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DESIGN OF INTEGRATED SUGARCANE BASED BIOREFINERY
Priya Garg-091420 Ritu Lavania-091422
MAY 2013
Submitted in partial fulfillment of the Degree of Bachelor of Technology
DEPARTMENT OF CHEMICAL ENGINEERING JAYPEE UNIVERSITYOF ENGINEERING & TECHNOLOGY, A-B ROAD, RAGHOGARH, DIST. GUNA-473226, M.P, INDIA
JAYPEE UNIVERSITY OF ENGINEERING AND TECHNOLOGY

(Establishment under MP Private University Act, 2007) A.B. ROAD, P.B. No.1, RAGHOGARH, DIST. GUNA (M.P) INDIA. Phone: 07544 267051, 267310-14 Fax: 07544 267011 Website: www.juet.ac.in
CERTIFICATE
This is to certify that the work titled DESIGN OF INTEGRATED SUGARCANE BASED BIOREFINERY submitted by PRIYA GARG and RITU LAVANIA in partial fulfillment for the award of degree of B.Tech in Chemical Engineering of Jaypee University of Engineering and Technology, Guna (M.P.) has been carried out under my supervision at JUET campus. This work has not been submitted partially or wholly to any other University or Institute for the award of this or any other degree or diploma.
Signature of Supervisor Name of Supervisor Designation Date
................................................... Dr. Hari Mahalingam Associate Professor & Head of Department (Chem. Engg) ....................................................
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ACKNOWLEDGEMENT
This project report represents the combined efforts of a large number of individuals and we feel pride in acknowledging to all those who rendered help to us either directly or indirectly. First and foremost, we are indebted to our Project Supervisor, Dr. Hari Mahalingam, for his valuable suggestions during the period and for providing all necessary information related to our project. We consider it our good fortune in having worked under his guidance. We express our deep sense of gratitude to Professor K.K. Tiwari owing to his untiring help, ever- encouraging attitude and energizing us to complete this project. We express our deep sense of indebtedness to our Vice-Chancellor Professor N.J. Rao for his encouragement, help and constant support. Our heart feels regards and thanks to all the faculty members of CHE department for inspiring, encouraging and uplifting us by their enlightened and compassionate care during the course of project. It would have been an impossible task for us to complete the project without the support of these above mentioned people.
Signature Name
.............................................. Priya Garg (091420)
............................................... Ritu Lavania (091422)
Date
................................................
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EXECUTIVE SUMMARY
This project report contains the final year project entitled Design of an integrated sugarcane based biorefinery. The concept of biorefinery is analogous to today's petroleum refinery, which produce multiple fuels and products from petroleum. By producing multiple products, a biorefinery takes advantage of the various components in biomass and their intermediates therefore maximizing the value derived from the biomass feedstock. This project gives deep insight into this problem and the need of bio-based fuels which are environment friendly and that lessen the independence on the petroleum based products A process for the production of 30 ton/day of 1st generation bio-ethanol using fermentation of molasses, 4 ton/day of second generation bioethanol, using bagasse as the raw material is presented. Here the selected process for the pretreatment of bagasse is dilute acid pretreatment method. Other products in the biorefinery like sugar and vinasse (a bio-fertilizer) are also produced. To improve the overall efficiency of the process to 37%, cane trash and some part of bagasse is also used to convert into fuel and electricity to make the biorefinery energy independent and energy efficient. The processes are simple, high yield and highly energy efficient. The 1st generation bioethanol is worldwide produced by using molasses, and the production of 2 nd generation bio-ethanol is still under pilot plant study. It is mainly used as a fuel like E85, E95, and E90 etc. In accordance with the process selected for the production of 1st generation bioethanol, 2nd generation bioethanol, vinasse and raw sugar, process description and process flow diagram is developed, including various specifications regarding the operations undertaken in the process. To attain efficient production rate, control strategy for major equipment is formulated. The material balance and the energy balance around the equipments as well as for the overall process with appropriate assumption is worked out. Further process design of all the equipments and detailed equipment design of 2 main equipments followed by complete economic evaluation of plant and costing of equipments is performed. Cost information Total Fixed Capital Investment Total Working Capital Manufacturing cost Payback period= 7years = = = Rs 8.108*10^8 Rs 1.216*10^8 Rs 4.5*10^8
The Pay Back period is 7 years which is close to the acceptable payback period. Hence the project is profitable
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TABLE OF CONTENTS Certificate Acknowledgement Executive Summary Table of Contents List of Figures List of Tables List of Symbols and Acronyms Chapter 1: Historical profile 1.1 Introduction 1.2 Natural occurrence of the products 1.3 Traditional applications of Ethanol 1.4 Manufacturers 1.5 History of the products 1 1 2 2 2 i ii iii iv vi vii viii
Chapter 2: Application and grades 2.1 Current Applications of our products 2.2 Various grades/standards/product specifications 4 5
Chapter 3: Economic Scenario 3.1 Worlds Scenario for ethanol 3.2 Indias Scenario for ethanol 7 8
Chapter 4: Properties, Handling and Storage 4.1 Properties 4.2 Bio-environmental Characteristics 10 12
Chapter 5: Manufacturing Processes 5.1 Location of the plant 5.2 Manufacturing Process 5.3 Sugar manufacturing process 5.4 Bioethanol production from Molasses 5.5 Bioethanol production from Sugarcane Bagasse 14 15 15 16 17
Chapter 6: Selected Process
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6.1 Process Flowsheet 6.2 Process Description 6.3 Plant Capacity
22 22 24
Chapter 7: Material Balance 7.1 Material Balance for the production of Bioethanol from molasses 7.2 Overall Material Balance for the other products in our biorefinery 25 33
Chapter 8: Energy Balance Energy balance for the equipments in the process 34
Chapter 9: Control Strategy 9.1 Control Strategy of the Distillation Column 9.2 Description Chapter 10: Detailed Equipment Design 10.1 List of equipments 10.2 Process design of all the equipments 10.3 Mechanical design of the equipments Chapter 11: Economic Evaluation 11.1 11.2 Economic Evaluation Cash Flow Statement 59 62 40 40 49 38 39
Chapter 12: HAZOP Analysis and Plant Layout 12.1 12.2 Conclusion References Appendix Hazop of Distillation Column Plant Layout 64 66 67 68 70
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LIST OF FIGURES
Fig 3.1 Current and projected demand and supply of Bioethanol worldwide Fig 3.2 Price and price variations of Bioethanol Fig 3.3 Demand of bioethanol in the form of pie-chart Fig 4.1 Structure of Sucrose Fig 5.1 District wise Sugar Contribution % in Maharashtra Fig 5.2 Block flow diagram for the manufacturing of sugar Fig 5.3 Process flow diagram for the production of first generation bioethanol from molasses Fig 5.4 Simplified Block flow diagram of the overall process (of treatment of bagasse) Fig 6.1 Simplified flow sheet for the production of bioethanol from molasses Fig 7.1 Material balance across fermenter Fig 7.2 Material balance across Yeast treatment Reactor Fig 7.3 Material balance across centrifuge Fig 7.4 Material balance across Distillation column Fig 7.5 Material balance across Rectification Column Fig 7.6 Material Balance across Dehydration Column Fig 9.1 Control Strategy of the Distillation Column Fig 10.4 Valves sequencing for adsorption and regeneration steps Fig 12.1 Plant Layout of the Biorefinery 7 8 9 10 14 15 15 20 22 25 27 28 29 30 31 38 49 66
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LIST OF TABLES
Table 3.1 Application wise Demand Growth Table 3.2 Projected Demand and supply of Bioethanol in India Table 5.1 Comparison of the pretreatment methods on the basis of different properties Table 5.2 Comparison of selected pre-treatment processes Table 7.1 Material Balance across Fermenter Table 7.2 Material Balance across Yeast treatment tank Table 7.3 Material Balance across Centrifuge Table 7.4 Material Balance across Distillation Column Table 7.5 Material Balance across Rectification Column Table 7.6 Material Balance across Molecular Sieve Dehydrator Table 7.7 Overall Material Balance of the process Table 7.8 Overall Material Balance of all the products in the biorefinery Table 8.1 Energy Balance across the fermenter Table 8.2 Energy Balance across the Distillation Column Table 8.3 Energy Balance across the Rectification Column Table 8.4 Energy Balance across the Dehydrator Table 10.1 Material balance across the distillation column Table 10.2 Values for Antoine Constants Table 11.1 Cost of storage tanks Table 11.2 Cost of Process Equipments Table 11.3 Cost of all the equipments Table 11.4 Cost of Raw Materials Table 11.5 Cost of Utilities Table 11.6 Cash Flow Chart Table 12.1 HAZOP Analysis applied to the Distillation Column 8 9 18 19 27 28 29 30 31 32 32 33 35 36 37 37 44 45 59 59 60 61 61 62 65
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LIST OF SYMBOLS AND ACRONYMS

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. F feed D distillate R residue f percentage of ethanol in feed d percentage of ethanol in distillate r percentage of ethanol in residue H enthalpy change mi mass flow rate of inlet materials Hi enthalpy of inlet materials Ek change in kinetic energy Ep change in potential energy Ws work done by shaft U change in internal energy T temperatue P pressure H out change in enthalpy of outlet materials nin number of moles in n out number of moles out extent of reaction Cp specific heat capacity value T change in temperatue FC-Flow Controller LC-Level Controller PC-Pressure Controller TC-Temperature Controller Q volumetric flow rate V volume avg average density Kla overall mass transfer coefficient u superficial velocity D diameter L length mix average density of the mixture g acceleration due to gravity viscosity avg average relative volatility Rmin minimum reflux ratio Vmin minimum vapour flowrate Lmin minimum liquid flowrate N number of plates N actual number of plates Uv maximum allowable velocity of vapour Lt Tray Spacing Density of liquid, l Density of vapour, v
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46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68.
