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DEPARTMENT OF CHEMICAL ENGINEERING JAYPEE UNIVERSITYOF ENGINEERING & TECHNOLOGY, A-B ROAD, RAGHOGARH, DIST. GUNA-473226, M.P, INDIA
Contents
Chapter 1: Historical profile 1.1 Introduction 1.2 Manufacturers 1.3 Feedstocks 1.4 Advantages 1.5 Disadvantages Chapter 2: Application 2.1 Current Applications of Bioethanol Chapter 3: Economic Scenario 3.1 Worlds Scenario for ethanol 3.2 Indias Scenario for ethanol Chapter 4: Properties 4.1 Properties Chapter 5: Manufacturing Processes 5.1 Manufacturing Process 5.2 Bioethanol production from Molasses 5.3 Bioethanol production from cereals 5.4 Bioethanol production from lignocellulosic materials 5.5 comparisons of different processes for production of Bioethanol Chapter 6: Selected Process 6.1 Process Flow chart 6.2 Process Description 6.3 Plant Capacity
Chapter -1
HISTORICAL PROFILE
1.1INTRODUCTION 1.1.1 WHAT IS BIOETHANOL
The principle fuel used as a petrol substitute for road transport vehicles is Bioethanol. Bioethanol fuel is mainly produced by the sugar fermentation process, although it can also be manufactured by the chemical process of reacting ethylene with steam. The main sources of sugar required to produce ethanol come from fuel or energy crops. These crops are grown specifically for energy use and include corn, maize and wheat crops, waste straw, willow and popular trees, sawdust, reed canary grass, cord grasses, jerusalem artichoke, myscanthus and sorghum plants. There is also ongoing research and development into the use of municipal solid wastes to produce ethanol fuel. [1] Ethanol or ethyl alcohol (C2H5OH) is a clear colourless liquid; it is biodegradable, low in toxicity and causes little environmental pollution if spilt. Ethanol burns to produce carbon dioxide and water. Ethanol is a high octane fuel and has replaced lead as an octane enhancer in petrol. By blending ethanol with gasoline we can also oxygenate the fuel mixture so it burns more completely and reduces polluting emissions. Ethanol fuel blends are widely sold in the United States. The most common blend is 10% ethanol and 90% petrol (E10). Vehicle engines require no modifications to run on E10 and vehicle warranties are unaffected also. Only flexible fuel vehicles can run on up to 85% ethanol and 15% petrol blends (E85). [2]
1.1.3 HISTORY
It was one of the first fuels used in an automobile engine It was used extensively in Germany during World War II and also in Brazil, the Philippines and the United States. During the postwar period, as petroleum supplies became cheap and abundant, gasoline largely replaced Bioethanol as an automotive fuel In 1970s, when the supply of oil was restricted, Bioethanol re-emerge as an alternative to or extender for petroleum-based liquid fuels (ethanol as an extender is added to these fuels to increase their volume). Around 12 countries produce and use a significant amount of Bioethanol. In Brazil, for example, one third of that countrys automobiles use pure Bioeth anol as fuel; the remaining two-thirds use mixtures of gasoline and ethanol. France, the United States, Indonesia, the Philippines, Guatemala, Costa Rica, Argentina, The Republic of South Africa, Kenya, Thailand and Sudan are other countries with government or private ethanol fuel programs. [4]
1.2 MANUFACTURERS
The currently operating biorefineries in the world are: Endreas + Hauser
Green Plains Renewable Energy - Headquartered in Omaha, Neb., Green Plains produces 740 million gal./yr. at different production plants. ADM - This Decatur, Ill.-based grain and oilseed processor produces 1.75 billion gal. /yr. It operates seven ethanol production plants. Poet - Headquartered in Sioux Falls, S.D., Poet produces 1.6 billion gal./yr. at 27 production plants. Valero Energy Corporation - This company produces 1.2 billion gal./yr. at 10 production plants. It is headquartered in San Antonio, Texas. [5]
1.3FEEDSTOCKS
A variety of feedstocks are potentially suitable for Bioethanol production, including: Alfalfa Bagasse (sugar production by-product) Barley Corn (Stover & cobs)
Cotton Fruit (e.g. orange or apple pulp waste) Grass clippings Jerusalem artichoke Hemp Leaves Molasses Paper Potatoes Skimmed milk Sorghum Spent hops Straw Sugar beet Sugar cane Sunflower Sweet potatoes Wheat Whey Wood (e.g. process waste or willow) This list is far from exhaustive, and the output in terms of usable alcohol varies considerably (dependant largely on starch content and how accessible the starch is for fermentation). There has even been some research in the USA on using municipal solid waste (household waste and paper products) as a feedstock (US Department of Energy). Much of the current commercial production of Bioethanol is from sugarcane, maize and sugar beet, as these all represent fairly high yield, readily accessible sugar sources. The technology to produce ethanol from lignocellulosic feedstock is still struggling to become economically competitive. Lignocellulosic biomass is a readily available and often waste material, particularly from the food processing and forest products industries. This makes it an ideal candidate for those seeking locally-sourced, low cost feedstocks.
