in product condenser and passed to product storage. The life of molecular sieve may be around five to seven years. However, the operating cost is considerably less than azeotropic distillation.

MEMBRANE PREVAPORISATION

In this the overhead from preco Pervaporation differs from other membrane processes in that the membrane constitutes the barrier between feed which is liquid and permeate which is vapor The driving force for the process is the chemical potential on the two sides of the membrane

In this the overhead from preconcentrator, which is a distillation column with 50-60%ethanol is sent to another distillation column (known as stripping column) giving 95% pure ethanol as top product (Rectified spirit). The vapors’ are condensed and collected in a buffer tank (accumulator), which feeds the Pervaporation unit. The vacuum is maintained on the other side of the membrane at which water is obtained as permeate in the vapor form. The membrane has higher permeability towards water. it is condensed and recycled to the stripper column.

CHAPTER 7

SELECTION OF PROCESS

The choice of process for the production of any product must include consideration of several factors:

The capital cost involved. Availability of raw material The demand both present and anticipated Simplicity/Complexity of operation Availability of skill both for the creation of plant, as small as for its

operation The problems of fluent disposal. The technology of availability. The economics of the process.

Choice of Process:

Our basic aim can be divided in to two parts

To produce ethanol. (Hydrous containing approximately 95% ethanol) To obtain 100% pure anhydrous ethanol from Step 1

To produce ethanol (hydrous) we can go for fermentation process or by petroleum processing.

After obtaining hydrous ethanol, we need to obtain anhydrous ethanol. For this, we can go for Molecular Sieve technology or by azeotropic distillation.

Ethanol is produced mainly from black strap molasses in India, sugar juice in Brazil, Corn in U.S.A and Beet in Europe. With abundant supply of sugarcane, India has an advantage in switching to the fuel ethanol program by fermentation of molasses.

Alcohol by fermentation in India is limited to sources substrate starch and paper mill wastes. Fermentation of alcohols served a good purpose in starting of the organic chemical industry knows how to incorporate in larger plants.

Now for anhydrous ethanol we usually prefer for Molecular Sieve technology than azeotropic distillation because of its (Molecular Sieve technology's) advantages over azeotropic distillation.

ADVANTAGES OF MOLECULAR SIEVE TECHNOLOGY FOR ETHANOL DEHYDRATION ARE AS FOLLOWS: -

1 The basic process is very simple, making it easy to automate which reduces labour and training requirements.

2. The process is inert. Since no chemicals are used, there are no material handling or liability problems, which might endanger workers.

3. Molecular sieves can easily process ethanol-containing contaminants, which would cause immediate upset in an azeotropic distillation system. In addition to ethanol, a properly designed sieve can dehydrate a wide variety of other chemicals, thereby providing added flexibility in future operating options.

4. The molecular sieve desiccant material has a very long potential service life, with failure occurring only due to fouling of the media or by mechanical destruction. A properly designed system should exhibit a desiccant service life in excess of 5 years.

5. It can be configured to function as a stand-alone system or to be integrated with the distillation system. This lets the customer make the trade-off between maximum operating flexibility versus maximum energy efficiency.

6. If fully integrated with the distillation system, steam consumption rate only slightly above the absolute theoretical minimum for the separation can be achieved.

7. Most of the ethanol dehydration plants for production of absolute alcohol are based on Azeotropic distillation; it is a mature and reliable technology capable of producing a very dry product. However, its high capital cost, energy consumption, reliance on toxic chemicals like benzene and sensitivity to feedstock impurities, has virtually eliminated the use of azeotropic distillation in modern ethanol plants. Benzene has been used as entrained of choice of ethanol dehydration but it is now known to be a powerful carcinogen.

A properly designed molecular sieve can reliably dehydrate 160-proof ethanol to 190 + proof, making strict control of rectifier overhead product quality unnecessary. So, to produce Ethanol (Hydrous containing we use fermentation process. Approximately 95% ethanol.

Further, to obtain 100% pure anhydrous ethanol we use Molecular Sieve technology.

DETAILED MANUFACTURING PROCESS

First we would discuss various raw materials and then later actual flow sheet in detail

RAW MATERIAL

YEAST

Organism alternation: Yeast is the only Organism Currently used for large-scale ethanol production· Yeast produces ethanol with very high selectively (only traces of by products) is very hardy and large compared with bacteria (allowing simplified handling). Clostridium thermosaccharolyticum, thermoanaerobactor ethanolicus and other thermophilic bacteria as well as Pachysolen tannophilus yeast are under intensive study for use in fermenting pentose sugars, which are non-fermentable by ordinary yeast· These bacteria also convert hexos sugars and have been considered as an alternative to yeast science very high temperature reaction would allow simple continuous stripping of yeast from one of the importantsubgroups of fungi like bacteria are widespread in the nature although they usually live in the soil and in the region of very lower humidity than bacteria· They are unable to extract energy from sunlight and usually free-living.

YEAST STRAIN SELECTION

Yeast strain are generally chosen from among zymase Saccharomyces cerevisiae, s. ellypsoideus, s. carisbergensis, s. fragilis and schizosaccharomyces pombe. For whey fermentation, torula cremories or candida pseuodotropicalis is used.

Yeasts are carefully selected for:

High growth and fermentation rate. High ethanol yield. Ethanol and glucose tolerance. Osmo tolerance low pH fermentation optimum High temperature fermentation optimum. General hardliness under physical and chemical stress.

High growth and fermentation rate allows the use of smaller fermentation equipment· Ethanol and glucose tolerance allows the conversion of concentration feeds toconcentrated products, reducing energy requirements for distillation and stilling handling· Osmotolerance allows the handling of relatively dirty raw materials such as blackstrap molasses with its high salt cintent. Osmetolerance also

allows the recycle of large portion of stilling liquids, thus reducing stilling handling costs. Low pH fermentation combats contamination by competing organisms· High temperature tolerance simplifies fermenter cooling. General hardliness allows yeast to survive both the ordinary stress of handling (such as centrifugation) as well as the stresses arising from the plant upset.

FERMENTATION KINETICS

YEAST METABOLIC PATHWAYS

In the anaerobic pathway, glucose is converted to ethanol and carbon dioxide via glycolysis. The overall reaction produces two moles of ethanol and carbon dioxide for every mole of glucose consumed, with the reaction energy as two rnoles of ATP for use in biosynthesis or maintenance.

Glycolysis

C6H12O6 2C2H5OH +2CO2+energy (stored as ATP)

Via this pathway, every gram of glucose converted will yield 0.511 g of ethanol. Secondary reaction will consume a small portion of glucose feed, however, to produce biomass and secondary products and Pasteur found that actual yield of ethanol from fermentation by yeast in reduced to 95% of the theoretical maximum. When complex substrates, typical of industries practice, are used, further by-products and generated and the ethanol yield is reduced typically only to 90% of the theoretical.

Optimum yields from Anaerobic

Via aerobic metabolism, sugar is converted completely to carbon dioxide, cell mass and by-products, with no ethanol formed, and aerobic metabolism must be avoided.

Products G per 100 grm of Glucose

Ethanol 48.4

Carbon dioxide

46.6

Glycol 3.3

Succinic acid 0.6

Cell mass 1.2

EFFECT OF SUGAR CONCENTRATION

HEXOSE SUGAR (glucose, fructose, glactose or maltose) is the primary reactant in the metabolism Under fermentative conditions, the rate of production is related to the available sugar concentrations by a Monode type equation:

V = Vmax Cs

(Ks +Cs)

Where,

V = Specific ethanol productivity Cs = Sugar substrate concentration

Ks = Saturation constant

At very Iow substrate concentrations (below about 3gl -1), the yeast is starved and productivity decreases. At higher concentrations a saturation limit is reached, so that, the rate to produce the ethanol per cell is essentially at its maximum up to 150g/I catabolite (sugar) inhibition of enzymes in the fermentative pathway becomes important and the conversion rate is slowed. An important secondary effect of sugar is catabolite repression of the oxidative pathways (the Crabtree effect) At above 3.30 gl-1 sugar concentration (depending on yeast strain), the production of oxidative enzymes is inhibited, thus forcing fermentative metabolism. The catabolite repression is not found in all yeast and is a desirable property, which is selected, in the industrial strains.

EFFECT OF ETHANOL

Ethanol is toxic to yeast and high tolerance is a desirable trait selection in the industrial strains The inhibitory effect of ethanol is generally negligible a Iow alcohol concentrations (20 gl-l) but increase rapidly at higher concentrations. For most strains ethanol production and cell growth are halted completely at above 110 gl-1, although some very Iow fermenting sake yeast (saccharomyces sake) can tolerate ethanol concentrations as high as 160/gl at Iow temperatures. Ethanol inhibition is directly related to inhibition and denaturation of important glycolic enzymes, as well as to the modification of cell membrane. It is important to avoid a high degree of aerobic metabolism, which utilizes the sugar substrate but produces no ethanol, it has been found ,however the trace amounts of oxygen may greatly stimulate yeast fermentation. Oxygen is required for yeast growth, as a building block for the biosynthesis of polyunsaturated fats and lipids required in aerobic sugar consumption in yeasts, which slows the Crabtree effect. For other yeast or at Iow sugar concentration, the oxygen supply should be limited. Trace amounts (0.7 mm hg oxygen tension) of oxygen are adequate and do not promote aerobic metabolism.

Effect of pH:

Fermentation rate is sensitive to pH, but most distiller's yeasts show a broad optimum from at least pH 4-6. Its range is lower than that for typical bacteria. Further, rnost yeasts can tolerate exposure to acid solution of pH as Iow as 2 without permanent damage.