Vw max vapour rate Column Diameter, Dc Column area, Ac Downcomer area, Ad Net area, An Active area, Aa Hold area, Ah Weir length, lw Weir height, hw Hole diameter, dh Allowable stress, f t thickness of shell material ft tangential or hoop stress f1 stress in axial direction fs stress due to offset piping fR equivalent stress M max bending moment zp axial stress due to pressure zs The stress induced by shell weight at a distance X m from the top: zi The stress induced in the shell due to insulation zl The stress induced in the shell due to liquid hold up za The stress induced in the shell due to attachments zw total dead load stress
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Design of integrated sugarcane based biorefinery
Chapter -1 HISTORICAL PROFILE

1.1 INTRODUCTION 1.1.1 WHAT IS A BIOREFINERY? A biorefinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power, heat, and value-added chemicals from biomass. The biorefinery concept is analogous to today's petroleum refinery, which produce multiple fuels and products from petroleum. By producing multiple products, a biorefinery takes advantage of the various components in biomass and their intermediates therefore maximizing the value derived from the biomass feedstock. At the same time generating electricity and process heat, through combined heat and power (CHP) technology, for its own use and perhaps enough for sale of electricity to the local utility[1] 1.1.2 WHAT IS THEIR NEED? It is essential to establish solutions which reduce the rapid consumption of fossil resources, which are not renewable (petroleum, natural gas, coal, minerals). A forward looking approach is the stepwise conversion of large parts of the global economy into a sustainable biobased economy with bioenergy, biofuels, and biobased products as its main pillars. [2] 1.1.3 THE VARIOUS PRODUCTS THAT CAN BE PRODUCED IN A BIOREFINERY: Raw Sugar First generation bioethanol from blackstrap molasses obtained as the by-product of the sugar manufacturing process Second generation Bioethanol from the sugarcane bagasse obtained as the by-product of the sugar manufacturing process Biofertilizers like vinasse Energy obtained by using bagasse as a fuel, generation of electricity etc Bulk organic chemicals: acetic acid, butanol, ethyl acetate etc Speciality Chemicals: ethyl lactate, cinnamic alcohol, cinnamic acid etc
1.2 NATURAL OCCURRENCE OF THE PRODUCTS: 1.2.1 Sucrose: It is found naturally in many food plants along with the monosaccharide fructose. In many fruits, such as pineapple and apricot, sucrose is the main sugar.
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1.2.2 Ethanol: It is a byproduct of the metabolic process of yeast It is present in any yeast habitat It is commonly found in an overripe fruit It is also produced during the germination of many plants as a result of natural anerobiosis. Ethanol produced by symbiotic yeast can be found in Bertam Palms blossoms.[3] Ethanol has been detected in outer space, forming an icy coating around dust grains in interstellar clouds.
1.3 TRADITIONAL APPLICATIONS OF ETHANOL: The traditional applications of ethanol are as follows: Beverage : Due to its high organoleptic quality, alcohol is used by the leading European spirits manufacturers to produce many famous alcoholic beverages. Pharmacy: The alcohol used by the pharmaceutical industry must meet various stringent requirements in terms of purity and neutrality. Perfume: Due to the high and constant neutrality, alcohol is used for preserving the fragrance of the perfumes. It is also used in many cosmetic products. Certain other applications, such as hair spray, also need dehydrated neutral alcohol. Industry: It offers a large range of industrial applications. This ensures that all the needs of the manufacturers involved in this sector, including printing ink, screen wash, paints and explosives can be satisfied. Alcoholic products can be supplied undenatured or denatured. [4] 1.4 MANUFACTURERS The currently operating biorefineries in the world are: Godavari Biorefineries Ltd- It has plants located in the states of Karnataka (Sameerwadi, Mudhol Taluka, Dist: Bagalkot, Karnataka, India) and Maharashtra, Mumbai The Blue Marble Energy Company has multiple biorefineries located in Odessa, WA and Missoula, MT Amyris Brasil Ltda. is located in Campinas, Brasil [5]
1.5 HISTORY OF THE PRODUCTS: 1.5.1 Sucrose: Its history begins with the discovery of sugarcane in the South Pacific, probably New Guinea and as the time passed, the plant was grown in Southeast Asia and India, eventually making its way to China. Sugar was relatively rare in Europe until the 13th century, when trading with Asia expanded. The cultivation of sugar cane in the New World also increased its availability. In Europe, the use of sugar beets for making sugar also increased during the 1800s. Today, the production of sugar using both sugar beets and sugar cane continues around the world.
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1.5.2 Bioethanol: 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 bioetha nol 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.[6]
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Chapter-2 APPLICATIONS AND GRADES

2.1 CURRENT APPLICATIONS OF THE PRODUCTS: 2.1.1 Sucrose: Granulated sugars are used at the table to sprinkle on foods and to sweeten hot drinks and in home baking to add sweetness and texture to cooked products. Milled sugars are ground to a fine powder. They are used as icing sugar, for dusting foods and in baking and confectionery. Screened sugars are crystalline products separated according to the size of the grains. They are used for decorative table sugars, for blending in dry mixes and in baking and confectionery. Brown sugars are granulated sugars with the grains coated in molasses to produce a light, dark or Demerara sugar. They are used in baked goods, confectionery and toffees. Sugar cubes are white or brown granulated sugars pressed together in block shape. They are used to sweeten drinks. Liquid sugars are strong syrups consisting of 67% granulated sugar dissolved in water. They are used in the food processing of a wide range of products including beverages, ice cream and jams. Invert sugars and syrups are blended to manufacturers specifications and are used in breads, cakes and beverages for adjusting sweetness, aiding moisture retention and avoiding crystallization of sugars In winemaking, fruit sugars are converted into alcohol by a fermentation process. It must be formed by pressing the fruit has a low sugar content, additional sugar may be added to raise the alcohol content of the wine in a process called chaptalization. In the production of sweet wines, fermentation may be halted before it has run its full course, leaving behind some residual sugar that gives the wine its sweet taste. [7]
2.1.2 Bioethanol: The current applications of the ethanol are as follows: As a fuel: The largest single use of ethanol is as a motor fuel and fuel additive. Brazil has the largest national fuel ethanol industry. Gasoline sold in Brazil contains at least 25% anhydrous ethanol. Hydrous ethanol (about 95% ethanol and 5% water) can be used as a fuel in more than 90% of new cars sold in the country.
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Feedstock: Ethanol is an important industrial ingredient and has widespread use as a base chemical for other organic compounds. These include ethyl halides, ethyl esters, diethyl ether, acetic acid, ethyl amines, and to a lesser extent butadiene Antiseptic: Ethanol is used in medical wipes and in most common antibacterial hand sanitizer gels at a concentration of about 62% v/v as an antiseptic. Ethanol kills organisms by denaturing their proteins and dissolving their lipids and is effective against most bacteria and fungi, and many viruses, but is ineffective against bacterial spores. Solvent: Ethanol is miscible with water and is a good general purpose solvent. It is found in paints, tinctures, markers, and personal care products such as perfumes and deodorants. It may also be used as a solvent in cooking, such as in vodka sauce. [8]
2.1.3 Molasses: Molasses is a waste product of sugar industry of which further extraction of sugar is uneconomical The majority of this waste product of sugar industry of which dried pulp from the sugarcane is used for animal feed Ethanol production is one growing application of this plentiful material
[9]
2.2 VARIOUS GRADES/STANDARDS/PRODUCT SPECIFICATIONS 2.2.1 Sucrose: SUGAR STANDARDS & SPECIFCATIONS: REFINED SUGAR GRADE A - ICUMSA 45 Origin Colour ` Granulation : : : Brazil Sparkling White Fine
RAW BROWN CANE SUGAR GRADE E ICUMSA 600-1200 (International Commission for Uniform Methods of Sugar Analysis) Origin Colour Granulation : : : South America/Brazil Brown Fine
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2.2.2 Bioethanol: Several grades of ethyl alcohol are available in the marketplace today. They differ primarily in the amount of impurities present. Generally, as you move down the chain to a lower quality ethanol, higher amounts of impurities are present. The Purest: GNS or grain neutral spirits. The highest level of ethanol purity is GNS or grain neutral spirits, beverage quality. This is only domestically produced from fermentation grain sources, typically corn or wheat. In addition to meeting all of the quality requirements for USP and FCC grade materials, GPC beverage alcohol must pass stringent organoleptic analysis. Since GNS is intended for human consumption, this test is the most important screening tool. Organoleptics are normally run at 40 proofs (20% by volume). Purer: FCC Grade ethanol (Food Chemical Codex) adds heavy metal specification limits to the grades below since most FCC grade materials are used in food applications. This can be either of fermentation or synthetic origin. Pure: Industrial Grade ethanol can be of either fermen tation or synthetic origin. It has most of the impurities removed. USP Grade ethanol (U.S. Pharmacopoeia) has specific tests that measure impurities present, setting limits on each type. NF Grade ethanol (National Formulary) lowers the amount of impurities further to the 20 to 25 ppm levels. Not-as-pure: The highest impurity levels are found in fuel grade ethanol that is produced via the fermentation process. It is added to gasoline as an octane enhancer/extender and to reduce carbon monoxide and nitrous oxide pollution. Manufacturers of this grade dont take great care in removing the impurities produced in the process because they burn easily in a combustion engine . [10] 2.2.3 Molasses:
Fancy molasses: It is a direct product of sugarcane and also known as gold star molasses. Blackstrap molasses: It is the byproduct of sugar making process. Cooking molasses: It is the blend of fancy and blackstrap molasses.[11]
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Chapter-3 ECONOMIC SCENARIO

3.1 WORLD SCENARIO (ETHANOL) 3.1.1 Current and projected demand and 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 3.1.2 Application wise Consumption pattern: Of the total ethanol world demand 28% is for the blending purpose to be used as a fuel and the remaining 50% and 22% by the portable and industrial sector in year 2011. Future demand analysis shows that demand for industrial and portable sector is increasing that means ethanol consumption in this sector is more than that for fuel purpose. Thus we should lay more emphasis on the production of ethanol from lignocellulosic material specially sugarcane bagasse to meet heavily growing demand.
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Year
Portable sector demand 1.6 2 2.6 3.1
Industrial sector demand 0.6 0.8 1 1.2
2011 2013 2015 2017
Fuel ethanol demand @5% blending 0.9 1 1.2 1.4
Total ethanol demand 3.2 3.8 4.7 5.7
Ethanol demand growth rate (%) 10%
Table 3.1 Application wise Demand Growth 3.1.3 Price and price Variations: There is a very unpredictable change in price of ethanol during the recent past years so there is a need to stabilize the price by increasing the production of bioethanol which will cut short the gap of demand and supply.
Fig 3.2 Price and price variations of Bioethanol 3.1.4 Manufacturing Capacities: Current and Projected: 3.1.5 Worlds Current manufacturing capacity : 11,874 million gallons Worlds projected manufacturing capacity : 14,346 million gallons Manufacturers and Capacities: The top 2 Global Bioethanol Manufacturers alongwith their production capacity is as follows: ADM in USA with capacity 6,937 million litre/year POET in USA with capacity 5,957 million litre/year
3.2 INDIAS SCENARIO (FOR ETHANOL) 3.2.1 Current and Projected demand and Supply
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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. Demand all over Country Existing Production Total demand Demand in Maharashtra 5000 1840 2460 700 Lac liters Lac liters Lac liters Lac liters
Table 3.2 Projected Demand and supply of Bioethanol in India [12] The above data for the projected demand and supply of bio-ethanol in India is calibrated in terms of percentage and is shown in fig. 3.3 using a pie chart. As per the data existing production is only 37% of the demand. Moreover of the total demand 14% demand is in Maharashtra alone. So it justifies our project the need of bio refinery for production of bio ethanol in Solapur, Maharashtra.