1.4 ADVANTAGES
Bioethanol has a number of advantages over conventional fuels. It comes from a renewable resource i.e. crops and not from a finite resource and the crops it derives from can grow well in the UK (like cereals, sugar beet and maize). Another benefit over fossil fuels is the greenhouse gas emissions. The road transport network accounts for 22% of all greenhouse gas emissions and through the use of Bioethanol, some of these emissions will be reduced as the fuel crops absorb the CO2 they emit through growing. Also, blending Bioethanol with petrol will help extend the life of the UKs diminishing oil supplies and ensure greater fuel security, avoiding heavy reliance on oil producing nations. By encouraging bioethanols use, the rural economy would also receive a boost from growing the necessary crops. Bioethanol is also biodegradable and far less toxic that fossil fuels.
In addition, by using Bioethanol in older engines can help reduce the amount of carbon monoxide produced by the vehicle thus improving air quality. Another advantage of Bioethanol is the ease with which it can be easily integrated into the existing road transport fuel system in quantities up to 5%, Bioethanol can be blended with conventional fuel without the need of engine modifications. Bioethanol is produced using familiar methods, such as fermentation, and it can be distributed using the same petrol forecourts and transportation systems as before.[6]
1.5 DISADVANTAGES
Biodiversity A large amount of arable land is required to grow crops. This could see some natural habitats destroyed including rainforests. The food V fuel debate There is concern that due to the lucrative prices of Bioethanol some farmers may sacrifice food crops for biofuel production which will increase food prices around the world. Carbon emissions There is debate over the neutrality of Bioethanol when all elements are taken into consideration including the cost of changing the land use of an area, transportation and the burning of the crop. During the production process of Bioethanol a huge amount of carbon dioxide is released which makes its ecological effectiveness close to zero. The production of ethanol fills the air with greenhouse gases (GHG) in the amounts comparable to the emissions of internal-combustion engines The energy content of the petrol is much higher than the one of Bioethanol. Burning 1 liter of ethanol gives 34% less energy than burning the same amount of petrol. There are also concerns over the fuel systems used. Too many older cars are currently unequipped to handle even 10% ethanol while there is concern that using 100% ethanol decreases fuel economy by around 15-30% compared with 100% petroleum. The octane number of Bioethanol is at around 105. It means that this substance can be burned in the engines with much higher compression ratio. The engines made for working on the new energy cannot be used for their petrol or diesel variants. It can negatively affect electric fuel pumps by increasing internal wear and undesirable spark generation. [7] It is not compatible with capacitance fuel level gauging indicators and may result in erroneous fuel quantity indications in vehicles that employ that system. Phosphorous and nitrogen used in the production have negative effect on the environment Transportation ethanol is hygroscopic, it means that it absorbs water from the air and thus has high corrosion aggressiveness. Thats why it is transported only by auto transport or railroad. Pure ethanol is also difficult to vaporize which can make starting a car in cold weather difficult and that is why most fuels retain at least a small amount of petrol such as E85 cars with 85% ethanol and 15% petrol
Chapter-2
APPLICATIONS
2.1 CURRENT APPLICATIONS OF THE PRODUCTS:
Bioethanol - mobility with a future The future of Bioethanol is proverbially on the road. Bioethanol is already available as a fuel in several different forms today. Renewable and climate-friendly, it is helping to ensure that mobility has a future. Over eighty percent of the worlds ethanol production is used in the fuel sector. Bioethanol as a fuel for all internal combustion engines Most of the petrol fuels in Europe, contain Bioethanol or ingredients manufactured from it. Standards determine what chemical properties the various grades of petrol may have, and what ingredients they may contain. It also permits the addition of Bioethanol in various ways: as additive E10 With the amendment of the European Fuel Quality Directive of April 2009 the European Union established the technical parameters for the introduction of E10 fuel, i.e. the blending of 10 vol.