Effect of temperature:

High temperature tolerance is a desirable characteristic for in distillery yeasts and most distillery yeasts have temperature growth optimum growth optimum 30-35 degree Celsius

The optimum fermentation temperature at Iow alcohol concentrations is often higher up to exposure to temperatures above the optimum results in excessive enzyme degradation and loss of yeasts viability. Yeast metabolism liberates 11.7 kcal of heat for each kg of substrate consumed. Yeasts can be stored inactive at Iow temperatures i.e. above zero degree Celsius and are readily revived.

Additional nutrient requirements

In addition to providing a sugar source for ethanol production, fermentation mash also provides the secondary nutrients necessary for cell maintenance and growth. In laboratory tests, very rapid cell growth and ethanol production and high yields are achieved with a glucose medium supplemented with NH4CI,MgSO4, CaCI2 and yeast extract. Ammonium ions provide nitrogen for protein and nucleic acid synthesis.

Yeast extract is the water soluble extract of auto catalysed yeast and contains all necessary yeast growth factors: amino-acids, pureness, pyrimidines and vitamins as well minerals Phosphorus, potassium (from the yeast extract), magnesium and calcium are incorporated into cell used is apparent from oura's (1974) comparison of 12 of the best-known culture media.

Raw material selection

For production of ethanol, sweet sorghum can be best option over sugarcane & molasses.

Some drawback by molasses method Production of ethanol is totally depended on sugar industry & as sugar

production is excess in our country so we cannot increase the production of sugar, ultimately we cannot increase production of ethanol because molasses is obtain from sugar industries.

Our sugar is not a export quality so increasing production means unnecessary blockage of capital

Our sugar industries is working only in particular period so there is not continuous supply of molasses.

So it is necessary to find a new raw material to meet this huge demand of ethanol.

Advantages of sweet sorghum over molasses

Free from sulfur and easy for blending Continuous production of ethanol is possible Along with this it has got following agriculture advantage Production of ethanol per hector is 7600 liter while from sugarcane, it is 1000

liter. Percentage of water required is much less than sugarcane Fertilizer input required is also less than sugarcane. So overall cost of production is less.

Sweet sorghum stalk processing for ethanol production

Juice extraction

Juice is extracted by series mills. The juice coming out of milling section is first Screened, sterilized by heating up to 1000C and then clarified the muddy juice is first sent to Rotary vacuum filter and the filtrate juice is sent to evaporation section for concentration. The juice can also be directly sent to fermentation section. depending on the scheme selected the juice can be concentrated using evaporators to attend various brix. In case of juice to ethanol, it is advisable to partially increase the concentration of juice to 16-18 brix. The syrup which needs storage for using during off season needs to concentration to minimum 65 brix.

Fermentation

Fermentation is a multidisciplinary process based on the chemistry, biochemistry and microbiology of the raw materials. Juice or syrup is converted into ethanol by the yeast saccharomyces cerevisiae.sugar is converted ethanol, carbon dioxide and yeast biomass as well as much smaller quantities of minor end products such as glycerol, fuel oil, aldehydes and ketones.

Distillation

In the distillation section, alcohol from fermented mash is concentrated up to 95% v/v. this is further concentrated to produce ethanol with 99.6% v/v concentration. The treatment of vinasse generated in the distillation section can be done using following option: concentration of part of vinasse to 20 to 25% solids followed by composting using press mud available and concentration of the vinasse to 55% solids and use as a liquid fertilizer..

Manufacturing process of ethanol from sweet sorghum juice

Our basic aim is can be divided in to two parts

1.To produce ethanol.(hydrous containing approximately 95% ethanol)2.To obtained 100% pure anhydrous ethanol from step 1.

Process description

The gradually cultured distillers yeast along with nutrient is poured rate the tank Then in the proportion of 1 gm of yeast per lit juice of sweet sorghum that has been heated and sterilized is introduced into the tank aerobic condition with 32oC temperature is maintain in the tank, yeast completes the growth in 18-24 hr. after the yeast has reproduced, open the valve of tank. Let juice of sweet sorghum and yeast flows into the fermentation tank. Then nutrient in yeast provide for saccharomicyne to reproduce it in a large quality anaerobic condition are maintain here. This Produce takes about 24hr. and above 95% sweet sorghum juice could fermented to become alcohol and CO2.

Separation of the 8-10% alcohol in the fermented liquor called beer is accomplished by a series of distillations. In the beer still, alcohol (50-60% conc.) and undesirable volatiles such as aldehydes are taken off the top and fed to the Aldehydes still. Alcohol is pulled off as a side-stream split to the rectifying column. In this final column, the azeotropic alcohol-water mixture of 95% ethanol is taken off as a top side-stream,

Now to obtain 100% pure anhydrous ethanol we will use MOLECULAR SIEVE TECHNOLOGY

LEGENDS

Notation DescriptionC110 DISTILLATION COLUMND113 SETTLING DEVICED110A 1ST MOLECULAR SIEVE BEDD110B 2ST MOLECULAR SIEVE BEDE111,E113,E114,E115 HEAT EXACHANGERE112 CONDENSERE110 REBOILER

PROCESS DECRIPTION -MOLECULAR SIEVE TECHNOLOGY

1) The feed (rectified spirit) pumped from the storage tanks, is heated through the heat exchanger (El14) by dehydrated alcohol, then heated RS of 93% to 96% is fed to the top of the distillation column Cl10.

2) The liquid passes through the distillation column where ethanol is stripped of, The alcohol free liquid called spend lees is separated and discharged from the bottom of distillation column and ethanol stream, with strength of about 96% by volume, is removed as vapour, at the top section of the distillation column and feed to the molecular sieve unit after a super heating about 1 15°C by steam in the heat exchanger (El11).

3) Fusel oils are removed from an intermediate points of the column in order to avoid any risk of flooding of the column and feed to the static setting device (D-113) where they are separated from the weak water which are recycled to the column.

4) The distillation column (C-110) has an operating pressure of about 160 kpa (A) and is heated with low pressure steam by menace of reboiler (E-110).

5) The super heated ethanol stream removed at the top of the distillation column feeds one of the two sieve beds (D-110A) is now in regeneration mode.

6) The second sieve bed (D-110OB) is now in regeneration mode under vacuum) and receives a small amount of vapors from (D-110A) working in over pressure. As soon as regeneration is finished ( a regeneration cycle lasts about 5 minutes), an automatic control system changes the operating conditions of two sieve beds in order to have the first sieve D-110A) in regeneration and the second one (D-110B) in dehydration mode.

7) The dehydration process release a vapors ethanol stream with a very small amount of water (500 p.p.m or less), which is condensed in the condenser E 113, cooled in the heat exchangers E-114 and E-115 and sent to the storage as dehydrated alcohol.

8) The regeneration process releases a certain amount of absorbed water and ethanol, which are condensed in the condenser E-112 and recycled to the column.

9) Cooling media of the first cooling steps of the dehydrated alcohol is the regeneration stream recycled to the distillation column and cooling media of the second cooling step of dehydrated alcohol is the fed stock coming from the storage tanks, which is preheated as hereinabove described.

10) Remaining vapors and liquid are condensed and cooled by cooling water in S&T or P&F heat exchangers.

STORAGE AND HANDLING

Storage tanks are made of almost any structural material steel and reinforced concrete are most widely used., resistance to corrosion, light weight and Iow cost are taken into consideration while selecting the storage materials, plastic and glass coating are also applied to steel plants. Aluminum and other non ferrous material are used. Neopress tanks are best suited for ethanol storage. Since these chemicals are flammable and leakage may cause 'nothing but death'The distance between two tanks should be at least be 7-8 meters away from each other because of which storage is more secure.

Ethanol is volatile liquid. These liquids are stored in specially designed tanks which are capable of conserving the contents if these are stored in normal fixed bed volume tanks a loss takes place due to the following causes.

Breathing losses

A space above the liquid level is filled with air and vapour mixture. Vaporization increases with rise in temperature during the day. Increase in temperature will there fore result in expansion of mixture and a loss of certain volume through the vent. The temperature drops during the night and some condensation takes place, the air-vapour mixture contracts and fresh air is sucked into the tank.

Filling losses

When liquid is discharged from fixed volume tank the tank will be filled with air vapor mixture, if the tank is then filled gain with the fresh batch of liquid certain volume of air vapour will be vented and loss. This loss can be subtenant if such filling takes place very frequently.

Waste Treatments

Molasses based distilleries produce large amount of wastewater variously called spent wash, vinasse, stillage or distillery slops. Depending upon the processes used in fermentation and distillation, it's volume varies from. 6 to 15 liters per liter of Alcohol. The characteristics of the wastewater like COD BOD and dissolved solids also vary accordingly. Wastewater treatment system for the distilleries needs to be decided based on the various factors such as

Quality of sorghum stem and properties of the wastewater Climatic conditions and location of the distillery Availability of raw materials. Availability of land. Cost of fuel and electricity. Market for bi-products Pollution control norms

Any one of the above factors can have deciding effect on selection of the wastewater treatment system. It is therefore essential to select the wastewater treatment method depending upon above and choose the suitable fermentation and distillation process accordingly.

In other words cane molasses based distillery and its wastewater treatment system should be made for each other. With one or more options from the basket of technologies available, a system can be conceptualized and designed for requirement of distillery complex OR with resources available at distillery site/location for disposal of final treated effluent

Wastewater treatment solutions for Breweries

Brewery requires treatment before it can be used as water for irrigation. The treatment method comprises of Bio-methanation followed by aeration or a two-stage aeration system. The former method has advantage of less power consumption and less sludge generation while the latter has advantage of easy start up and operation. While Industries like PRAJ can provide both types of system, considering the overall benefits bio-methanation followed by aeration system is recommended.

Bio-methanation & Aeration

Brewery wastewater though very weak in nature poses typical problem of fluctuating loads and characteristics due to various cycles of operations. The treatment method needs to be designed to cater to such fluctuations without affecting the output parameters of the wastewater treatment system.

Anaerobic bio-methanation system uses a special reactor, called Bio-digester, to convert organic matter into useful energy in the form of Biogas. The biological process of conversion takes place at Mesophilic temperature in a controlled atmosphere ensuring maximum conversion efficiency & production of biogas.