Fig 3.3 Demand of bioethanol in the form of pie-chart 3.2.2 Application wise consumption pattern: Supply of ethanol as per their application in various Industries as on 2011 is as follows: Fuel ethanol Industrial sector Portable sector 0.56 billion liters 0.65 billion liters 1.7 billion liters 20% 22% 58%
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Chapter - 4 PROPERTIES, HANDLING AND STORAGE

4.1 PROPERTIES 4.1.1 Sucrose: Sucrose is the organic compound commonly known as table sugar and sometimes called saccharose. A white, odorless, crystalline powder with a sweet taste, it is best known for its nutritional role. Sucrose is a molecule with five stereo centers and many sites that are reactive or can be reactive. The molecule exists as a single isomer. Structure:
-D-glucopyranosyl--D-fructofuranoside Fig 4.1 Structure of Sucrose 4.1.1.1 Physical Properties: Molecular Formula Molar Mass Appearance Density Melting point Solubility in water 4.1.1.2 Chemical Properties: Sucrose is readily soluble in aqueous protic solvents such as methanol and ethanol. It is insoluble in ether and chloroform and anhydrous ethanol and glycerol. It is moderately soluble in DMF, pyridine, and dimethyl sulphoxide. C12H22O11 342.30g/mol white solid 1.587 g/cm3, solid 186o decomp. 2000g/L (25oC)
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Under mild acid catalysis, usually dilute HCl, sucrose is easily hydrolysed and inversion occurs (change in the sign of polarization from +66.5 to a negative value, owing to the large negative rotation of fructose). A small amount of the fructose formed is converted to D-fructose dianhydrides. A small degree of inversion is detectable under alkaline conditions. Sucrose is hydrogenated with Raney nickel to a mixture of sorbitol and mannitol; under more drastic conditions, glycerol and propylene glycol are produced. Mild oxidation gives oxalic and tartaric acids, as well as acidic materials designated as saccharic acids. 4.1.2 BioEthanol: 4.1.2.1 Physical Properties: It is a volatile, colourless 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, viscosity and surface tension 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[13] 4.1.2.2 Chemical Properties: Combustion of Ethanol: Ethanol burns with a pale blue, non luminous flame to form carbon dioxide and steam. C2H5OH + 3O22CO2 + 3H2O Dehydration of Ethanol: When ethanol is mixed with concentrated sulphuric acid with the acid in excess and heated to 170oC, ethylene is formed. (One mole of ethanol loses one mole of water)
H2SO4
C2H5OHC2H4 + H2O 4.1.3 Molasses: It is a dark reddish coloured jelly like material. pH- 6.8 to 8.5 High osmotic pressure of molasses protects it from microbial spoilage.
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It can be easily transported by tankers etc. It can be pumped easily
4.2 BIO ENVIRONMENTAL CHARACTERISTICS: 4.2.1 Sucrose: 4.2.1.1 Metabolic fate in Human beings and other organisms: In humans and other mammals, sucrose is broken down into its constituent monosaccharides, glucose and fructose, by sucrose orisomaltase glycoside hydrolases, which are located are located in the membrane of the microvilli lining the duodenum. The resulting glucose and fructose molecules are then rapidly absorbed into the bloodstream. In bacteria and some animals, sucrose is digested by the enzyme invertase. 4.2.1.2 Health Impact: Diabetes: It is a disease that causes the body to metabolize sugar poorly, occurs when either: the body attacks the cells producing insulin, the hormone that allows the metabolizing of sugar (Type 1 diabetes) The body's cells exhibit impaired responses to insulin (Type 2 diabetes).
Obesity: The National Health and Nutrition Examination Survey I along implies that obesity may correlate better with sugar consumption than with fat consumption, and that reducing fat consumption while increasing sugar consumption actually increases the level of obesity
Gout: A diet rich in sucrose may lead to gout as it raises the level of insulin, which prevents excretion of uric acid from the body.
4.2.2 Bioethanol: 4.2.2.1 Environmental Fate and Impact: Ethanol contains 35% oxygen, is non-toxic, water-soluble and quickly biodegradable. These properties make it an ideal substance to formulate fuel blends the use of which will mean a cleaner and less polluted environment and, as a consequence, a healthy planet for us all and for future generations. Compared to petroleum-based fossil fuels, Ethanol blends contribute significantly towards the safety and conservation of the environment. 10% Ethanol blends reduce greenhouse gas emissions by 12-19%. In 2005, Ethanol use in the US reduced CO2 -greenhouse gas emissions by about 7.8 million tons. According to the American Lung Association of Metropolitan Chicago, Ethanol-blended, reformulated gasoline reduces smog-forming emissions by 25% since 1990.
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Ethanol brings down tailpipe emissions by 30%, toxic content by 13% (mass) and 21% (potency), and tailpipe fine particulate matter (PM) emissions by 50%. Ethanol has a positive energy balance, for it generates more energy than is consumed during production. It yields 67% more fossil energy than is used to grow, harvests and process the grain. Ethanol reduces formaldehyde emissions.[14]
4.2.2.2 Metabolic Fate in Human beings and other organisms: The first and foremost concern for public health is its carcinogenic effects, as there is unambiguous evidence for the carcinogenicity of ethanol orally consumed in the form of alcoholic beverages. Limited and conflicting epidemiological evidence is available on the link between the use of ethanol in the oral cavity in the form of mouthwashes or mouth rinses and oral cancer. Some studies pointed to an increased risk of oral cancer due to locally produced acetaldehyde, operating via a similar mechanism to that found after alcoholic beverage ingestion. In addition, it acts as a skin penetration enhancer and may facilitate the transdermal absorption of xenobiotics (e.g. carcinogenic contaminants in cosmetic formulations). Ethanol use is associated with skin irritation or contact dermatitis, especially in humans with an aldehyde dehydrogenase (ALDH) deficiency. After regular application of ethanol on the skin (e.g. in the form of hand disinfectants) relatively low but measurable blood concentrations of ethanol and its metabolite acetaldehyde may occur, which are, however, below acute toxic levels. Only in children, especially through lacerated skin, can percutaneous toxicity occur. [15]
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Chapter - 5 MANUFACTURING PROCESSES

5.1 LOCATION OF THE PLANT: We have selected the location of our proposed integrated sugarcane based biorefinery in SOLAPUR, MAHARASHTRA. The reasons for choosing it are: Uttar Pradesh and Maharashtra are the 2 leading sugarcane producing states of India. We have preferred Maharashtra over Uttar Pradesh because: Near Maharashtra, sea port is there which helps in transportation of raw materials from abroad and export of our products to other countries i.e. helps in reducing transportation cost. Compared to Uttar Pradesh, Maharashtras level of industrial facilities like electricity and water supply are better. Security is good. Raw material availability. Product market.
In Maharashtra, we prefer SOLAPUR because: Sugar production is highest in Solapur(as shown in Fig 5.1)
Fig 5.1 District wise Sugar Contribution % in Maharashtra
There are about 35 sugar mills in Solapur, from which we could get our bagasse for increased ethanol production. Labor will be easily available.
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Climatic conditions are as per our needs. Infrastructure 5.2 MANUFACTURING 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 5.3 SUGAR MANUFACTURING PROCESS: The basic block flow diagram for the production of sugar from sugarcane is as follows:
Fig 5.2 Block flow diagram for the manufacturing of sugar The basic steps followed in the manufacturing of sugar are as follows: 1. MILLING: Sugarcane cannot be stored more than a few hours after it is cut, so raw sugar mills are located in the cane fields. The cane is washed and broken into pieces. The juice is extracted either by milling, in which cane is passed between heavy rolls , or by diffusion in which the cane is leached with water. The sugar recovered is nominally 10% of the cane. 2. CLARIFICATION:
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The first step in the process is to add lime, which raises the pH ,stop inversion and hepls to settle the suspended matter. Although clarification removes most of the mud, the resulting juice is not necessarily clear . Suppliment schemes complete the clarification. 3. EVAPORATION: The clarified cane juice is not much concentarated and a large amount of water must be removed. Multiple effect evaporators are used; about three or four are used in series in which the first operates at atmospheric pressure and subsequent effects are at higher vaccum. The juice after evaporation is called syrup and is almost black and little turbid. 4. CRYSTALLISATION: Crystallisation from the concentrated syrup is traditionally a batch process. After seeding, the evaporation and feeding of the syrup are balanced for the fastest possible rate of growth. 5. VACCUM PANS: Crystallisation is done under a vaccum such that the water boils at about 65oC in order to minimise thermal destruction of sucrose. The vaccum pans has a very large discharge opening, typically 1m dia. At the end of the strike, the massecuite contains more crystals than syrupand is very viscous. The large opening is required in order to empty the pan in a reasonable time. 6. CENTRIFUGING: The massecuites from the vaccum pans enter a holding tank calleda mixer that has a slowly turning paddle to prevent the crystals from settling.the centrifuge is fed from the mixer.a centrifugal force of about 1000 G is applied. The starting and stopping of the centrifugal batch consumes a large amount of energy, much of which can be saved by the use of a continuous centrifuge consisiting of a conical basket with a screen. 7. BOILING SYSTEMS: In raw sugar munufacture, the first strike is called the A strike and the mother liquor obtained from the centrifuges is called A molasses. The so called B sugar obtained from the second strike is only half as pure as obtained from the first strike. We are obtaining the A strike raw sugar and now we have theoption o either to sell it to vendors or to convert it to the refined sugar. The B molasses we are using for the production of our first generation bioethanol. 5.4 ETHANOL PRODUCTION FROM MOLASSES Syrup B molasses is used for the production of Anhydrous Ethanol. The Process flow diagram for the production of bioethanol from molasses is shown in Fig 5.3[16]
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5.4.1 Basic Raw Materials: Molasses are one of the most common raw materials used in the manufacture of alcohol. This is because they are cheap and readily available in large quantities. Micro-organism used: Selected strains of the yeast Saccharomyces cerevisiae are commonly employed for fermentation. This is because (a) they grow vigorously, (b) they have high tolerance for alcohol and (c) they have a high capacity for producing a large yield of alcohol. 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[16] 5.5 BIO-ETHANOL PRODUCTION FROM SUGARCANE BAGASSE: The production of fuel ethanol from lignocellulosic biomass includes the following steps: 1. 2. 3. 4. 5. 6. biomass pre-treatment, cellulose hydrolysis, fermentation of hexoses, separation, effluent treatment, Gathering, depending upon, the feedstock which may have an additional cost.