-% of Bioethanol in petrol, throughout Europe. France was the first EU member state to start introducing E10 fuel nationwide in April 2009. E10 was introduced at German petrol stations in early 2011. as additive E5 E5 may contain a maximum of 5 vol.-% Bioethanol. It is currently the standard petrol in Europe. At fuel pumps, however, this fuel is not labeled E5, but rather super, premium or similar. The quality parameters for E5 are defined in Norm EN228. Before the European fuel quality directive was adapted, all petrol fuels in Europe had to meet this standard. as a high-performance fuel component The production of the octane booster ETBE (ethyl tertiary butyl ether) has for a long time been the main application of Bioethanol in the European fuel sector. The increasing direct blending of Bioethanol to petrol has led to ETBE becoming less important. ETBE is composed of around 47% ethanol and 53% isobutylene and is used as a petrol additive to enhance its anti-knock properties. Bioethanol in E85 E85 fuel blends - such as the CropPower85 produced by Crop Energies - have a Bioethanol content of up to 86% and can be used on vehicles that have been specially designed or converted to run on it, so-called "Flexible Fuel Vehicles" (FFVs). A technically relatively simple modification enables FFVs to run both on conventional petrol and on Bioethanol-petrol blends with a Bioethanol content of up to 86%. For the motorist, this means a unique flexibility as it is possible to choose between two types of fuel according to availability and price. As it is also possible to use ordinary
petrol Mobility is assured also during the transition phase while a nationwide network of filling stations selling E85 is being built up in Germany. A number of car manufacturers are already selling models with flexible fuel technology in Germany, and others are due to follow. For technical reasons, it is not advisable to use 100% Bioethanol as fuel in our temperate climatic regions. That is why E85 is used in Europe. The addition of petrol improves cold-starting characteristics in the winter. Owing to its high Bioethanol content the use of E85 on a nationwide basis offers the greatest potential for reducing the dependence on fossil fuels. [8]
Chapter-3
ECONOMIC SCENARIO
3.1 INDIAN ECONOMIC SCENARIO (ETHANOL) 3.1.1 Current and projected demand and supply:
The fourth-largest consumer of energy after US, China, and Russia, accounting for 3.8% of global consumption Demand for petroleum fuel constitutes 40 percent of total energy requirement in India, and is projected to be the third largest net importer of oil in the world .There is an increasing gap in production and consumption of crude oil in India. With limited domestic energy resources most energy requirements are met through imports, estimated to be 76 percent of it's demand. Liquid biofuels, namely bioethanol, is used to substitute petroleum-derived transportation fuels. Indias biofuel strategy is focused on using non-food sources for the production of bioethanol such as sugar molasses as second generation biofuels in the near future. In the year 2003, the Report of the Committee on Development of Biofuels was published by the Planning Commission of India. It gave projections of demand and supply of ethanol for India for the end of each five-year plan. This report shows the break-up of production and consumption of ethanol in terms of molasses and cane. Data from different sources shows that as of 2010, the actual production of ethanol in India has not kept pace with the demand.
Worldwide ECONOMIC Scenario (Bioethanol) Current and projected demand & supply:
On the basis of data projected on demand and supply of ethanol in 2015 and 2020 it can be clearly seen that from 2015 to 2020 in just a time period of 5 years, a gap between demand and supply increases from about 10000 million litres in 2015 to 20000 million litres in 2020 which is a sign of danger for the world community. Its a global matter of concern as gap between demand and supply is continuously increasing. Demand is going high and high and our production rate is going down. As petroleum and crude are depleting at a faster rate there is a need to produce Bioethanol from biomass to fill the gap between demand and supply.