The bio-methanated wastewater from the bio-methanation plant mixed along with other wastewater streams from brewery such as condensate water and floor washings is treated in the Secondary Aeration System. This system comprise two stages namely, Conventional Activated Sludge System followed by Extended Aeration System. The wastewater can be discharged to common wastewater treatment plants or can be further treated before recycling by employing activated charcoal and chlorination techniques. Alternatively reverse osmosis membranes can be employed for water recovery and recycle. Sludge drying beds need to be provided for drying of sludge.

CHAPTER 8

THERMODYNAMIC FEASIBILITY

The enthalpy and Gibbs free energy data of the compounds are given below:

Reactions involved in the manufacture of ethanol are as follows: -

1) C12H22O11+H2O 2 C6H12O6

2) C6H1206 2 C2H5OH + 2CO2

FOR REACTION 1)

C12H22O11+H2O 2 C6H12O6

∆H°R = ∆ H° PRODUCTS - ∆ H° REACTANTS

= (2 X (-1274.45))-((-2222.12)+(-285.84))

= -40.94 KJ/GMOLE

SINCE THE ENTHALPY OF REACTION IS NEGATIVE,THE REACTION IS EXOTHERMIC.

NOW,

∆Go R= ∆ G° PRODUCT - ∆ G° REACTANTS

SR.NO COMPOUNDS H (KJ/Gmole) G (KJ/Gmole)

1 C6H12O6 -1274.45 -910.522 C2H5OH -276.98 -174.1383 CO2 -393.51 -394.384 C12H22O11 -2222.12 -1544.655 H2O -285.840 -228.61

= (2 X (-910.52))-((-1544.65)+(-228.61))

= -47.78 K J/MOLE.

SINCE THE FREE ENERGY IS NEGATIVE, THE REACTION IS FEASIBLE

FOR SECOND REACTION 2

C6H1206 2 C2H5OH + 2CO2

∆H°R=∆H° PRODUCT - ∆ H° REACTANTS

= (2 X (-276.98) + 2X(-393.51))-(-1274.45))

= -66.53 KJ/GMOLE.

SINCE THE ENTHALPY OF REACTION IS NEGATIVE, THE REACTION IS EXOTHERMIC.

NOW,

∆G°R = ∆G° PRODUCT - ∆ G°REACTANTS

= (2 X (-174.38)+2X(-394.38)) - (-910.52)

= -226.576 KJ/GMOLE

∆S° = (∆G298+∆H298)/298

FOR Reaction 1

∆S° = ((+47.78-40.94)X103 )/298

∆S° = 22.953 J/GMOLE K.

FOR Reaction 2

∆S° = ((226.576 -66.53)X103)/298

∆S° = 537.067 J/GMOLE K.

∆S° for both reaction >>0

This implies reaction is feasible.

CHAPTER 9

MATERIAL BALANCE

BASIS – 1100 Kg SWEET SORGHUM JUICE (1000 Lit)

(YEAST) (NUTRIENTS & H2SO4) CO2

(WATER)

SWEET SORGHUM

JUICE (ETHANOL 100% PURE)

WASTES

SWEET SORGHUM JUICE COMPOSITION

CONTENTS WT %SUCROSE (C12H22O11) 11.4GLUCOSE (C6H12O6) 2.85WATER (H2O) 83.79OTHER 1.96

OVERALL PLANT

Our basic aim can be divided into two parts

1) To produce ethanol. ( hydrous containing approximately 95% pure Ethanol)2)To obtain 100% pure anhydrous ethanol

To produce ethanol. ( hydrous containing approximately 95% pure Ethanol)

CO2

FEED WATER

SORGHUM STEM

ALDEHYDE

YEAST

SORGHUM JUICE H2SO4 ETHANOL

NUTRIENTS

BOTTEMS

Feed is 1100 kg of sweet sorghum stem. A composition of which is given in the range of percentage in table. For calculation purpose, it is assume fix value as shown in below table.

CONTENTS WT %SUCROSE (C12H22O11) 11.4GLUCOSE (C6H12O6) 2.85WATER (H2O) 83.79OTHER 1.96

SCRU

BBER

3 DI

STIL

LATI

ON

CO

LUM

N

FERMENTATION TANK

MIXER

CRUSHER

1.SUCROSE in feed = 1100 x 0.114 = 125.4kg. = 125.4 / 342 = 0.3667 kmol.

2.GLUCOSE in feed = 1100 x 0.0285 = 31.35 kg.

= 31.35 / 180 = 0.174 kmol.

3.WATER in feed = 1100 x 0.8379 = 921

= 921.69/18 =51.205kmol

4. Waste in feed = 1100 x 0.0196 =21.56 kg

So therefore, we can say total moles of feed on Mole percent calculation (waste free basis): -

Total moles= 51.7457 kmol

Mole present calculation (waste free basis):-

Sucrose =0.3677 x100/51.7457=0.7%

Glucose = 0.174 x 100 / 51.7457 = 0.336%

Water = 51.205 x 100 / 51.7457 = 98.955%

BALANCE ON MIXER

NUTRIENTS+H2SO4

FEED, M Hm

REACTION

C12H22O11+H2O 2 C6H12O6

Hm=M =1100 Kg =51.7457 kmole

(Nutrients & H2SO4 are in very small quantities )

From reaction

1 mole of sucrose produced 2 mole of glucose

0.3667 kmole sucrose produce 0.7334 kmole of glucose

1 mole of sucrose react with 1 mole of water

0.3667 kmole react with 0.3667 kmole of water

Water remaining =51.205-0.3667=50.8382 kmole

= 915.09 Kg

Glucose in Hm=0.7334+0.174=0.9074 kmole

= 163.332 Kg

Total moles in Hm=50.8383+0.9074

MIXER

=51.7454 kmole

Mole % of Hm (waste free basis)

Glucose=0.9074x100/51.7454=1.753%

Water=50.8383x100/51.7454=98.247%

Weight % of Hm

Glucose=163.332x100/1100=14.84%

Water=915.09x100/1100=83.19%

Waste=21.56x100/1100=1.96%

BALANCE ON FERMENTOR

It is two days fermentation in fermentor

(CO2+ETHANOL TRACES)

Hm Fm

Reaction

C6H12O6 + YEAST 2C2H5OH +2CO2

1 Mole of glucose = 2 mole of ethanol

0.9074 kmole of glucose produce 1.8148 kmole of ethanol

1 mole of glucose= 2mole of CO2

0.9074 kmole of glucose produce 1.8148 kmole of CO2

FERMENTOR

Ethanol produce= 0.95x1.8148=1.7240 kmole

Considering 95% of efficiency of fermentor including traces of ethanol losses

CO2 removed =0.95x1.8148x44=75.875 Kg

Ethanol in Fm=1.7240x46=79.3067 Kg

Water in Fm=50.8383x18=915.089 Kg

Waste in Fm=21.56 Kg

Total moles in Fm=1.7240+50.8383=52.562 kmole

Total weight in Fm=79.306+915.089+21.56=1015.953 Kg

Mole % (Waste free basis)

Ethanol=1.7240x100/52.562=3.279%

Water=52.562x100/52.562=96.72%

Weight %

Ethanol=79.306x100/1015.953=7.805%

Water=915.089x100/1015.953=90.07%

Waste=21.56x100/1015.953=2.122%

DISTILLATION COLUMN

D2 D3

L1

Fm D1 S1 S2

95% ETHANOL

W1 W2 W3

Let,

W1constitute 0.2% alcohol and rest water and wastes

D1constitute 10% of alcohol and rest water

Considering presence of waste 21.56 Kg

Let Xf= 0.03279

Overall Balance

Fm=D1+W1

52.562=D1+W1 ……… (1)

Component Balance

FxXf=D1xXd1+W1xXw1

52.562x0.03279=D1x0.1+W1x0.002 …….. (2)

Solving eqn 1 & 2 we get

D1=16.5141 kmole

W1=36.0478 kmole

Water in Bottoms=36.0478x0.998=35.975 kmole

=647.562 Kg

Waste in Bottom=21.56 Kg

Composition of D1

Ethanol in D1=0.1x16.5141=1.6514 kmole

= 75.964 Kg

Water in D1=16.5141x0.9=14.8626 kmole

= 267.52 Kg

Now in the aldehyde column, undesirable volatiles such as aldehydes are taken off and azeotropic alcohol-water mixer are obtained from the rectification column where 95% pure ethanol is taken off as a side stream, condensed and run to storage.