1.
Biomass pre-treatment: Pre-treatment is one of the key unit operations for the successful conversion of lignocellulosic materials to ethanol. This is due to the close association that exists among the three main components of the plant cell wall (cellulose, hemicelluloses and lignin), which is by far the most determinant factor for the low accessibility of plant
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carbohydrates to biological processes such as enzymatic hydrolysis and fermentation. Therefore, the main role of a pre-treatment method is to decrease the interaction between the main that are inhibitory to the subsequent hydrolysis and fermentation processes. Many methods have been used for pretreating lignocellulosic materials. These are steam explosion ammonia fiber explosion among others. Each one of these methods has advantages and disadvantages and no one seems to be optimal for all practical applications. The best pre-treatment conditions must be defined as those in which the maximum recovery of water-soluble hemicellulose sugarsis obtained, along with the production of the best possible substrate for enzymatic hydrolysis and fermentation The comparison of various methods of pre-treatment with the perspective of various properties and their advantages and disadvantages is given below.
Table 5.1 Comparison of the pretreatment methods on the basis of different properties [17] Now on the basis of above comparison, we have selected 4 pretreatment methods are selected and their net energy ratio, renewability index, energy efficiency and energy emissions are compared.
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Acid catalyzed steam Explosion Diluted acid Liquid hot water Organosolv
Ethanol production 185,540 L/d
NER <1
RENEWABILITY INDEX
ENERGY EFFICIENCY HIGHEST
ENERGY EMISSIONS
200,741 L/d 196,314 L/d 203,193 L/d
<1(HIGHEST) <1(LOWEST) <1
HIGHEST LOWEST MINIMUM LOWEST HIGHEST
Table 5.2 Comparison of selected pre-treatment processes Net energy ratio (NER = net energy output/net energy Input) Due to NER< 1 indicates that the fuel ethanol system has not net energy gain, thus these processes have higher energy consumption and it is necessary to apply energy integration methodologies to reduce the external energy input Although Case 4 have higher energy requirement in pretreatment stage because of solvent recovery process, the highest energy output by means of produced ethanol improved the net energy ratio. Renewability index (net bioenergy outputs/net fossil energy inputs) higher than 1 is a minimum requirement to indicate that the biofuel system can help to reduce dependency on fossil energy. However, it is higher than 1 when at least 53% of energy input is from renewable resources. Thus we have selected dilute acid for the pretreatment of bagasse for the production of second generation bioethanol.
Process Overview involving all the steps required for the production of second generation bioethanol from Bagasse: The process described here uses co-current dilute-acid pretreatment of lignocellulosic biomass followed by enzymatic hydrolysis (saccharification) of the remaining cellulose, by fermentation of the resulting glucose and xylose to ethanol. The process design also includes feedstock handling and storage, product purification, wastewater treatment, lignin combustion, product storage, and required utilities. The process is divided into nine areas as shown in the fig 5.5 1. Area 100: Feed handling. The feedstock, in this case milled SUGAR CANE is delivered to the feed handling area from a uniform-format feedstock supply system. Only minimum storage and feed handling are required. From there, the biomass is conveyed to the pretreatment reactor (Area 200). 2. Area 200: Pretreatment and conditioning. In this area, the biomass is treated with dilute sulfuric acid catalyst at a high temperature for a short time to liberate the hemicellulose sugars and break down the biomass for enzymatic hydrolysis. Ammonia is then added to the whole pretreated slurry to raise its pH from ~1 to ~5 for enzymatic hydrolysis. 3. Area 300: Enzymatic hydrolysis and fermentation. Enzymatic hydrolysis is initiated in a high-solids continuous reactor using a cellulase enzyme prepared on-site. The partially hydrolyzed slurry is next batched to one of several parallel bioreactors. Hydrolysis is completed in the batch reactor, and then the slurry is cooled and inoculated with the co-fermenting microorganism Zymomonas mobilis. After a total of five days of sequential enzymatic hydrolysis and
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fermentation, most of the cellulose andxylose have been converted to ethanol. The resulting beer is sent to the product recovery train (Area 500). 4. Area 400: Cellulase enzyme production. An on-site enzyme production section was included in this design. Purchased glucose is the primary carbon source for enzyme production. Media preparation involves a step in which a portion of the glucose is converted to sophorose to induce cellulase production.The enzyme-producing fungus (modeled after Trichoderma reesei) is grown aerobically in fed-batch bioreactors. The entire fermentation broth, containing the secreted enzyme, is fed to Area 300 to carry out enzymatic hydrolysis. 5. Area 500: Product Recovery. The beer is separated into ethanol, water, and residual solids by distillation and solidliquid separation. Ethanol is distilled to a nearly azeotropic mixture with water and then purified to 99.5% using vaporphase molecular sieve adsorption. Solids recovered from the distillation bottoms are sent to the combustor (Area 800) while the liquid is sent to wastewater treatment (Area 600).
Fig 5.4 Simplified Block flow diagram of the overall process (of treatment of bagasse) [18]
6.
Area 600: Wastewater treatment. Plant wastewater streams are treated by anaerobic and aerobic digestion. The methane-rich biogas from anaerobic digestion is sent to the combustor (Area 800), where sludge from the digesters is also burned. The treated water is suitable for recycling and is returned to the process.
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7. Area 700: Storage. This area provides bulk storage for chemicals used and produced in the process, including corn steep liquor (CSL), ammonia, sulfuric acid, nutrients, water, and ethanol. 8. Area 800: Combustor, boiler, and turbo generator. The solids from distillation and wastewater treatment and the biogas from anaerobic digestion are combusted to produce high-pressure steam for electricity production and process heat. The majority of the process steam demand is in the pretreatment reactor and distillation columns. The boiler produces excess steam that is converted to electricity for use in the plant and for sale to the grid. 9. Area 900: Utilities. This area includes a cooling water system, chilled water system process water manifold, and power systems.
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Chapter-6 SELECTED PROCESS

6.1 FLOWSHEET
Fig 6.1 Simplified flow sheet for the production of bioethanol from molasses [16] 6.2 PROCESS DESCRIPTION: 6.2.1 RAW MATERIALS MOLASSES: The most widely used sugar for ethanol fermentation is blackstrap molasses which contains about 35 40 wt% sucrose, 15 20wt% invert sugars such as glucose and fructose, and 28 35 wt% of non-sugar solids. Blackstrap (syrup) is collected as a by-product of cane sugar manufacture. The molasses is diluted to a mash containing ca 10 20 wt% sugars. 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 non-aseptically at 20 32C for about 1 3days. The fermented beer, which typically contains ca 611 wt% ethanol, is then set to the product recovering purification section of the plant. YEAST: Yeast, under anaerobic conditions, metabolizes glucose to ethanol primarily by way of the EmbdenMeyerhof pathway. The overall net reaction involves the production of 2moles each of ethanol, but the yield attained in practical fermentations however does not usually exceed 90 95% of theoretical. 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
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and disturbs the entire section. To avoid this molasses is first diluted hence water also takes a part among raw materials [19] 6.2.2 PROCESS: 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. [18] 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. 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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6.3 PLANT CAPACITY: The plant capacity which we have decided is 30 tons per day or 1250 kg/hr of first generation bioethanol (i.e. from molasses) and 3.2 tons of second generation bioethanol (from lignocellulosic material) therefore overall plant capacity for the production of bioethanol is 33.2 tons per day.
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Chapter-7 MATERIAL BALANCE

7.1 MATERIAL BALANCE FOR THE PRODUCTION OF BIOETHANOL FROM MOLASSES: BASIS: 30 tons per day of bio ethanol from the rectification column (95% by weight) 7.1.1 FERMENTER Assumptions: Molasses contain 52% fermentable sugar in the form of sucrose and 48% water 95% of sucrose will convert to bio ethanol 10% less alcohol is produced due to pipe losses 1 kg=2.694*10^-3 kg Ammonium sulphate 1 kg=2.1544*10^-3 kg H2SO4 1kg H2SO4=0.2 kg H2O Density of ethanol:0.789 kg/l The ratio of water to molasses is 4:1 For ethanol system, dx/ds=0.5[20]
Fig 7.1 Material balance across fermenter Streams: 1. 2. 3. 4. Mesh(Water + Molasses) Yeast culture + yeast cells CO2 Mixture of ethanol, water and biomass