Fig 3.1 Current and projected demand and supply of Bioethanol worldwide
Chapter 4
PROPERTIES
4.1.1Physical Properties:
It is a volatile, colorless liquid that has a slight odour. It burns with a smokeless blue flame that is not always visible in normal light. Due to the presence of its hydroxyl group and the shortness of its carbon chain, it is able to participate in hydrogen bonding, rendering it more viscous and less volatile than less polar organic compounds of similar molecular weight, such as propane. Ethanol is slightly more refractive than water, having a refractive index of 1.36242 (at =589.3 nm and 18.35 C). The triple point for ethanol is 150 K at a pressure of 4.3 * 10-4 Pa. Ethanol has higher values than diesel for fuel density and surface tension. [10] Ethanol has about 30% lower energy content than gasoline on a per unit volume basis. It has a resistance to self-ignition because of its higher octane number. The value of octane number is high in ethanol because of the high heat of vaporization
C2H5OH
H2SO 4
C2H4 + H2O
5.1MANUFACTURING PROCESS
In our sugarcane based bio refinery we are producing following products: 1) Raw Sugar 2) First generation Bioethanol from blackstrap molasses obtained as the by-product of the sugar manufacturing process 3) Second generation Bioethanol from the sugarcane bagasse (lignocellulosic biomass) obtained as the by-product of the sugar manufacturing process 4) Biofertilizers like vinasse 5) Energy obtained by treating bagasse as a fuel, generation of electricity etc
Addition nitrogen in the form of di-ammonium phosphate is added. The more the sucrose from sugarcane starch that is removed for crystalline sugarproduction, the poorer the quality of molasses. For Bioethanol production, molasses is diluted by 25% total sugar (measured in brix) treated with dilute sulphuric acid and heated to 90 C for impurity removal prior to cooling, centrifugation, PH adjustment and addition of yeast. Sugar cane juice can either be directly fermented, clarified following heat (105C) treatment, or mixed with molasses in different proportions. Constituents in molasses that are important for Bioethanol production include: sugar content: sugar % (w/w) and degrees Brix, colour, total solids, specific gravity, crude protein, free amino nitrogen, total fat, fibre, minerals, vitamins and substances toxic to yeast. The yeast S. cerevisiae is the predominant microorganism employed in industrial molasses fermentations, but yeast, Kluyveromyces marxianus and a bacterium, Zymomonas mobilis, have potential in this regard. [11]
Fig 5.1 Dry and wet milling corn processes for Bioethanol
The principal stages in dry mill Bioethanol processes encompass: Milling (maize kernels ground to a fine powder or meal) Liquefaction (water is added to the maize meal and temperature increased in the mash to solubilize starch). Saccharification (enzymatic hydrolysis of starch liberates simple sugars, mainly glucose). Fermentation (starch hydrolysate is fermented by yeast to ethanol, CO2 and secondary metabolites). Distillation (the fermented wash, or beer, at around 10%v/v ethanol is distilled to ~96% v/v ethanol with the solid residues processed into animal feed). Dehydration (water remaining in the ethanolic distillate is removed by molecular sieves to produce anhydrous ethanol).
Wheat-to-ethanol processes share similarities with the maize processes described above and Fig 5.4 summarizes main stages taking place in a major wheat biorefinery.
Fig 5. 4 Basic features of lignocellulose pre-treatments The following criteria are characteristics of an effective pre-treatment method: preservation of pentose sugars from the hemicellulosic fraction, limitation of lignin degradation products, minimization of energy input and employment of low cost materials and methods. Pre-treatments employed can be divided into physical, chemical and biological methods (see Table 5.2), but there is a strong inter-dependence of these processes. There is not a perfect pre-treatment method employed and remaining bottlenecks include generation of inhibitory chemicals (acids, furans, and phenols), high particle load, high energy input and efficient
separation of soluble sugars from solid residues. Specific pre-treatment conditions are required for individual feedstocks and mechanistic models can help in the rational design of such processes. It is especially important to optimize lignocellulose pre-treatment methods because they are one of the most expensive steps in the overall conversion to Bioethanol. Fundamentally, pre-treatment methods should render cellulose more amenable to enzymolysis by disrupting its crystalline structure and in order to do this, the lignin seal
needs to be broken. Table 5.2 Lignocellulose pre-treatment and fractionation technologies By comminuting the material by physical pre-treatment the surface is enlarged proportionately to its volume and makes it more accessible for enzymes or chemicals which hydrolyze the substrate. However, this process is energy-intensive and expensive and may not always be feasible. Pyrolysis involves treating lignocellulosic materials to >300C to produce gaseous product and residual char. Ultrasound (eg. 36 KHz frequency) can be employed to pretreat wastepaper to enhance subsequent cellulolytic ability of enzymes. Steam explosion (or hydro-thermolysis, or auto hydrolysis) is commonly employed and this involves treatment of biomass with high pressure steam (160-260C, 0.69-4.83 MPa pressure) followed by rapid decompression to degrade hemicelluloses and transform lignin, increasing cellulose hydrolysis potential. Liquid hot water (LHW) treatments and wet oxidation (hot water plus oxygen) also involve high temperatures (eg. 200C), but lower energy input technologies such as AFEX (ammonia fibre/freeze explosion involving impregnation with high-pressure ammonia followed by decompression , ARP (ammonia recycling) and ACOS (acid catalyzed organosolv saccharification (cooking in aqueous alcohols, with an acid catalyst) processes are attractive.