Aldehyde Column

Assuming

Xd2=0.9

Xs1=0.4

Xw2=0.01

Recovery of alcohol in side stream be 75%

Alcohol in side stream=0.75x1.65214=1.2385 kmole

Side stream removed=S1=1.2385/0.4=3.0963 kmole

Overall Balance

D1=D2+W2+S1

16.5141=D2+W2+3.0963

D2+W2=13.4178 ……..(3)

Component Balance

D1xXd1=D2xXd2+W2xXw2+S1xXs1

16.5141x0.1=D2x0.9+W2x0.01+3.0963x0.4

D2x0.9+W2x0.01=0.41289 …….(4)

Solving eqn 3 & 4 we get

D2=0.3131 kmole

W2=13.1046 kmole

S1=3.0963 kmole

Ethanol in side stream S1=3.0963x0.4=1.2385kmole

= 56.971 Kg

Ethanol in D2=0.3131x0.9=0.28179

=12.96 Kg

Water in D2=0.3131x0.1=0.03131 kmole

= 0.56 Kg

Rectification Column

Assuming

Xd3=0.97

Xs2= 0.95

Xw3=0.01

Recovery of alcohol in side stream be 96%

Alcohol in side stream =0.96x1.2385=1.188 kmole

Side stream removed = S2=1.188/0.95=1.2515 kmole

Overall Balance

S1=D3+W3+S2

3.0963=D3+W3+1.2515

D3+W3=1.8449 kmole ….(5)

Component Balance

S1xXs1=D3xXd3+W3xXw3+S2xXs2

3.0963x0.4=D3x0.97+W3x0.01+1.2515x0.95

D3x0.97+W3x0.01=0.04959 …..(6)

Solving eqn 5 & 6 we get

D3=0.0324 kmole

W3=1.8124 kmole

S2=1.2512 kmole

Alcohol in side stream=1.2515x0.95=1.188 kmole

=54.64 Kg

Water in side stream= 1.2515x0.05=0.0625 kmole

=1.125 Kg

At D3

Ethanol in D3=0.0324x0.97=0.3142 kmole

=1.445 Kg

Water in D3=0.0324x0.03=9.72x10-4 kmole

=0.0174 Kg

To Obtained 100% pure anhydrous ethanol

D

F

WATER

S

W ETHANOL 100%

FUSEL OIL

STILLAGE

F=1.2515 kmole

Ethanol in F=1.188 kmole=54.64 Kg

Assuming

Water in F=0.0625 kmole=1.125 Kg

Xf = 0.95

Xd=0.98

PREH

ATER

MOLECULAR SIEVE

BEDS

Xs=0.5

Xw=0.001

Recovery of alcohol in side stream be 1%

Alcohol in side stream=0.01x1.188=0.01188 kmole

Side stream remove=S=0.01188 /0.5=0.02376 kmole

Overall material Balance for Preheater

F=D+W+S

1.2515=D+W+0.02376 kmole …..(7)

Component Balance

FxXf=DxXd+WxXw+SxXs

1.2515x0.95=Dx0.98+Wx0.001+0.02376x0.5

Dx0.98+Wx0.001=1.177 kmole ……(8)

Solving eqn 7&8 we get

D=1.2 kmole

W=0.0267 kmole

S=0.02376 kmole

Ethanol in D=1.2x0.98=1.176 kmole

=54.096 Kg

Water in D=1.2x0.02=0.025 kmole

=0.432 Kg

Assuming Separation unit (Molecular sieve Bed) gives 100% separation

So,

Ethanol obtained=1.176 kmole=54.096 Kg

=67.62 Lit.

OVERALL MATERIAL BALANCE

B C D

E

A F

G

H

J I

INPUT= 1100KG

A= SWEET ORGHUM JUICE = 1100 KG

B=YEAST + NUTRIENTS

OUTPUT = 1100KG

C=CO2 REMOVED=79.85 KG

D=ETHANOL WITH CO2=4.17 KG

E=ETHANOL 100% PURE =54.906 KG

F=STILLAGE AND FUSEL OIL=1.359 KG

G=WATER IN MOLECULAR SIEVE BED=1.125 KG

H=ETHANOL IN WASTE =23.7 KG

I=WATER IN WASTE=913.33 KG

J=WASTE=21.56 KG

OVERALL PLANT

CHAPTER 10

ENERGY BALANCE

Energy balance for fermentor.

In Fermentor the following reaction takes place.

C6H12O6 + Yeast 2C2H5OH + 2CO2

CONTENT OF FEED

WATER = 50.8383 KMOL = 915.09 kg.

GLUCOSE = 0.9074 KMOL = 163.332 kgh

TOTAL CONTENT OF GLUCOSE & WATER = 1078.422 kg

WASTES PRESENT = 21.56 kg

FEED TO FERMENTOR = 1.1 tons per batch

TEMP RANGES FROM 30-250C

T = 303 0 K, T0 = 298 0 K

∆ Hf (FEED) = m Cp ∆T = m Cp (T-T0)

= 1100 x 0.936 x (303-298)

= 5148 kcal / batch

∆ Hp (product) = ∆ Hethanol + ∆ H water + ∆Hco2

= 83.48 x 0.58 + 915.09 x 1 + 79.85 x 0.21

= 980.277 kcal / hr

∆Hr (reaction) = product formed x ∆H

=83.48 x 15600 / 46

= 28649.739 kcal / hr

∆H removed = ∆ Hr – (∆Hp - ∆Hf)

=28649.739 - (980.277 - 5148)

= 32817.462 kcal / hr

Therefore cooling water required = ∆H removed /Cp ∆ T

= 32817.462 / 1 x 2 = 16408.73 cal / hr

Avg Cp = 0.936

Ethanol out of Fermentor = 79.3067 kg

= 1.7240 kmol

Now heat exchange between ethanol and slops

M1Cp1∆T1 (ethanol) = M2 Cp2∆ T2 (slops)

79.3067 x 0.58 x 10 = M2 x 0.7 x 20

M2 = 32.85 kg

Ethanol preheated before beer still

79.3067 x 0.58 x 10 = 0.58 x 15

M2 = 52.87 kg

BEER STILL ALDEHYDE COLUMN

RECTIFICATION COLUMN

De (kmole)

1.6514 0.28179 0.031429

Dw (kmole)

14.8626 0.03131 9.72 x 10-3

D (kmole)

16.5144 0.3131 0.0324

V (kmole)

28.83 3.276 0.181

Qc (Kcal/hr)

9625.41 9263.28 11842.64

Qr (Kcal/hr)

280227.6 31842.72 1759.32

De=D x Xd

Dw=D x (1-Xd)

Qc = Deλe + Dw x λw/D

λe=9218.21 kcal/kmole

λw=9668 kcal/kmole

λv=9720 kcal/kmole

λs=506.22 kcal/Kg

Qr=V x λv

Q1+Q2 +Q3 = TOTAL Qr

Qr (Total) = 313829.64 kcal/hr

Ws1=Qr (total)/λs

Ws1 =313829.64/506.22 = 619.94 kg/hr

Total steam requirement = 619.94kg/hr

Now,

Total Qc=(Qc1+Qc2 + Qc3)

Total Qc = 30631.33 kcal/hr

WCl = 30631/20 = 1531.56 kg/hr

Total cooling water requirement = 1531.56 kg/hr

Now for molecular sieve technology

We will start directly from molecular sieve bed for better understanding of energy balance.

Ethanol out from molecular sieve bed = 54.096 Kg

Water out from molecular sieve bed = 0.432 Kg

1) The water will recycled before that it cooled in a H.E.

Therefore the water contain = Q= 0.423 x 1 x 15 = 6.48 Kcal

Therefore water required to cool it

6.48 = m x 1 x 10

m = 0.648 Kg

2)Heat exchange between water out and ethanol out

Therefore Q contains of water out = 6.48 Kcal

And heat contain of ethanol out = 470.63 Kcal

3)Heat exchange takes place with incoming ethanol

Now the outgoing ethanol is again cooled

Q= 54.096 x 0.58 x 15 = 470.63 Kcal

470.63 = M x Cp x ∆T

M= 81.143 Kg of ethanol is heated

4)Now product ethanol is again cooled in a heat exchanger preferably in a condenser

Total Q of ethanol = 54.096 x 0.58 x 10 = 313 Kcal

Therefore amount of water required is

m x 1 x 15 = 313

m = 20.86 Kg of water required to cool

5) In the final heat exchanger the heat content of ethanol (product) is same

Therefore the amount of water required to cool ethanol finally is

M x 5 x 1 = 313

M = 62.6 Kg of water

6)Now moving to the preheater section, we have obtained fusel oil + stillage = 1.24 Kg

Now we have to calculate the steam reqired for preheating

Therefore,

feed M= 0.432 Kg of water out + 54.64 Kg of ethanol

= 55.072 Kg

Q= 55.072 x 80 = 4405.072 Kcal

λs = 506.22 Kcal/Kg

Ws= 4405.76/506.22 = 8.70 kg/hr

7)The feed is preheated sent to the molecular sieve bed the preheated feed again superheated By steam, now calculating steam reqired for that

Q= M x ∆T = 55.072 x 50 = 2753.6 Kcal

Therefore steam reqired is Ws = 2753.6/506.22 = 5.439 Kg/hr

CHAPTER

DESIGN

Design for fermentation tank

Capacity of 1000 lit

Shell Design

Internal Design=1000 mm

M.O.C.=S.S.

Wt Pressure=1.013 bar=1.013 Kg/cm2

Design Pressure=1.013 x 1.1= 0.0111 Kg/mm2

Permissible stress=0.49823 Kg/mm2

Thickness of Shell

t=PDI/2fj-p

=0.0111 x 1000/2 x 0.85 x 0.4982-0.0111

=13.28=15 mm.

Shell Volume= (π/4) x Di3L

= (π/4) x (1000)2 x 1500

=1178.09 lit.

Volume of head=0.085 x Di3

= 0.085 x (1000)3

=85 lit.

Volume of two head= 2 x 85=170 lit.

Total Volume=Shell volume + two head volume

= 1178.09+170

=1348.09 lit.

Considering the effect of combine loading stress in circumferential direction due to internal.

Ft = P(Di+t)/2t

=0.0111(1000+15)/2 x 15

=0.187 Kg/mm2

Stress due to longitudinal direction or axial.