Overall Reaction: C12H22O11+H2O2C6H12O64C2H5OH+4CO2 Mol. Wt of sucrose= 342
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Mol. Wt of ethanol=184 CALCULATIONS: Input to the fermenter 342 kg of sucrose gives 184 kg of bio ethanol 342 kg of sucrose will give= 184*0.95=174.8 kg bio ethanol Molasses for 342 kg sucrose = 342/0.52=657.69 kg molasses 174.8 kg bio ethanol requires 657.69 kg molasses Or 1 kg bio ethanol requires 3.76 kg of molasses Due to 10% pipe losses, 1kg bio ethanol requires =3.76+(0.1*3.76)= 4.136 kg of molasses 1 l bio ethanol requires (4.136*0.789)=3.26 kg of molasses Acc to our capacity (i.e. 12500 kg/hr), molasses required= 12,50*4.136 = 5170 kg/hr molasses Water added to molasses is 4 times of molasses = (4*5170)=20,680 kg/hr Therefore, total feed (i.e. Mesh) produced= (5170+20680) =25850 kg/hr Since molasses contain 52% fermentable sugar in the form of sucrose, sucrose in the molasses (feed)=(0.52*5170)=2688.4 kg sucrose/hr From our reaction, we know that, 342 kg sucrose gives 174.8 kg pure ethanol; therefore 2688.4 kg sucrose/hr gives 1374.071 kg ethanol/hr. Yeast culture needed =5% by weight of mesh Therefore, yeast culture= (0.05*25850) =1292.5 kg/hr Cell concentration=12.5 gm/kg of mesh So, cells present in the culture=12.5*10^-3 *25850 =323.125 kg cells/hr Nutrients in the culture is Ammonium Sulphate Ammonium sulphate in 25850 kg/hr mesh= 69.6 kg/hr H2SO4 in 25850 kg/hr mesh= 55.692 kg H2SO4 Water formed by 55.692 kg H2SO4=11.138 kg/hr As per the stoichiometric equation given, water required for the reaction= (18/342*26,884)=141.495kg water/hr Water Balance Water in-Water used in the reaction=Water out = (20680+11.138)-141.495=20549.643kg/hr CO2 produced According to the stoichiometry, Moles of CO2 produced is equal to the moles of ethanol produced Moles of CO2 produced= moles of ethanol produced/46= 1374.071/46 = 29.871 kmol/day Therefore, CO2 produced when 1374.071 kg/hr of ethanol is produced= 29.871*44=1314.324 kg CO2/hr Biomass Material balance over fermenter wrt yeast bacterial mass is
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[Change within vessel]= [Increase due to feed] + [Increase due to growth]-[Decrease due to loss in effluents][decrease due to death] dx/ds=0.5g/g=(x-xo)/(s-so) =y*x/s Where, X is dry cell mass finally Xo is dry cell mass initially S is substrate mass finally So is substrate mass initially Xo=323.125 kg/hr cells So=2688.4 kg of sugar/hr S is the final weight of substrate or the left moles of ethanol=1374.071/46=29.871 kmol/hr From stoichiometry of reaction, moles of sucrose converted=29.871/4=7.468 kmol/hr Initial moles of sucrose=2688.4/342=7.861 kmoles/hr Therefore, moles unconverted=7.861-7.468=0.393 kmoles/hr Kgs of substrate at the end(S) =0.393*342=134.406 kg/hr Now, X=1600.122 kg of cells/hr Along with cells, about 50% water also goes out=0.5*1600.122=800.061kg water/hrs Therefore, wt. of biomass=800.061+1600.122=2400.183 kg/hr Kg/hr(inlet) 25850 5170 20680 323.125 1292.5 55.692 Components Diluted Molasses Molasses Water Yeast cells Yeast culture H2SO4 CO2 Bioethanol Biomass Sucrose Residual molasses matter 27521.317 Total 27521.317 55.692 1314.324 1374.071 2400.183 2481.6 654.196 20549.643 Kg/hr(outlet)
Table 7.1 Material Balance across Fermenter
7.1.2
YEAST TREATMENT Assumptions:
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Yeast culture needed is 5% by weight of mesh Cell concentration is 12.5g in 1kg of feed Nutrients by ammonium sulphate pH control by H2SO4
Fig 7.2 Material balance across Yeast treatment Reactor Streams: 5. H2SO4 6. Yeast culture + yeast cells 2. Mixture of streams 5&6
Kg/hr (inlet) 2400.183 55.692 323.125 1292.5 4071.5
Components biomass H2SO4 Yeast cells Yeast culture Total
Kg/hr(outlet) 2400.183 55.692 323.125 1292.5 4071.5
Table 7.2 Material Balance across yeast treatment reactor 7.1.3 CENTRIFUGE:
Fig 7.3 Material balance across centrifuge
Streams: 4. Mixture of ethanol, water, biomass and sucrose 5. Mixture of ethanol, water and sucrose 7. Biomass recycled
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Kg/hr(inlet) 1374.071 20549.643 2400.183 2481.6 26805.497
Components bioethanol Water Biomass sucrose Total Table 7.3 Material Balance across Centrifuge
Kg/hr(outlet) 1374.071 20549.643 2400.183 2481.6 26805.497
% of alcohol in spent wash= 1374.071/ (26805.497-2400.183)*100 = 7.2 % 7.1.4 DISTILLATION COLUMN: Assumptions: 80% by weight of ethanol in distillate 2 % by weight of ethanol in bottom product
Fig 7.4 Material balance across Distillation column Streams: 7. Mixture of ethanol, water and sucrose Distillate: 80% ethanol Bottom: Vinasse % of alcohol in feed=7.2 CALCULATIONS: Overall material balance: F=D+R F=26,805.497-2400.183-5137.4=19,267.914 kg/hr Therefore, 19,267.914=D+R F=feed D=Distillate R=Residue Component balance over distillation column for ethanol: F*f=D*d + R*r
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19,267.914*0.072=D*0.8+ (119,267.914-D)*0.02 We have 2 equations and 2 variables to solve; hence solving we get the values as given in the table 7.4
Kg/hr(inlet) 1374.071 15412.2322
Components ethanol water Ethanol (80%) Vinasse (residue)
Kg/hr(outlet)
1284.528 17983.386 19,267.914
19,267.91
Total
Table 7.4 Material Balance across Distillation Column So, D=1284.528 kg/hr R=17983.386 kg/hr 7.1.5 RECTIFICATION COLUMN:
Assumptions: 95% by weight of ethanol in the distillate 1% by weight of ethanol in residue
Fig 7.5 Material balance across Rectification Column
Streams: 8. Distillate from distillation column Recycle from molecular sieve dehydrator Distillate: 95% ethanol Bottom: residue
CALCULATIONS:
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Overall material balance: R+1250=x+1284.528 x=R-34.528 Component balance: 0.01*R+0.95*1250=0.97*x+0.8*1284.528 Therefore, R=201.385 kg/hr x= 166.857 kg/hr
Kg/hr(inlet) 1284.528 166.857
Components Ethanol (80%) Recycled ethanol (96%) Ethanol (95%) Residue
Kg/hr(outlet)
1250 201.385 1451.385
1451.385
Total
Table 7.5 Material balance across Rectification Column 7.1.6 DEHYDRATION COLUMN:
Fig 7.6 Material Balance across Dehydration Column
Streams: Feed: Hydrous Ethanol (95% by weight of ethanol) Top Product: Recycle stream to the rectification column Bottom Product: Anhydrous ethanol (99.5% by weight of ethanol) CALCULATIONS: D=x +E+W 1250=166.857+E+W 0.95*12500=0.96*1712.817+0.995E E=1030.803kg/hr
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W=52.34 kg/hr Kg/hr(inlet) 1250 Components Ethanol (95%) Water Anhydrous ethanol (99.5%) Recycled ethanol (96%) 1250 Total 52.34 1030.803 166.857 1250 Kg/hr(outlet)
Table 7.6 Material balance across Dehydration Column
7.1.7 OVERALL MATERIAL BALANCE OF THE PROCESS:
kg/hr (inlet) 5170 20680 1292.5 323.125
components molasses water yeast culture yeast cells vinasse residue(rectification column) Anhydrous ethanol (99.5%)
kg/hr (outlet) 6991.419
17983.386 201.385 1030.803 1314.324 27521.317
55.692
H2SO4 CO2
27521.317
Total
Table 7.7 Overall Material Balance of the process
7.2 OVERALL MATERIAL BALANCE FOR OTHER PRODUCTS IN OUR BIOREFINERY Basis: 5170 kg/hr of molasses Assumptions: From 1 ton of sugarcane, 240 kg sugar, 30 kg molasses, 280 kg of bagasse, 450 kg cane trash and other residues can be produced 1200 ton/day of bagasse produces 158384.649 kg bioethanol 50.5% of bagasse is converted to bioethanol[21]
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CALCULATIONS: 5170 kg/hr of molasses can be produced from 172333.33 kg of sugarcane 1 ton of sugarcane can produce 240 kg of raw sugar Therefore, 172333.33 kg of sugarcane can produce 41360 kg raw sugar From 172333.33 kg of sugarcane, 48253.33 kg of bagasse can be produced Cane trash and remaining residues amounts to 77550 kg 50,000 kg/hr of sugarcane bagasse can produce 6599.36 kg/hr bio ethanol Therefore, 3216.25 kg of bioethanol is produced from bagasse
Kg (inlet) 172333.33
Components Sugarcane Sugar Molasses Bagasse Cane trash + residues 2nd generation bioethanol Fuel and electricity 24367.93(50.5%bagasse) 48253.33
Kg (outlet)
41360 5170
77550 3216.25 23885.4 172333.333
172333.333
Total Table7.8 Overall material balance of all products of biorefinery
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Chapter- 8 ENERGY BALANCE

Energy Balance Reactions: For Non-reaction processes: H=miHi(outlet)-miHi(inlet) Q-Ws=H+Ek+Ep Ws=0 (when no moving parts) Q=U (for closed systems) Q=H (for open systems) 8.1 FERMENTER: Stoichiometric Equation: C12H22O11+H2O2C6H12O64C2H5OH+4CO2 T=298K (assuming isothermal conditions) P=1atm Energy Balance in fermenter: H=4(Hformation Ethanol) +4(Hformation CO2) -2(Hformation glucose) Enthalpies of formation [22] Hformation (Ethanol) =-276.5kJ/mol Hformation (CO2) =-393.5kJ/mol Hformation H2O (l) = -285.8 kJ/mol Hformation H2O (g) = -241.8 kJ/mol Hformation (glucose) (g) =-1250 kJ/mol Hformation (sucrose) (g) =-2220kJ/mol Therefore, H= [4(-276.5) +4(-393.5)-2(-1250)] =-180kJ/mol CALCULATIONS: From the stoichiometric reaction: Sucrose balance: Min of molasses=51,700 kg/hr
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But, sucrose content in molasses=52% Sucrose=0.52*1240, 800=26,884 kg/hr Moles of sucrose=26884/342=78.6 mol Nout of sucrose= 1344.16/342=3.93 mol Water balance: Nin=206,800/18=11488.88 moles Nout=197495.85/18=10,971.99 moles CO2 balance: Nout =13143.288/44=298.71 moles C2H5OH balance: Nout= 13,740.71/46=298.71 moles nin (mol) 15.117 1148.89 0 0 Hin(kJ/mol) -2220 -285.8 -276.5 -393.5 species C12H22O11 H2O C2H5OH CO2 nout(mol) 7.256 1141.646 29.871 29.871 Hout(kJ/mol) -2220 -285.8 -276.5 -393.5