Lime pre-treatments using calcium hydroxide with high temperature and pressure selectively reduce lignin contents of biomass without affecting carbohydrate content. Combined physico-chemical approaches include the use of concentrated hydrochloric acid (CHAP) or dilute sulphuric acid at 200C. [14] Ionic liquids (eg. n-butyl-methyl-lilidazolium chloride) which are stable liquid salts up to 300C can solubilise cellulose within a few hours. Other pre-treatment methods include ozonization which has been used effectively to improve enzymolysis of straws (ozone, a powerful oxidant, degrades lignin and slightly solubilises hemicellulose).
Table 5.3 Key parameters for Bioethanol production from starch and sugar
Fig 6.1 process flow diagram for the production of Bioethanol from molasses
WATER: Molasses when introduced into the fermenter is first diluted because molasses is
basically a thick syrup which cannot be fermented easily as choking of materials takes place and this thick liquid may stick to the walls of the reactor and disturbs the entire section. To avoid this molasses is first diluted hence water also takes a part among raw materials.
6.2.2 PROCESS:
The basic Steps involved in the process are: It is a large scale biotechnological process requiring large scale tubular tower fermenters (bio-reactors) and involves the following steps. 1. Preparation of the medium: Water is added to the molasses to bring down the sugar concentration to the desired level (usually 30 to 40 percent). A measured quantity of acid is then added so as to adjust the pH on the acidic side. 2. Addition of yeast: After adjusting the desired temperature, a yeast starter is allowed to be mixed thoroughly with the molasses mash in the fermentation tank. 3. Fermentation: Fermentation by the yeast process starts and soon becomes vigorous. A large quantity of carbon dioxide is evolved during the process. The gas (by-product of the alcohol industry) is collected, purified and used in various other industries. 4. Separation of ethyl alcohol: Alcoholic fermentation is completed in about 48 hours. The fermented medium contains alcohol as well as other volatile constituents and unused constituents of the molasses. Therefore, separation of ethyl alcohol from other impurities is necessary. This is done by distillation. 5. Distillation (Purification): Finally, alcohol is purified with the help of rectifying columns and stored in bonded warehouses.
As it was already mentioned that molasses is the by-product of sugar industry, molasses is first diluted with water. For the sugar content of nearly20-25% (w), 75-80 %( w) is added and will be sent into fermenter and allow them to react or ferment for 1-3days. In the fermenter, the formation of ethyl alcohol takes place. In brewing, alcoholic fermentation is the conversion of sugar into carbon dioxide gas (CO2) and ethyl alcohol. This process is carried out by yeast cells using a range of enzymes. This is in fact a complex series of conversions that brings about the conversion of sugar to CO2 and alcohol. To be specific yeast is a eukaryotic micro-organism. Not all yeasts are suitable for brewing. In brewing we use the sugar fungi form of yeast. These yeast cells gain energy from the conversion of the sugar into carbon dioxide and alcohol. The carbon dioxide by-product bubbles through the liquid and dissipates into the air. In confined spaces the carbon dioxide dissolves in the liquid making it fizzy. The pressure build up can be quite immense. Certainly enough to cause the explosion of a sealed glass bottle. The other by-product alcohol, remains in the liquid which is great for us but not for the yeast, as the yeast dies when the alcohol exceeds its tolerance level. Wine yeast is more tolerant at a range of 10-15%. Especially cultured strains of yeast with the correct environment can withstand alcohol levels up to 21% alcohol. Then the beer stream which consists of alcohol (10-15%) and water mixture and CO2 will be separated into two different streams where CO2 will be sent into the beer column where the CO2 stream will be separated by varying temperature or pressure conditions. In general pressure would be increased to separate the gas stream because if temperature is increased, the quality of alcohol is affected. Much of the CO2 that is generated during the fermentation process can be captured and converted into marketable products, such as dry ice, liquid CO2 for soft drinks, fire-fighting foams, filtration products and various industrial uses. [18] After separating CO2, the ethanol-water mixture will be sent into distillation column and the ethanol will separated and collected at the top and water at the top. In practice, maximum of 95% of ethanol can be recovered. This mixture is often referred to as hydrous sugarcane ethanol because it contains 5% water. Hydrous alcohol is preheated, vaporized and superheated before being admitted to the vessels containing molecular sieve material. In this superheated, excited and vapor phase at controlled temperature and pressure, adsorption of water molecules by sieve is optimized while the alcohol molecules pass through Water accumulated on sieve is removed by means of vacuum applied to column, reducing partial pressure of H2O, making it evaporate again and allowing molecular sieve to be reused in next cycle. It is repeated for continuous operation and referred to as pressure sieving mechanism. By further dehydration, absolute or anhydrous ethanol is obtained with 99.5%.
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