Due to internal pressure

F1= PDi/4t

= 0.0111 x 1000/4 x 15

= 0.185 Kg/mm2

Due to weight of vessel

F2= w/t (Di + t)

Volume of total material= volume of total material shell + volume of material for 2 head

Volume of material for shell

= (π/4) x (Do2-DI2) x L

= (π/4) x (10302-10002) x 1500

=71.74 x 106 mm3

=0.0713 m3

Volume of material for head

=0.085 (10303-10003)

= 7.88 x 106 mm3

= 7.88 x 10-3 m3

Total volume of material = 0.0717 + 7.88 x 10-3 + 7.88 x 10-3

Weight of vessel = volume x density

Density of S.S. weight = 8000 Kg/m3

Weight of vessel = 0.0874 x 8000

= 699.68 Kg

Weight of vessel = 699.68 + 1100

= 1799.68 Kg

Weight of accessories =0.20 x 1799.68

= 359.93 Kg

Total weight of vessel = 1799.68 + 359.93

= 2159.616 Kg

Total weight including jacket= 1.5 times of fermentar weight

= 1.5 x 2159.616

= 3239.42 Kg

F2 = w/t (Di + t)

=2159.616/15 x (1000 + 15)

=0.14184 Kg/mm2

Fn =F1 + F2

= 0.185 + 0.14184

= 0.326 Kg/mm2

Stress due to wind is negligible = 0

Fs = 0

Combining above stress on the basis of shear strain energy theory

FR = (Ft2-Ft Fn + Fn

2 + 3 Fs2) (1/2)

= (0.1872-0.187 x 0.326 + 0.3262 + 3 x 0) (1/2)

= 0.2833 Kg/mm2

FR < Permissible stress design is satisfactory.

Head Design

Torrispherical head

Diameter = 1000 mm

M.O.C.=S.S.

Th = PRcW/2Fj

P=design pressure

Rc = crown radius

W= stress intrerification factor

Rk= knucle radius

= 6% of crown radius

Rk= 0.06 x 1000

= 60 mm

Rc = 1000 mm

W= (1/4) x 3 + (Rc/Rk) (1/2)

= (1/4) x 3 + (1000/60) (1/2)

= 4.83

Th= 0.011 x 1000 x 4.83/2 x 0.49823 x 0.85

= 62.72 mm = 63 mm

Nozzles

Internal diameter = 1000 mm

M.O.C. =S.S.

J = 0.85

Th = PDin/2fj – P

= 0.011 x 1000/2 x 0.49823 x 0.85 – 0.011

= 13.15 mm = 15 mm

Take thickness of vessel 15 mm

A= (DIN + 2C) Tr

Tr = PDI / 2 FJ + P

= 0.0111 x 1000 /2 x 0.49823 x 0.85 + 0.0111

= 12.93 = 15 mm

A = (1500 + 2 x 15) x 15 = 22.95 x 103 mm2

Design of Distillation Column

Molecular weight of feed Mf = ∑Mi.Xi

= 0.4 x 46 +0.6 x 18

=29.2

Molecular weight of distillate = ∑Mi.Xi

= 0.98 x 46 + 0.02 x 18

= 45.44

Molecular weight of residue = ∑Mi.Xi

= 0.02 x 46 +0.98 x 18

= 18.56

Specific heat of ethanol CPE = 3.03 KJ/Kg.K

Specific heat of Water CPW = 4.18 KJ/Kg.K

Average specific heat of liquid CPL =3.03 + 4.18 /2

= 3.605 KJ/Kg.K

Latent heat of ethanol λe = 842 KJ/Kg.K

Latent heat of water = 2257 KJ/Kg.K

Enthalpy of liquid HL = CPL x MF x (TL-TF)

= 3.605 x 29.2 x (351-301)

=5052.76 KJ/Kg.K

Calculate X and Y values using following formula

Y = αX /1 + (α-1) X

For values X= 0.1

Take α = 2.5

Y = 2.5 x 0.1/ 1+ (2.5-1) x 0.1

= 0.217

X 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0Y 0 0.217 0.385 0.517 0.625 0.714 0.789 0.854 0.91 0.957 1.0

No of theoretical plates including reboiler n = 14

No of theoretical plates required = 13

No of theoretical plates in rectification section = 6

No of theoretical plates in stripping section = 8

Feed is sub cooled.

From equilibrium curve we have XD = 0.98

Intercept of q line = XD / R + 1

= 0.98 /2.5 +1 = 0.28

Calculation of flow stream

L = R x D

= 2.5 x 58.32

=145.8 Kg

Material Balance on enriching section

G = vapour flow rate

G = L + B

= 145.8 + 58.32

= 204.12 Kg/h

q=1

L1 – L /F =q

L1 = q x F +L

= 1 x 90.41 + 145.8

= 236.21 Kg/kmole

G1 –G/F= q – 1

G1 = (q – 1) x F +G

= (1-1) x 90.41 + 204.12

= 294.53 Kg/kmole

Plate diameter is calculated as follows

Molecular weight of feed MF = ∑Mi.Xi

= 0.4 x 46 +0.6 x 18

=29.2

Gas Density = P x MF/RT

= 101.325 x 29.2 /8.314 x 303

= 1.174 Kg/m3

Liquid Density = ethanol density x mole % of ethanol in feed + water density x mole % of water

= 800 x 0.4 + 955 x 0.6

= 893 Kg /m3

Liquid and Gas contact in column

L/G x (ρL/ρG) 0.5 =145.8/204.12 x (893/1.174) 0.5

= 19.69 Kg mole/h

= 5.47 x 10-3 Kg mole/sec.

Unf = vapour velocity through net area at flood

Csbf = capacity parameter = 0.28 = constant

Surface tension σ = 37.3 dyne/cm

= 0.037 N/m

Unf = Csbf (σ/20)0.2 (ρL – ρG / ρG) 0.5

= 0.28(0.037/20) 0.2(893-1.174/1.174) 0.5

= 0.865 m/s

We can take 80% of Unf= 0.6924 m/s

Net area for vapour flow An

An = Ac – Ad

Where,

Ac = the column area

Ad = the down comer area = 12 % of column area

Net area for vapour flow An

An = volumetric flow rate of vapour / vapour velocity through net area at flood

= 0.04846 /0.6924

= 0.0699 m2

Ac = An /(1-8% of down comer area)

= 0.0699/ (1-0.088)

= 0.07664 m2

Therefore,

Ac = (π/4) x D2

0.07664= (π/4) x D2

D = 0.312 m

D = 312 mm= 320 mm

D = 32 cm

Aa = active area

Aa = Ac - 2Ad

= 0.07664 – 2 x (0.12 x 0.07664)

= 0.0582 m2

Weir length (Lw) = 0.75 x 0.32

= 0.24 m

Weir height (Hw) = 0.80 x 0.32

= 0.256 m

Area of coming zone (Acz) = 2 x (Lw + Hw)

= 2 x( 0.24 + 0.256)

= 0.122 m2

Area of periphery waste (Awz) = 2 x (π/4 x Dc2 x α/360) – (π/4 x (Dc2 – 0.12)) x α/360

Θ = 2 sin-1(Lw/Dc)

= 2 sin-1 (0.24/0.32) = 97.180o

A = 180 - 97.180

= 82.81o

Awz = 2 x[(π/4 x 0.322 x 82.81/360) - (π/4 (0.322 -0.12) x 82.81/360)]

= 3.61 x 10-3 m2

Perforated area Ap

Ap = Ac – 2Ad – Acz – Awz

= (0.07664 – 2 x (0.123 x 0.7664) – 0.122 – 3.61 x 10-3 )

= 0.067 m2

Ah = hole area

Ap = perforated area

Ah/Ap = 0.1

Ah = 0.1 x Ap

= 0.1 x 0.0673 = 6.73 x 10-3

Check for weeping

Head loss across the hole (dry hole)

hd = k1 + k2 (ρg - ρL) (Uh) 2

k1 = 0 ……. (for sieve plate tower)

k2 = 90.113

Uh2 = 1/6.73 x 10-3 m/s

hd = [0 + 90.113(1.174/893) 148.582]

=533 = 535 mm liquid.

Liquid creast over the weir (how)

how = 44300 (q/Lw) 0.704

q = 1455.8 / 893 x 3600

= 4.535 x 10-5 m3/s

how = 44300 x (4.535 x 10-5/0.24) 0.704

= 105.91 mm

hd and how is higher so no weepning will occour

Calculation for height of distillation Column for enriching

H1 = No of plate enriching section x plate spacing

= 6 x 100 = 600 mm

Height Distillation Column for stripping section

H2 = No of plate x plate spacing

= 8 x 100 = 800 mm

Total height of column = 600 + 800

= 1400 mm

Mechanical design for distillation column

Material of construction = stainless steel (304 L)

Inner diameter of column (Di) =320 mm

Operating pressure distillation column = 1 atm = 101.3 KN / m2

Design pressure (Pi) = 10% more than operating pressure

= 1.1 x 101.3

= 0.113 N /mm2

Design temperature = 100 0C

Weld joint efficiency (j) = 0.85

Corrosion allowance (C) = 2 mm

Stress analysis of vessel

Material of construction = stainless steel (304 L)

Design stress = 150 N /mm2

Density of stainless steel = 7800 Kg / m3

Design pressure = 0.113 N /mm2

Corrosion allowance (C) = 2 mm

Inner diameter of column (Di) =320 mm

Weld joint efficiency (j) = 0.85

No of trays including reboiler = 15

Tray spacing = 100 mm

Seismic force = negligible

Calculation for minimum thickness of shell

Thickness of shell (ts) =PiDi/2fj -2xPi+C

= 0.113 x 320/2 x 0.85 x 150-0.2 x 0.113 + 2

= 2.1418

But minimum thickness required for construction is 6 mm. so the minimum required thickness of the cover is taken as 6 mm.

For stability of shell the column is divided into five parts and thickness is increased from top to bottom of shell as 6,8,10,12,14 mm. for all other calculation thickness is used the average thickness is 10 mm.