Table 8.1 Energy Balance across the fermenter Now, extent of reaction: = [(nC12H22O11) out-(n C12H22O11) in]/ ( C12H22O11) = (7.256-15.117)/1=-7.861 mol/hr Now, energy Balance: Q-Ws=H+Ek+Ep Now, Ek=0 (Kinetic changes) Ep=0(horizontal unit) Q-Ws=H Assumption: Power input=1.6 watt/kg of input Total input=275213.135kg/hr Power Input=Ws=440.341 Ho=793.126 KW
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Q=H+Ws=793.126+440.341= 1233.47kw/hr 8.2 DISTILLATION COLUMN: Assumptions: Temperature of distillate=82oC Boiling point of ethanol=78.5oC Boiling point of water=100oC Feed enters at 25oC CALCULATIONS: For ethanol. In distillate: H=Hv + CpdT=38.58 + = 44.034 kJ/mol For water in distillate: H=Hv+ + dT =38.58+5.516
=40.656+5.655-1.6211=44.69 kJ/mol Ethanol in residue: H =Hv+ Water in residue: H =Hv+ =40.656+75.4*10^-3(100-25) =46.311 kJ/mol =38.58+103.1*10^-3(100-25) =46.3125kJ/mol
Species
Feed nin(mol) Hin(kJ/mol) 0 9.57
Distillate nout(mol) 222.847 2562.74 Hout(kJ/mol) 44.034 44.69
Residue nout(moles) 75.835 9496.26 Hout(kJ/mol) 46.3125 46.311
Ethanol Water
301.20 9632.19
Table 8.2 Energy balance across the Distillation Column H=475455.042 kJ Q=mCpT=H Cp=43.99kJ/kgoC T=75oC ,Therefore, Steam required, m=144.11 kg/hr
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8.3 RECTIFICATION COLUMN: Assumptions: Feed Temperature- 78.5oC Distillate Temperature-78.5oC Residue-100oC
Species
Feed nin(mol) 258.59 146.18
Hin(kJ/mol) 0 11.45
Distillate nout(mol) 258.15 34.72
Hout(kJ/mol) 38.58 40.656
Residue nout(moles) 0.44 111.46
Hout(kJ/mol) 40.797 40.656
Ethanol Water
Table 8.3 Energy Balance across the Rectification column H=14246.71kJ/mol Q=mCpT=H therefore, m= 4.32kg of steam/hr 8.4 DEHYDRATION COLUMN Species Ethanol nin(mol) 258.152 Hin(kJ/mol) 0 nout(mol) 35.746 222.406 3.806 2.856 28.06 Hout(kJ/mol) 38.58 34.61 40.656 37.75 37.7531
Water
34.722
11.45
Table 8.4 Energy Balance of the dehydration column H=10,000 KJ Therefore, steam requirement is, m=10.571kg of steam/hr
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Chapter-9 CONTROL STRATEGY

9.1 CONTROL STRATEGY OF THE DISTILLATION COLUMN: For the production of anhydrous bio ethanol from the molasses, we have utilised two distillation columns-first one takes beer(which is containing 7.3% ethanol by weight) as feed and the top product of which is hydrous ethanol(80% by weight of ethanol) and the bottom product contains vinasse which is further treated to give biofertilizers. The second distillation column used is the Rectification Column after the first distillation column which gives 95% by weight of ethanol as the top product and the other residues are taken from the bottom. In the figure 9.1 given below, we have discussed the control strategy of the first distillation column. [23]
Fig 9.1 Control Strategy of the distillation column
FC-Flow Controller
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LC-Level Controller PC-Pressure Controller TC-Temperature Controller
9.2 DESCRIPTION: Controlled variables include product compositions, column temperatures and pressure, and tower and accumulator levels. Manipulated variables include reflux, coolant, heating medium and product flows. Load and disturbance variables include feed-flow rate, feed composition, steam-header pressure, feed enthalpy, environmental conditions (e.g., rain, barometric pressure and ambient temperature) and coolant temperature. The five manipulated variables are so assigned to the five controlled variables that the heat input at the reboiler (QB) and the distillate composition (y) are fixed and, therefore, the bottoms flow (B) and composition (x) are allowed to change with the variations in feed flow (F) or composition (z). In a binary distillation process, the number of independent variables is eleven, and the number of defining equations is two. Therefore, the number of degrees of freedom is nine. Consequently, the maximum theoretical number of automatic controllers that can be used on a binary distillation process is nine, but usually only five are controlled. These variables are the compositions of the bottom and top products (x and y), the levels in the column base and accumulator, and the column pressure. The manipulated variables that can be assigned to control these are the distillate ( D), bottoms (B) and reflux(L) flows, the vapor boil-up (V set by heat input QB), heat removal (QT) and the ratios of L/D or V/B. Column pressure almost always is controlled by heat removal (QT). This loop closes the heat balance around the column, while the levels are controlled to close its material balance. No matter how we make that selection, these two loops will interact. A change in one will upset the other because whenever the openings of their control valves change, the material and heat balance of the column will also change. Thus, we are able to control the composition of the distillate which is 80% (by wt) of ethanol and residue which is 2% (by wt) of ethanol, the flow rate of distillate which is 1281.37 kg/hr and of residue which is 17576.52 kg/hr. Temperature and pressure for the stable and efficient working of distillation column is also controlled.
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Chapter-10 DETAILED EQUIPMENT DESIGN

10.1 LIST OF EQUIPMENTS: The lists of major equipments in the process flow diagram (Fig 5.3) are as follows: Equipment 1 Equipment 2 Equipment 3 Equipment 4 Equipment 5 Fermenter Yeast treatment Tank Centrifuge Distillation Column Molecular Sieve Dehydrator
10.2 PROCESS DESIGN OF THE EQUIPMENTS: Equipment 1: FERMENTER Standard specifications of a Fermenter: [24] 1. 2. 3. 4. 5. 6. Material: Stainless steel, free of cervices, mechanically ground and polished Approx proportions: Height/diameter=2 Impeller/vessel diameter=0.35 Baffle width/vessel diameter=0.1 Maximum working volume=75-80% Minimum working volume=25% Ports and penetrations, Steam-sterilizable inoculation/addition port Air inlet line Air exhaust line Well for temperature control sensor and temperature recording sensor Well for thermometer Water inlet line to jacket of vessel Side-entry port for pH electrode Foam breaking: Injection port provided for chemical breaking; mechanical breaker optional, consists of a double disk rotated at high speed with its own drive 7. Agitation system has 3 six-bladed turbine impellers adjustable along the shaft, maximum tip speed of 1200ft/min, standard drive of 40HP for a 5000-L vessel, bottom drive standard, top drive optional
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8. Controls and monitors: liquid level, pH, dissolved oxygen, reduction-oxidation potential, air rate, temperature, optional automatic sterilization cycle control, rupture disk on vessel, relief valve on jacket. Process Design of a Fermenter: Feed to fermenter = 27521.317 kg/hr (from Table 7.1) Outlet concentration of ethanol in fermenter=7.3% No. of working days = 200 days Total time taken for fermentation i.e. residence time = 21 hrs avg = 1128.508 kg/m3 Volumetric flow rate, Q= 27521.317 / 1128.508 Q=24.38 m3/hr Volume of fermenter, V= Q*residence time =24.38*21 V=511.98 m3 Typical size of fermenter used= 66 m3 200 m3 Therefore, 4 fermenters of volume= 127.995 m3 each Rate of dissolution of gas into fermenter: dc/dt= Kla *(Cs-C) Where dc/dt = rate of O2 transfer Kla = overall mass transfer coefficient Taking aspect ratio L/D= 7.5 Superficial velocity, u=14 m/hr For Kla= 12 /hr Now v= (/4)*D*D*L 0.85*127.995= (/4)*D*D*(7.5D) D=2.643m L=19.825m Now O2 flow rate required, q= area*us Q=76.81(approx...) m3/hr --------- (ii) ---------- (i)
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Equipment 2: YEAST TREATMENT TANK Here, yeasts are grown separately to be added to the fermenter. The nutrients Ammonium Sulphate (NH 4)2SO4 are added to facilitate proper growth of yeast and sulphuric acid H 2SO4 is added to control the pH of the mixing tank. The most popular yeast strain used is Saccharomyces cervisiae. It is able to produce and tolerate high concentrations of ethyl alcohol. It a lso possesses uniform and stable characteristics. Data: 1. 2. Material of construction is Stainless Steel Feed Rate: (from table 7.2) 3. 4. H2SO4=55.692kg/hr Yeast culture=1292.5 kg/hr
Mass flow rate=4071.5 kg/hr Density of components mixture =1426.085 kg/m3
Or, Volumetric flow rate=2.855m3/hr Assuming residence time to be 8 hrs Therefore, calculating the volume of the tank or vessel; V=2.855*8=22.8 or 25 m3 Let us assume aspect ratio H/D=4 Therefore, diameter and height can be calculated: V=D2H/4=25 D=2.99m =3m and H=8m Equipment 3: CENTRIFUGE Centrifuge helps in the removal of insoluble, the capture of product as a solute in a particulate free liquid. Here, centrifuge is separating biomass from ethanol which is formed in the fermentation tank and then ths ethanol of 7.4% concentration is sent to the distillation column for further separation. Data: 1. 2. 3. Ethanol concentration=7.2% Slurry feed rate in=26805.497 kg/hr Density of the components(in kg/m3): Ethanol= 789
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4. Calculations: mix inlet=(789*0.058)+(1000*0.835)+(1587*0.005)+(550*0.1015)=1004.32 kg/m3 Q=overflow rate=0.53*(feed rate/density) =0.53*(26805.497/1004.32) =14.15 m3/hr =solid density-liquid density=361 kg/m3 g=*g*d2/18 Where, g= velocity of the particle d=diameter of particle g=acceleration due to gravity =viscosity of water Let us assume d=100m=100*10^-6 m water=1*10^-3kg/ms Therefore, g =361*9.8*(100*10^-6)2/ (18*10^-3) =1.965*10^-3 m/s =Q/ (2*g*), =area -------- (v) ---------- (iv) --------- (iii) Water=1000 Biomass=550 Sucrose=1600