Axial stress due to pressure

fap = PiDi/4(ts - C)

= 0.113 x 320/4 x (10-2)

= 1.13 N/mm2

Stress due to dead weight of vessel (fdw)

Wt = Total weight of shell

Total weight of the column between tangent line

= 1600 mm

Mechanical design for distillation column

Material of construction = stainless steel (304 L)

Inner diameter of column (Di) =320 mm

Operating pressure distillation column = 1 atm = 101.3 KN / m2

Design pressure (Pi) = 10% more than operating pressure

= 1.1 x 101.3

= 0.113 N /mm2

Design temperature = 100 0C

Weld joint efficiency (j) = 0.85

Corrosion allowance (C) = 2 mm

Stress analysis of vessel

Material of construction = stainless steel (304 L)

Design stress = 150 N /mm2

Density of stainless steel = 7800 Kg / m3

Design pressure = 0.113 N /mm2

Corrosion allowance (C) = 2 mm

Inner diameter of column (Di) =320 mm

Weld joint efficiency (j) = 0.85

No of trays including reboiler = 15

Tray spacing = 100 mm

Seismic force = negligible

Calculation for minimum thickness of shell

Thickness of shell (ts) =PiDi/2fj -2xPi+C

= 0.113 x 320/2 x 0.85 x 150-0.2 x 0.113 + 2

= 2.1418

But minimum thickness required for construction is 6 mm. so the minimum required thickness of the cover is taken as 6 mm.

For stability of shell the column is divided into five parts and thickness is increased from top to bottom of shell as 6,8,10,12,14 mm. for all other calculation thickness is used the average thickness is 10 mm.

Axial stress due to pressure

fap = PiDi/4(ts - C)

= 0.113 x 320/4 x (10-2)

= 1.13 N/mm2

Stress due to dead weight of vessel (fdw)

Wt = Total weight of shell

Total weight of the column between tangent line

= 1600 mm

Cv = a factor account for nozzle, man ways, internal, support etc.

= 1.15 for distillation column

Dm =mean diameter of column

Mean diameter of column (Dm) = (Di+ts)

= (320+10)

= 330 mm = 1.33m

Total weight of shell (Wt) = 240 x Cv x Dm x (Hv +0.8 x Dm)

= 240 x 1.15 x 0.33 x (1.6 + 0.8 x 0.33 )

= 169.77 N = 17.30 Kg

Stress due to weight of plate

Ap = plate area

= (π/4) x Di2

= (π/4) x 0.322

= 0.0804 m2

Weight of plate = ρm x t x Ap

= 7800 x 6 x 10-3 x0.0804

= 3.762 kg

Total weight of no of plate = no. of plate x weight of one plate

= 14 x 3.762

= 52.67 Kg

Stress due to weight of plate (fp) = (weight of plate)/plate thickness x (Di + ts)

= (3.762 x 9.81)/ 3 x(320 + 6)

= 0.0377 N/mm2

Total weight of the vessel = Wt + Wp + extra fitting (20% of plate weight)

= 17.03 + 52.67 + 10.534

= 80.504 Kg

Stress due to total dead weight of vessel (fdw) = (Wt)/ts x (Di + ts)

= 80.504 / 10 x (320+10)

= 0.293 N/mm2

Longitudinal and circumferential stress due to pressure

σL = Longitudinal stress

σh = circumferential stress

use maximum thickness for bottom of vessel

σL = Pi Di / 4 t

= 0.133 x 320 / 4 x 12

= 0.7533 N/mm2

σh = Pi Di / 2 t

= 0.133 x 320 / 2 x 12

= 1.506 N/mm2

Outer diameter of column D0

D0 = Di + 2 x t

= 320 + 2 x 12

= 344 mm = 0.344 m

Design for support

A skirt support consists of a cylindrical or conical shell welded to the base of the vessel.

A flange at the bottom of the skirt transmits the load to the foundation. Skirt support is

Recommended for vertical vessel, as they do not impose concentrated loads on the shell;

They are particularly suitable for use tall columns subjected to wind loading. The skirt

Thickness must be sufficient to withstand the dead-weight loads and bending moments

Imposed on it by the vessel; it will not be under the vessel pressure. The maximum weight

will occur when the vessel is full with feed.

Total weight = load x distance at load applied

= 790.62 + 4.33 x 9.81

= 833.128 N

Load per plate = total weight / no. of plate including reboiler

= 833.128 / 14

= 59.509 N

Bending moment = load x distance at load applied

= 59.509 x 0.8

= 47.6 N-m

σbs = stress due to bending moment

σws = stress due total weight

ds = internal diameter of skirt

σbs = 4 x M / π (ds +t) x t x ds

= 4 x 47.6 / π x (50+12) x 12 x 50

= 1.69 x10-3 N/mm2

σws = total weight (w)/ π (ds +t) x t

= 833.128 / π x (50 + 12) x 12

= 0.356 N/mm2

CHAPTER

LICENSES & PERMISSIONS REQUIRED

1.MPCB - WATER/AIR Consent to Establish 2. EIA3. PIL4. Consent to oprate

2.Central Excise Registration

3.Factory Inspector's Certificate

4.Plantation Certificate from Forest Office for plantation carried out

5.NOC From Grampanchayat / Village

6.MSEB Power Sanction

7.BCC Certificate from MIDC or concern authority

8.State Excise permission for storage of SDS / Alcohol

9.State excise permission for manufacture of alcohol / SDS From sorghum

10.IEM - Registration certificate from Ministry of Industry / Letter of Intent

11.Labour office / Commissioner permission for employing contracted persons/ agencies

12. Boiler certificate from boiler inspector

13. Site layout plans approved from State excise / central excise / MIDC if existing

14.Explosive license for storage of explosive chemicals

15.DG Set approval from MSEB for stand-by power generation

16.MSEB Approval for co-generation of power

17.Weigh-bridge stamping from weights & measured

18.Storage tank calibrate from state excise authorities / its measurement

19.MPCB Permission for solid waste disposal in a scientific matter

CHAPTER

VARIOUS INDUSTRIES PRODUCING FUEL ETHANOL

All large sized plants to produce ethanol commissioned in Colombia. All plants are on stream for commercial production.

Few Fuel ethanol plants overseas

1. Incauca S.A.

Turnkey design and supply of 300,O00-1itres/day fuel ethanol plant using cane molasses B, juice and syrup.

2. Ingenio Providencia S.A.

Turnkey design and supply of 250,000-1itres/day fuel ethanol plant using cane molasses B+, juice and syrup.

3. Jilin Tianhe Ethanol Distillery China

It has an initial capacity of 600,000 tones a year or 2.5 rain liters per day. Potential final capacity can be raised to 800,000 tones per year. Ground breaking took place in September 2001 and by late 2003 the first trials had started.

4. Tianguan Ethanol Chemical Group Co., Ltd. (TICG)

In November 2002 construction on a plant designed to produce 300,000 tones of fuel ethanol annually started in Nanyang, Henan province. The project is expected to cost $155 mln and take two years to complete. Combined with the company's existing facility, TICG's total fuel ethanol capacity would reach 500,000 tonnes a year.

Few Fuel ethanol plants in India

1. Praj Industries Limited, Pune Manufacturer / Supplier / Exporter of: Water Treatment Plant, Waste Water Treatment Plant, Water Purification Plant, Alcohol Plant, Fuel Ethanol Plant, Beer Plant, Wastewater Plant Location: Praj House, Bavdhan, Pune, Maharashtra, India, 411 021

2. Metro Ethanol & Allied Products Private Limited, Aurangabad Manufacturer / Supplier / Exporter of: Ethanol-bio fuel Location: Bajajnager, M. I. D. C., Waluj, P-41, Aurangabad, Maharashtra, India, 431 !36

3. 0aisis Alcohol India Private Limited, Satara Manufacturer / Supplier / Exporter of: absolute alcohol, rectified spirit, specially denatured spirit, extra neutral alcohol, ordinary denatured spirit Location: S/6, Siddhi Complex, Krishna Nagar, Near Natraj Temple, Satara, Maharashtra, India, 415 004

4. Regency Cycles Private Limited, New Delhi Importers of newsprint paper, carbon black, Ethanol, pp powder chemical assorted etc. Location: S-102, Greater Kailash-II, New Delhi, Delhi, India, 110 048

5. Saj Globex, Mumbai Exporters of tomato paste, dairy products and also fuel grade Ethanol. Location: 6, Rajgir Court, Kohinoor Road Dadar East, Mumbai, Maharashtra, India, 400 014

6. Arss Biofuel Private Limited, Nasik Manufacturer / Supplier / Exporter of: denatured ethyl alcohol, anhydrous Ethanol Location: Gate No.196, Darna Road, Wadivarhe, Nasik, Maharashtra, India, 422 101

7. Xl Telecom Limited, Mumbai Manufacturers of anhydrous Ethanol. Location: 105, Centre Point, Andheri Kurla Road, Mumbai, Maharashtra, India, 400 059

NOTE: - Apart from these industries there are other industries in India, which produces ethanol, but they are hydrous one so they are not mentioned

CHAPTER 9.

FAQ's-FUEL Ethanol

Fuel ethanol or anhydrous alcohol is produced by dehydration of spirit or extra neutral alcohol. Ethanol used as part of the fuel, by with petrol, for a motor vehicle is called fuel-ethanol. Rectified blending with petrol, for motor vehicle is fuel ethanol.

What are the functions of fuel ethanol?

Fuel ethanol has following functions:

Octane enhancement / anti-knocking agent Oxygenating agent Fuel extender/fuel replacement.

What is an oxygenate?

Oxygenates are hydrocarbons that contain one or more oxygen atoms. The primary oxygenates are alcohols and ethers, including: fuel ethanol, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), and tertiary amyl methyl ether (TAME). Oxygenates are added to motor vehicle fuels to make them burn more cleanly, thereby reducing toxic tailpipe pollution, particularly carbon monoxide. Oxygenates are favoured not only for their vehicle emission benefits but also their blending properties in motor gasoline (e.g., octane).

How does it help in reducing pollution?

Use of ethanol in place of tetraethyl lead or MTBE, which acts as anti-knocking agents, will prevent dangerous and poisonous emissions containing lead or MTBE from petrol.

Will I have to change the engine of my Car?

Many states in the US have been using 10% ethanol blend in gasoline (petrol) for use in their cars. Brazil has been using up to 24 % ethanol in petrol. Engines of cars do not need any change to use petrol with up to 24 % ethanol in it.

Will the engine of my vehicle get damaged?

Ethanol has, apart from carbon and hydrogen, oxygen in it. This oxygen acts as oxygenating agent during combustion in the IC engine of petrol cars, two-

wheelers and three wheelers thus preventing formation of carbon monoxide. Gasoline with ethanol as anti-knocking agent will not cause any damage to the engine.

Can it be used in Two-wheelers/Three-wheelers without any change in vehicles?

Yes! Of course we can use gasoline in Two-Wheelers/Three-Wheelers as a normal fuel without changing the engine or any other things.

Can it be added in Diesel?

Ethanol is also added to diesel. Usually, 3% by volume is added. Tests have been conducted satisfactorily with up to 10% by volume addition.

Which are the other countries, which have promoted fuel ethanol?

Many states in the US have been using 10% ethanol blend in gasoline (petrol) for use in their cars. Brazil has been using up to 24 % ethanol in petrol. Engines of cars do not need any change to use petrol with up to 24 % ethanol in it. Fuel ethanol programs have now been initiated in countries like Australia, Nepal, Columbia, Poland, and Sweden etc.

What is the experience of countries that have promoted fuel ethanol?

Reduced oil imports, improved trade balance, reduced reliance on imported oil, increased ethanol production, more cane price to farmers, direct and indirect job opportunities, saving fossil fuels are some of the experiences.

CHAPTER

Success factors

Fuel ethanol production and use is expected to rise strongly and it will go along with an ever wider geographical spread. Ten years ago, there were only a handful of countries producing ethanol. The largest was Brazil, where ethanol is produced from molasses and sugar cane juice. The US produces mostly corn alcohol and in France, sugar beets are being used. In some African countries, sugar cane was processed into fuel alcohol.

In 2003, we there were some 13 countries spread over all five continents that actually use ethyl alcohol as a fuel component. Looking into the future, the world fuel ethanol map may look like this in ten years time: the Americas are likely to be almost completely covered by fuel ethanol programs. Moreover, the green fuel will likely be established in the European Union as well as in India, Thailand, China, Australia and possibly Japan to name the largest nations.

Reasons for the overwhelming success of fuel ethanol: -

As fuel ethanol is competing with gasoline, a direct comparison between the two products is possible. Because ethanol is invariably more expensive to produce than gasoline, if actual market prices are taken account of, political objectives come into play.

Ethanol has been promoted because it has a positive net energy balance, which means that the energy contained in a tonne of ethanol is greater than the energy required to produce this tonne. Moreover, it has been demonstrated that it has a less severe impact on the environment than conventional gasoline or other petroleum derived additives. As such it is also less dangerous to health.

From a macro-economic point of view, it is thought to be good for the development of disadvantaged rural areas by promoting an industry that creates jobs. Furthermore it can help to reduce the dependence on oil imports and, finally, it may be regarded as a means to promote advances in biotechnology, particularly if one thinks of all the research that is going on in the biomass-to-ethanol sector.

CHAPTER

PLANT LOCATION AND LAYOUT

PLANT LOCATION

The location of plant can have further expansion a crucial effect on the profitability of a product and the scope for further expansion. Many factors must be considered selection a suitable site.

Location with respect to the marketing area Raw material supply Transport facilities Availability of labor Available of utilities water fuel power Availability of suitable land Environmental impact and effluent disposal Local community consideration Climate Political and strategic consideration

Marketing area

From material that are produced in bulk quantities where a cost of product is relatively low and cost of transport is significant fraction the sale price the plant should be located nearer to primarily market. This consideration will be less important for low value production high price product.

Raw materials

Plant producing bulk chemicals is best located close to the source of major raw materials.

Transport

A site selection should be closet to at least two major forms of transport. Road transport is suitable for local distribution from a center where house Rail transport will be cheaper for the long distance transport of bulk chemical Air

transport is convenient and efficient and efficient for the movement of personal and essential equipment and suppliers.

Availability labor

Skilled construction worker will usually be brought in from outside area. Skilled trade man will be needed for plant maintained Unskilled labor must be available locally.

Utilities

Plant must be located near a source of suitable quality. Process water may be drawn from river, from wells or purchased from a local authority. General cooling tower is used for process water cooling electrical power will be needed at all site and can be taken fr.om electricity board For steam and power generation a competitive price fuel must be available.

PLANT LAYOUT

A preliminary site layout has been sketched. The layout of the plant is decided keeping the following factors in mind:

The Process units and ancillary buildings should be laid to give the most economical flow of materials and personnel around the site. Hazardous processes must be located at a safe distance from the buildings. Consideration must also be given to future expansion of plant. The ancillary buildings and services required are storage, maintenance, workshops, stores for maintenance, laboratories for quality control, fire station, utilities, offices for general administration, canteens and car parks.

When roughing the preliminary site layout the process units will normally be cited first and arranged to give a smooth flow of materials through the various processing steps from raw materials to final product. Storage process units are normally placed at least 30m apart.

The cost of construction can be minimized by adopting a layout that gives the shortest run of connecting pipe between equipment, and the least amount of structural work.

Considerations In Layout:

1. Operation:

Equipments that need to have frequent operator attention should be near to the control room The main plant also has access to road on three sides for safety reasons.

2. Plant expansion:

Equipment should be located so that they can be conventionally tied up with any future expansion of the process.

3. Administrative Office:

It is located close to the main entrance so as to facilitate movement of personnel working there. This also prevents visitors from directly coming into the vicinity of main plant. Canteen is located close to security offices, administration office.

4. Tank& Storage Buildings:

They are close to the roads connecting main roads.Weigh bridge is located on the road connecting the storage buildings.

5. Fire Station and Medical Facility:

They are located in the vicinity of the main plant so that they can be easily accessed when required.

6. Effluent Treatment Plant:

It is located on that side of the plant such that effluent water can be directly discharged into the drain.

7. Wash and Changing Room:

It is located on the way of workers to the main plant.

PLANT LAYOUT :

CHAPTER

ENVIRONMENTAL EFFECT

Environmental Benefits of Ethanol as Fuel.

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 by l% in the soil organic matter means atmospheric reduction of over 40 tones of CO2 per hectare of farmland.

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 more complete. The result is a substantial reduction carbon monoxide emission. Research shows that reduction range up to 30%, depending on type and age of automobile, the automobile emission system used, and the atmospheric conditions in which the automobile Operates. Because of health concerns over carbon monoxide, the 1990 amendments to the U.S. clean air act mandate the use of oxygenated gasoline’s in many major urban centers during the winter (when atmospheric carbon monoxide levels are highest) to reduce this pollution

Nitrous Oxide (N20)

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

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 in Canadian gasoline.

Ozone

Because of its effect in reducing hydrocarbons and carbon monoxide to exhaust (that causes respiratory problems) adding ethanol to gasoline results in an overall reduction m exhaust ozone-forming potential. Adding ethanol to gasoline can potentially increase the volatility of gasoline. This potential is controlled if all ethanol-blended gasoline sold in Canada meets the volatility standards required for other types of gasoline. In contrast, the U.S. Clean Air Act allows gasohol (gasoline plus 10% ethanol) to have a higher volatility than that of gasoline. This results in greater “volatile organic compounds" emissions therefore, the Canadian ethanol blend has less potential to form ozone than the American counterpart. 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 to the exhaust systems of all recent-model cars. The Royal Society of Canada termed the possibility of negative health effects caused by aldehydes emissions with the use of ethanol-blended gasoline as being "remote."

The alcohol has its origins in the Middle East. The Arabs said to have made cosmetic. Paints by heating and vaporizing a mixture of compounds .The residue was tested to paints eyelids and 'KOHL'. When they later heated wines, they gave the same name as the cosmetic "KOHL" or "ALCOHOL" It was the genius of Louis Pasteur, who showed the world, the scientific understanding of fermentation, the action of all microorganism and hence the, economic control. He showed that life process of minute organism and hence their economic control. He showed that life processes of minute organism directly cause fermentation.

Environmental impacts

In this study, a wide range of environmental impacts has been analyzed quantitatively and qualitatively. The quantitative evaluation covers categories "resource depletion" (depletable primary energy carriers, i.e. mineral oil, natural gas, different types of coal as well as uranium ore) and "greenhouse effect". In the discussion of the results, a simpler, informal formulation is given priority over a scientific correct formulation .Results are named as fossil energy savings, whereas in the case of greenhouse gases results are called greenhouse gas savings.

The qualitative evaluation covers acidification, Eutrophication, photo smog, ozone depletion, soil erosion compaction, water consumption, soil organic matter and agro biodiversity. The different environmental impact categories are described.

Quantitative evaluation

1. Resource depletion (energy) - consumption of non-renewable primary energy carriers, i.e. fossil fuels such as; mineral oil, natural gas and different types of' coal as well as uranium ore.

2.Greenhouse effect- Anthropogenic greenhouse gas emissions are considered tocontribute to global warming and climate change. Besides carbon dioxide (CO2),a number of' other trace gases among them methane (CH4) and nitrous oxide (N2O)- are included .The latter are converted into carbon dioxide equivalents (CO2 equiv.) by a weighing of 23 for CH4 and 296 for N2O and are discounted over a period of 100 years.

3. Acidification – shift of the acid/base equilibrium in solids and water bodies by acids forming gases.

4. Eutrophication- diffuses aerial input of nutrients into soils and water bodies caused by Eutrophication substances such as nitrous oxide or ammonia.

5. Photo smog- formation of specific reactive substances, e.g. ozone, in presence of solar radiation in lower atmosphere.

6. Ozone depletion- Loss of the protective ozone layer in the stratosphere through certain gases such as chlorofluorocarbons (CFCs) or nitrous oxide.

7. Soil erosion / soil compaction- Soil erosion describes the soil transport caused by water, wind and temperature influence and causes the reduction of soil fertility. Soil compaction increases erosion and is caused by the use of heavy agricultural machinery. It further more leads to a decline of soil microorganisms and oxygen content and eventually decreasing bodies by the

input of nutrients and pesticides.