Mass fraction of the components(as per table 7.3) Ethanol=0.0513 Water=0.7666 Biomass=0.08954 Sucrose=0.0925
=12.96/ (2*4.426*10^-3*0.8) =1829.95m2 = (/4) D2 Or D= [(4*)/] ^0.5 D=7.46m or 8m Assume L/D ratio=0.8
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L=5.97 or 6m V= (*D2*L)/4 =301.5m3 or 302 m3 Equipment 4: DISTILLATION COLUMN Distillation Column is used to distil 80% ethanol as the top product. Distillation Column receives its feed from the centrifuge containing 7.4% by weight of ethanol which undergoes distillation giving 80% ethanol by weight from top and 20% by weight of water which further goes to rectification column for further separation to 95% by weight of ethanol. The bottom product of the distillation is vinasse. It is the residue left which acts as good fertilizer and a source of methane. Data: Table 10.1 gives the material balance of the components across the distillation column: S.No Component kmol/hr 1. 2. 3. Ethanol Water Sucrose Total 29.871 856.235 7.256 893.362 Feed Zi 0.0334 0.958 0.0081 1 Distillate kmol/hr 22.34 14.273 0 36.613 xD 0.61 0.389 0 1 Bottom kmol/hr 7.819 841.229 7.256 856.304 xW 0.00913 0.982 0.00847 1
Table 10.1 Material balance across the distillation column For calculation of vapour pressure of ethanol, we employ Antoine equation: log10P= A-B/ (T+C) P is the vapour pressure, ToC The values of Antoine constants, A, B and C for H2O and C2H5OH are given in Table 10.2: -------- (vi)
A H 2O C2H5OH 8.07131 8.20417
B 1730.63 1642.89 Table 10.2 Values for Antoine Constants
C 233.426 230.3
Calculations: 1. Calculation of vapour pressure of ethanol and water:
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Putting the values from Table 10.2 in equation (vi); Ethanol Log10P= 8.20417-1642.89/ (73.1+230.3) P=615.516 mm Hg P (C2H5OH) =615.516 mm Hg Water Log10P=8.07131-1730.63/ (73.1+233.426) P=266.294 mm Hg P (H2O) =266.294 mm Hg 2. Calculation of minimum no. of plates: A is the light key component ie ethanol B is the heavy key component ie water According to Fenskey equation: Nmin=log [(xA/xB) d*(xB/xA) B]/log (avg) =log [(0.61/0.389)*(0.982/0.00913)]/log (2.31) =6plates 3. Calculation of minimum reflux ratio (Rmin): 1-q=i iZi/ (i-) q=0 1= (2.31*0.61)/(1- ) + (1*0.389)/(2.31- ) =2.7545 Vmin=i iDxi,D/(i-) = [2.31*22.34*0.61/ (2.31-2.7545)] + [1*14.273*0.389/ (1-2.7545)] =73.9841 Vmin=73.9841 kmol/hr Lmin=Vmin-D D=22.34 kmol/hr ------ (ix) Underwood equation --------- (viii) -------- (vii)
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Lmin=73.9841-22.34 Lmin=51.6441kmol/hr Now, Rmin=Lmin/D =51.6441/22.34=2.311 4. Calculation of Reflux Ratio R=1.5*Rmin =1.5*2.311 R=3.465 5. Calculation of no. of plates X=R-Rmin/(R+1) Y=N-Nmin/ (N+1) X= (3.465-2.31)/4.465=0.2587 Y=1-exp [(1+54.4X/11+117.2X)*(X-1/X^0.5)] Y=1-exp [0.3648*(-1.457)] Y=0.4124 0.4124=N-6/ (N+1) N=11plates Assuming 80% efficiency, Actual no of plates N=11/0.8=14 plates 6. Calculation for position of feed plate: NR/NS= [(ZHK/ZLK)*(xLK, W/xHK,W)*W/D]^0.206 = [(0.61/0.389)*(0.00913/0.982)*856.304/36.613]^0.206 =0.801 NR+NS=N 0.801NS+NS=14 NS=8 NR=6 Feed plate is 6th plate from the top 7. Determination of column Diameter and height: Tray Spacing=Lt=0.8m Height of column=H=14*0.8=11.2m Density of liquid, l=895kg/m3 Density of vapour, v=0.7724 kg/m3 Uv is the maximum allowable velocity of vapour Uv= (-0.171Lt2+0.27Lt-0.047)/ [(l-v)/v] ^0.5 Uv =2.0265 Vw= max vapour rate ------ (xv) ------- (xiv) ------- (xii) ------- (xiii) ------- (xi) ------ (x)
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Vw=0.357 kg/s Column Diameter, Dc= [4Vw/ ( v*uv)] ^0.5 Dc=0.6 Plant Design: Column diameter, Dc = 0.6m Column area, Ac= (Dc^2)/4 = 0.283 m2 Downcomer area, Ad= 0.12 *Ac =0.03396m2 Net area, An= Ac-Ad=0.2491m2 Active area, Aa =Ac-2*Ad= 0.2151m2 Hold area, Ah=0.1*Aa =0.02151 m2 Weir length, lw= 0.76*Dc =0.456m Assumptions: Weir height, hw = 50 mm Hole diameter, dh= 5mm Plate thickness = 5mm Check Weeping: Max liquid rate, Lw= 4 .31kg/s Min. liquid rate, Lw= 4.31*0.7 = 3.017kg/s Max. how = 750 [Lw/(l*Lw)]^(2/3)=36.10 mm Min. how =750 [Lw/(l*Lw)]^(2/3) =28.46 At min. rate hw + how= 79mm K2= 30.3 Uh (min) = [{K2-0.9(25.4-Dh)}/ (v) ^0.5] = 8.63m/s Actual min. vapour velocity = min. vapour rate/ Ah [refer eq. 11.84 page 571, R&C vol. 6] [refer fig. 11.3 page 571, C& R Vol 6] [ref fig. 11.31, page-572, C&R volume 6] ------ (xvi)
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= 11.61m/s So, minimum operating rate is above weeping rate. Equipment 5: MOLECULAR SIEVE DEHYDRATOR Molecular Sieve dehydrators are used to dehydrate a liquid feed of 95% by weight of ethanol to 99.5% by weight of product of ethanol. For this purpose, we use Pressure Swing Adsorption. Design Specifications: [25] 1. 2. 3. Material of Construction for vessel- Stainless Steel Types of sieves- Type 3A molecular sieve, made up of alumina-silicate or zeolite Design of this equipment consists of the 2 parallel columns one of which is adsorbing while the other is desorbing or standby. 4. The liquid feed is first heated, vaporised then sent to the adsorbing column where it is dehydrated by a packed bed of Type 3A molecular sieve. 5. 6. Regeneration time -6.33 min Adsorption time- 23.9 min While the adsorption takes place, within 6.33 min, 40% of the dry ethanol product is sent to help regenerate desorbing column while 60% is condensed to the final product, while for the other 17.6 min, regenerating purge stream is no longer needed and 100% of the product stream is condensed to the final product. 7. 8. Bed 1(adsorbing column) pressure 107.3kPa, Inlet and Outlet Temperature-120oC Breakthrough time is the time at which water is first observed in the product. The time at which a 99.5% ethanol is reached is calculated using theoretical breakthrough curve. 9. Sequencing: adsorption cycle ends, bed is depressurised, and flow is diverted to next bottle set for adsorption. Heat and pressure are transferred to the next bottle and are not lost. 10. Molecular sieve: 1521 ft3per bed. Beds are 3.05 tall and 10 ft in diameter. Working capacity was set at 1%, 5 minutes cycle.
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Fig 10.4 Valves sequencing for adsorption and regeneration steps [26] 10.3 MECHANICAL DESIGN OF THE EQUIPMENTS: Equipment 2: YEAST TREATMENT TANK Data from process design: Design: 1. Design of Shell: Design pressure is 10% excess than pressure inside Design pressure=1.1*0.3=0.33N/mm2 t= [pDo/ (2fJ+p)] +C ------- (xvii) Outside Diameter of vessel (Do) =3000mm Material of Construction- Stainless steel Allowable stress, f= 130 N/mm2 Internal Pressure, p=0.3 N/mm2 Joint efficiency=0.85 Corrosion Allowance=3mm Crown Radius=1200mm Knuckle Radius=180mm Material of flanges is Carbon steel Material of construction of head=Stainless Steel
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t= [(0.33*3000)/ (2*130*0.85) +0.33] +3 Or t=990/221.33=4.47mm+3=7.47mm or 8mm Check for loadings: a) Tangential or hoop stress: ft =p (Di + t)/2t=p(Do-t)/2tJ ft = 0.33(3000-8)/(2*8*0.85)=72.6 N/mm2 (within permissible limit) b) Stress in axial direction due to internal pressure: f1=pDi*t/4 = (0.33*2984*8)/4=19.69N/mm2 i.e within permissible limit c) Stress due to weight of vessel: Volume of cylindrical portion=60m3 Volume of 2 dished ends can be calculated: Volume of head for knuckle radius to be min 6% of internal diameter of vessel V=0.081Di3=0.081(2.984)3=2.152m3 The straight length of dished end is 40mm Volume of cylindrical portion=0.045m3 Therefore, total volume of dished ends=2(2.152+0.045) =4.394 Total volume of vessel=60+4.394+vol of nozzles=65m3 Density of material is taken to be that of water=1000kg/m3 Therefore, total weight of the liquid filled in the vessel=65*1000=65000kg ------ (xviii)
Shell is fabricated out of SS plate of t=8mm Estimated wt= *D*H*t* D=3000-8=2992mm H=7480mm t=8mm =8020kg/m3 W=2.992*7.480*0.008**8020 W=4511.04kg or 4512 kg Wt of dished ends: W= (/4)*B2*t* Where, B is the blank diameter B=1.024Do+0.67R1+2Sf R1=0.06*R=0.06*3000=180mm B= (1.024*3) + (0.67*180)+(2*0.04) ------- (xx) -------- (xix)
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B=3.2726m W= (/4)*(3.2726)2*0.008*8020 W=539.68kg or 540kg We have 1 dished end=W=540kg Wt of carbon steel body flanges=160.5kg Wt of vessel including nozzles, manholes and support is considered to be 10-20% higher than the sum of weights of vessel shell, dished ends and flanges Wt of vessel=1.15(4512+539.68+160.5) =5994kg Total weight=vessel + content=65000+5994=70,994kg or 71000kg From eq, f2=W/ [t(Di+t)]=71000/(*8*2992) = 0.944kg/mm2=9.25N/mm2 Assuming no wind load, f3=0 Fa=f1+f2+f3 =19.69+ (-9.25)=10.44N/mm2 Assume T=500,000N-mm due to offset piping, Stress due to offset piping is given by: fs=2T/[tDi(Di+t)]=(2*500,000)/(*8*2984*2992) =0.00445 N/mm2 Combining the above stresses on the basis of shear strain energy theorywe get equivalent stresses from given equation (xxii): fR=[ft2-ft*fa+fz2+3fs2]0.5 = [(72.6)2-(72.6*10.44)+(10.44)2+3(0.00445)2]0.5=67.983N/mm2 Both fr and fa are less than permissible stress ie 130N/mm2 Therefore, thickness of 8mm is acceptable
--------
------ (xxi)
(xxii)
2.
Head design-flanged and shallow Dished head For torispherical head, Th = (p*Rc*W)/(2f*J) W=0.25{3+ (Rc/R1)0.5}=1.77 Th = (0.33*3000*1.77)/(2*130*0.85)=7.92mm or 8mm Straight length of dished end=40mm ------ (xxiii)
3.