8. Impact on soil organic mailer- A positive soil organic matter balance is crucial for the long-term preservation of soil fertility.

9. Resource depletion (water)-The total water consumption of a crop during its cultivation influences above and below ground water reserves, which is important in arid areas and areas with water shortages.

10. Impact on ground and surface water- pollution of ground and surface water.

11. Agro biodiversity-describes the above and belowground biodiversity in agricultural systems. It depends on various physical and biological Factors as well as different production methods and cropping cycles, on crop diversity, crop varieties, and soil and pest management. Diversity in agricultural system is crucial for the stability of the system and for the resilience of the system to pests, diseases.

CHAPTER

APPENDIX

1.Packaging and transportation:

(a) Road transportation:

1)Hazard warning sign: 1170 (flammable liquid)

2)Hazchem code: 2 SE

(b) Sea transportation:

1) IMDG code: 30

2)Lable: flammable liquid

3)Class: 3.2

4)Packaging group:II/III

(c) Air transportation:

1) ICAO/IATA code: 1170

2)Class: 3

3) Packaging group:II/III

4)Packaging instructions:

- Cargo: 307- Passenger: 305- Cargo(max. capacity): 60

- Passenger(max. capacity): 5 L

2.Chemical hazards:

Ethanol is a flammable liquid and whose vapors can form ignitable and explosive mixtures with air at room temperature. Thus an aqueous mixture containing 30% ethanol can produce a flammable mixture of vapors and air at 29°C and even one containing 5% alcohol can produce a flammable mixture at 62 °C. Ethanol reacts vigorously with wide range of oxidizing materials and other chemicals.

3.Biological hazards:

Ethanol is rapidly oxidized in the body to acetaldehyde ,then to acetate and rapidly to CO2 & H20.Unoxidised alcohol is excreted in the urine and expired in the air. ia) Vapour inhalation:

The effects of inhalation are not likely to be serious under reasonable laboratory or industrial use. There is no evidence that repeated exposure to ethanol vapors results in cirrhosis of the liver. Prolonged inhalation of high concentration over 5000ppm,besides irritation of eyes and upper respiratory tract, may produce headache, drowsiness, tremors and ether narcotic effects.

(b) Eye contact:

Very high concentrations can cause irritation (5000-10000ppm)

(c) Skin contact:

The liquid can affect the skin producing a dermatitis characterized by drying and fissuring.

(d) Swallowing:

Large doses lead to alcoholism. Alcohol abuse and dependence can have profound effect on workplace performance and tendency to accidents at work. The presence of denaturants in industrial alcohol greatly increases the toxicity ingestion.

4.Carcinogenicity:

There is no evidence of carcinogenetic due to ethanol itself, although some studies have shown an excess incidence of laryngeal cancer over the expected from exposure from synthetic alcohol, with diethyl sulphate probably being the causative agent.

5.Mutagenicity:

Ethanol has been found to be non-mutagenic in the "salmonella" micro some test, but some transient mutagenic changes have been observed in male, but not female mice treated with rather large doses.

6.Reproductive hazards:

Some evidence of foe toxicity and teratogenity has been observed in experimental animals treated with high doses of ethanol during gestation. Alcohol may induce spontaneous abortions.

7.First aid:

(a) Eyes:

Flush immediately with water or neutral saline solution for at least 10 mins. Seak medical attention.

(b) Lungs:

Remove the victim to fresh air. If breathing is weak, irregular or has stopped, apply artificial respiration. Oxygen may be beneficial.

(c) Mouth:

Do not induce vomiting. Avoid alcoholic drinks, as this will enhance toxic effects. Seek immediate attention.

(d) Skin:

Remove contaminated clothing, rinse contaminated area with soap and water. If skin irritatation persists, seek medical attention.

8.Handling and storage:

Large quantities should be stored in flammable liquid store in metal tanks or drums away from sources of ignition and oxidants. Small quantities can be kept in glass containers in laboratories. Good ventilation should prevent the formation of harmful concentrations of alcohol vapour. Hand protection should be used where there is possibility of prolonged skin contact.

9.Disposal

Shut off all sources of ignition and wear protective clothing. Absorb small spills onto paper and remove to safe area for burning or burying. Flush the contaminated area with plenty of water. For large spills, absorb with water and vermiculate and remove to a safe place for burning or burying. Incineration is the recommended method of disposal

INDIAN STAANDARD 321 OF 1964REQUIRMENTS FOR ABSOLUTE (ANHYDROUS) ALCOHOL

*For test methods, reference should be made to the appendix of the Indian standard323 of 1959 for rectified spirit, (with the expansion of item marked ***as noted below ). ** Test method c should be used, with the modification of Indian standard 323 of 1959.*** Reference should be made to test method A of this standard.

Please note: The figures in parentheses for parts per million (ppm) do not appear in the original standard, but have been added here to facilitate comparison with standards of countries.

CHAPTER

COMPARISON

Sugarcane Sugar beet Sweet sorghum

Crop duration

About 7 month About 5-6 month About 4 month

Growing season

Only one season Only one season Only season in temperature and two or three season in tropical area

Soil requirement

Grow well in drain soil

Grow well in sandy loam also tolerate alkalinity

All type of drain soil

Water management

36000 m3/h 18000 m3/h 12000 m3/h

Crop management

Requires good management

Greater fertilizer requirement ; require moderate management

Little fertilizer required less pest and diseas complex management

Yield per hector

70-80 tons 30-40 tons 54-69 tons

Sugar content on weight basis

10-12 % 15-18 % 7-12 %

Sugar yield 7-8 tons/ ha 5-6 tons/ha 6-8 tons/haEthanol productivity directly from juice

3000-5000 l/ha 5000-6000 l/ha 3000 l/ha

Table: Comparison of sugarcane, sugar beet and sweet sorghum .

For the production of ethanol sweet sorghum is comparatively better than sugar cane and sugar beet i.e. 30001/hector in less expenditure and area as sweet sorghum an grow 3 times in whole year in any session and all types of drain soil. it required very little fertilizer and pesticide as compared to sugar cane and sugar beet. Water for irrigation is less than half required for sugar cane and sugar beet.

Yield of sweet sorghum per hectare is good than both i.e. 54-69 tons per ha. And the sugar content is 7-12 % wt basis.

So we used sweet sorghum juice as raw material for production of ethanol and our production cost of ethanol is comparatively less than others i.e. only 25 Rs/lit and calculated market cost of ethanol is 17 Rs less other general market cost of ethanol.

CHAPTER

CONCLUSION

Ethanol was initially used for potable purpose and as solvent in chemical industries.After few, decades ethanol is started to use as fuel to fulfill the increasing demand of fuel. The crude oil resources are not renewable and will exhaust within next few decades, so ethanol can be used as renewable energy resource due to its nonpolluting properties obtained from biomass. The ethanol in tile end is blended with gasoline to improve vehicle performance and reduce air pollution. As India has to face the significant problem of oil lacking Ethanol should be an alternative fuel or additive.

Indian government has started 5% blending of ethanol with petrol Presently in India ethanol is Manufactured by petroleum and molasses route. But demand of power ethanol is so high that existing supply cannot meet this demand It is very necessary to shift For another Renewable raw material resource.

Ethanol is best produced from lower value grains such as barley, corn and feed wheat from this we conclude that there are number of method of production of ethanol of which fermentation is the best one. As the biomass as raw material of method of production is available in abundant quantity, locally which is cheaper and renewable also. Production cost is low and cost of ethanol in market is 17 Rs

also less than general ethanol cost of market. Between calculated market cost of Ethanol is nearly 25 Rs. This ethanol can be used various purposes as solvent intermediate of other chemicals or fuel.

So our method of production can be taken as alternative source of ethanol.

As a fuel

Fuel ethanol will not go away in the foreseeable future. On the contrary, world production is set to continue to grow vigorously. There are various fuel ethanol projects in the pipelines around the world and, even though their implementation may be delayed, there is enough momentum in the political arena to push them through. Political support is there and in many instances the industry and the authorities are very close to reaching an agreement over a viable framework of support for fuel ethanol. World trade is likely to grow as well but the rate of growth will depend on several factors. First of all, the sugar and alcohol economics as has been illustrated in the case of Brazil. Unless the strong link between sugar and alcohol production can be severed an additional element of volatility will be in the equation.

The same applies to the corn and corn products market in the United States, even though this relationship is not very obvious at present because of the depressed state of the corn sweeteners market. Of course, such a strong increase in import requirements would have to be preceded by an increase in output. Indeed there are several projects under way which could facilitate such a development. From above Chart it may be gleaned that most of the growth will happen in the United States under the renewable fuels standard. Growth would also be strong in Brazil, mostly because of the promises in the export market

The EU will be the third largest producer of fuel ethanol by 2005 and the rates of growth would be considerably above those seen in Brazil and the United States. India on other hand is developing on this field to great height.

Before significant increases in ethanol exports can be expected, new investments in the origins will have to be made. It cannot be expected that the sugar and alcohol industries in the origins will be able to make these investments all by themselves. Instead, a new partnership between the producers and the importers will have to be created in order to provide the significant funds, which are required to facilitate this growth. Moreover, a viable trading system would have to be established. Finally, the problem of subsidized production and exports would have to be resolved. Without an effective system of international exchange, fuel ethanol

supplies are bound to be volatile resulting in fluctuating prices and consumer uncertainty.

Farmers are part of the ethanol gold rush. But now, the field is dominatedby heavyweights, including agribusiness giants such as ADM and Cargill and hungry corporate upstarts such as Vera Sun and US Bio Energy. Even ethanol novices are getting in, from billionaire Bill Gates to hot-money Wall Street investors.

All this has made the outlook for fuel ethanol bright, and strong rates of growth in both production and trade can be expected for the next several years.