Mechanical design of an agitator: Data: Vessel diameter=3000mm
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Internal pressure=0.33 N/mm2 Diameter of agitator (impeller) =1000mm Width of blade=150mm Thickness of blade=16mm Speed=250rpm Liquid in vessel is sulphuric acid Density=1840kg/m3 Viscosity=26.7cP Overhang of agitator shaft=2000mm Permissible shear stress in shaft=55N/mm2 Elastic limit in tension=246N/mm2 Modulus of elasticity=1.95*10^5 N/mm2
(a) Power calculation: NRe= (Da2*N*)/ = {1*(250/60)*1840}/(26.7*10^-3) =2871.41 From graph, Np=4.5 P=Np**N3*Da5 =4.5*1840*(250/60)*1 =598958.33 Gland loss is assumed to be 5% and efficiency of power transmission is 95% Motor rating=598958.33/(0.95*0.95)=663665.74=889.63hp or 890 hp ------- (xxv) -------- (xxiv)
(b) Shaft design:
P=890hp=663940 W Tc=P/ (2N) =663940/ (2 (250/60)) =25360.64N-m Maximum torque during startup=1.5*25360.64 =38040.96N/m =38040*10^3 N/mm Permissible shear stress =55 N/mm2 Zp=Tm/fs =38040*10^3/55=691653.8182 mm2 Zp = (/16) d3 Therefore, d i.e. shaft diameter =152mm Fm=Tm/0.75Rb=38040*10^3/(0.75*500)
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Fm=101440 N
Maximum bending moment M at the bearing point from where the shaft overhangs; M=Fm*l M=101440*2000=202880 N-m Me=1/2{M+ (M2+Tm2)0.5} =1/2{202880 + (202880 +38040 ) } =204647, 722 N- mm f=Me/ {(/32) (ds) 3} Or f=204647722/ {(/32)*(152) } =593.57 N/mm2 Higher than the permissible elastic limit 246 N/mm2 If we take diameter=210mm F=225 N/mm2 which is within the elastic limit
3 2 2 0.5
------ (xxvi)
------- (xxvii)
------- (xxviii)
(c) The critical speed consideration: l =Wl3/3EI W=Fm=101440 N L=2000 mm E=1.95*10^5 N/mm2 I= (/64)*d4 I= (/64)*(2104) =1527.45*10^6 mm4 1= (101440*2000^3)/(3*1.95*10^5*1527.45*10^6) =0.908mm Deflection due to impeller and hub weight is 40 kg 2= {(40*9.807)*20003}/ (3*1.95*10^5*1527.45*10^6) =3.51*10^-3 mm=0.0035 mm Shaft weight per unit length W= (/4) d2*= (/4) (210/1000)2*7850 =271.89kg/m=0.272 kg/mm s =Wl4/8EI={(0.272*9.807)*(2000)^4}/(8*1.95*10^5*1527.45*10^6) =0.018mm Nc =946/ [1+ 2+ 3/1.25]0.5 Nc =483.12rpm Present speed is 250 rpm which is 51% of critical speed which is on the safer side ------- (xxix)
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(d) Design of Blade: BMmax=Fm (0.75Rb-Rh) =101440(0.75*500-210) =167360N-mm F=BMmax/Z Z=bt * bw2/6 F=22.31N/mm2 which is acceptable Equipment 4: DISTILLATION COLUMN 1. 2. 3. Data from process design: Shell inside diameter No. of trays Tray spacing Top disengaging space Bottom separator space Length of column (tangent to tangent) Skirt height Operating temperature Operating pressure Design temperature Design pressure Selection of shell material: Stainless steel Calculations: (a) Calculation of Thickness: Allowable design stress for the material specified,f= 1.18MN/m2 Welding joint efficiency factor, J=0.85 t = [PDi/ (2*f*J-P)] = [111.46x 10^3x0.6/ (2x1.18x10^6x0.85-111.46x10^3)] = 0.03635m Corrosion allowance = 3mm Thus thickness, t=40 mm Outer diameter Do= Di + t= 0.64m [ref appendix A, page 261. BCB] Di= 0.6m N=14 lt=0.8m 1m 1.75m 13.95m 4.5 m 82oC 101.325 KN/m2 82+8=90oC 1.1*101.325 = 111.46 KN/m2 [Ref art 2.8 page 260, BCB] ------ (xxx)
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(b) Calculation of axial stress due to pressure: zp= PDo/(4*t) = 111.46x10^3x0.64/ (4*0.04) =0.446 MN/m2
(c) Calculation of axial stress due to dead loads: (i) The stress induced by shell weight at a distance X m from the top: zs = Ws/(*t*(Di+t)) Assume Ws= 7850g zs =0.96*X MN/m2 (ii) The stress induced in the shell due to insulation at a distance X m from the top:
zi=
, where g is acceleration due to gravity
Wi/(*t*(Di+t))
Assume t (ins) = 0.075m Wins =5640g = (0.075x5640xXx10^-6)/0.04 zi =0.01*X MN/m2 (iii) The stress induced in the shell due to liquid hold up: zl=Wl/(*Do*t) Where Wl= wt. of liquid supported for a distance X m from the top Wl= (/4)*D*D x weir height x 9.8 x Wl =157.632 zl= 157.632/(*0.64*0.04) zl =0.00196MN/m2 (iv) The stress induced in the shell due to attachments: (a) Weight of top head = 7.5 x10^-3 MN (b) Weight of ladder =3.65x10^-4 MN (c) Weight of trays = no. of trays x tray loading Tray loading=1KN/m2 of tray area [ since weight =Vg]
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= 14x 1000x *D*D/4 = 0.00396 MN Thus total weight of attachments = 0.011825MN za= Wa/(*D*t) = 0.147MN/m2 Thus total dead load stress acting along the axial direction of shell at point is then given by zw=zs+ zi+ zl+ za zw= 0.97*X + 0.013785MN/m2 (v) Calculation of stress due to wind: Since the wind pressure does not remain constant throughout the height of the vessel it is recommended to calculate the wind load in 2 parts for top and bottom part separately. But here in this case since height of vessel is less than 20m pressure is calculated for bottom part. Pbw=k1*K2*p*h*Do Where Pbw is the total force due to wind load acting on vessel h is the height of the vessel p is the wind pressure p= 0.7-1 KN/m2 (coastal area) Do is the outer diameter including insulation Assume thickness of insulation=0.075m k1 is the coefficient depending upon the shape factor k1=1.4 (for flat plate 90o the wind) k1=0.7(for cylindrical surface) k2 is the coefficient depending upon the period of 1 cycle k2=1 (if period of vibration is 0.5 sec or less) k2=2 (if period exceeds 0.5 sec) thus, Pbw=0.7*1*0.4*10^3*X*(0.64+2*0.075) Pbw=221.2X N Now the BENDING MOMENT at the base of the vessel due to wind load is determined by the following equation: Mw=Pbw*h/2 =221.2X*X/2 Mw=110.6X^2 N-m [ref table 9.1 page 146, BCB] p=0.4 KN/m2 (area with moderate wind)
The resulting BENDING STRESS in the axial direction is then computed from the following co relation: zwm= 4Mw/[*t(Di+t)*Di] Where,
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zwm is the longitudinal stress due to wind moment (compressive on downward side and tensile on upward side) Mw is bending moment due to wind load Di is the inner dia of shell t is the corroded shell thickness zwm= 4*110.6 X^2/[*0.04(0.64)*0.6] zwm =0.009168 X^2MN/m2 (vi) Calculation of resultant longitudinal stress (a) TENSILE z(tensile) = zp + zw+ zwm =0.446 + 0.97*X + 0.013785 +0.009168 X^2 MN/m2 z(max.) =1.18 MN 1.18=0.446 + 0.97*X + 0.013785 +0.009168 X^2 MN/m2 0.009168 X^2 +0.97X+0.456=0 Solving for X, X= 17.55 m >> 13.95m Thus assumed thickness is correct. (b) COMPRESSIVE z(compressive)= zwm + zw- zp = 0.97*X - 0.446+0.009168 X^2MN/m2 z(compressive max.)= 0.125*E*(t/D o) =0.125*(2x10^7)*(0.0427/0.82) = 13.0256 MN/m2 13.0256=0.97*X - 0.446+0.009168 X^2MN/m2 X= 19.23 >> 17.55 m Thus assumed thickness is correct. (vii) Design check by equivalent stress consideration s= (r2 r*z+ z2)0.5 Now, r= P(Do-t)/(2*t)= 111.46x10^3*(0.64-0.04)/ (2*0.04) r= 0.836 MN/m2 z(tensile)= 1.576MN/m2
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Now substituting these values s=1.06 MN/m2 < 1.18 MN/m2 Thus under operating conditions shell thickness of 0.04 m is safe.
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Chapter-11 ECONOMIC EVALUATION

11.1 PROJECT COST: [27] Purchased Equipment Cost: Cost index in 2001 = 397; Cost Index for 2013=585 Cost Index Factor=cost index 2013/cost index 2001= 585/397=1.4736 Material of Construction-Stainless Steel-316 The costs of Storage Tanks as used in our process are given in Table 11.1 Correlations Used: log10 Cpo=K1+K2 log10 A +K3[log A]2 S.No. Compounds Cpo= Equipment Cost Storage Capacity(m3/3 days) 1. 2. Storage Tank(Molasses) Storage Tank (Ethanol) 232.65 94.066 52480 42619 77335 62803 Cost in US$ 2001 Cost in US$ 2013
Table 11.1 Cost of storage tanks The costs of Process Equipments estimated using correlations are given in Table 11.2 Correlations Used: log10 Cpo=K1+K2 log10 A +K3[log A]2 ; CBM=Cpo[B1+FP*FM*B2] S.No 1. 2. 3. 4. Equipment Yeast Treatment Tank Fermenter Centrifuge Distillation Column(Tower) Distillation Column(Trays) 5. Molecular Sieve Dehydrator(Tower) Molecular Sieve Dehydrator(Packing) Attributes Volume(m3) Volume(m ) Power(kW) Volume(m ) Area(m ) Volume(m3) Volume(m )
3 2 3 3
CBM= Bare Module Cost Cpo($) 25 128 200 4.488 0.126 1.1 0.831 21,590.42 83,057 21,225.89 1,994.24 820.352 3028.323 234.96 56,851 83,776 41,136 60,618 CBM(2001)($) 174,321 670,602.218 103,158 CBM(2013)($) 256,879 988,199 152,014
Table 11.2 Cost of Process Equipments .The combined table of all the equipments is shown in Table 11.3
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S.No. Equipments No. of Equipments 1. 2. 3. 4. 5. 6. Storage Tank(molasses) Storage Tank(ethanol) Yeast Treatment Tank Centrifuge Fermenter Distillation Column (tower) Distillation Column (trays) 7. Molecular Sieve Dehydrator (tower) Molecular Sieve Dehydrator (Packing) 8. 9. Heat Exchangers Pumps Total Table 11.3 Cost of all the equipments Therefore, Total Bare Module Cost CBM= $ 7,597,481 FIXED CAPITAL INVESTMENT: CBM= Direct Cost +Indirect Cost CTM=1.18* CBM CGR=CTM+0.5 From Calculations, Total Fixed Capital Investment (FCI) = $12, 763,768 = 6.892*10^8 MANUFACTURING COSTS: COM=DMC+FMC+GE DMC= Direct Manufacturing Costs FMC= Fixed Manufacturing Costs GE= General Expenses COM= 0.280 FCI +2.73*COL+1.23[CUT+CWT+CRM] Where, COL= Cost of operating labor CUT = Cost of Utilities 8 4 2 167552 352,192 198,000 7,597,481 3 3 1 1 6 2 121,236 232,005 188,409 256,879 152,014 5929,194 CBM($)
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CWT= Cost of waste Treatment CRM= Cost of raw materials Cost of Raw Materials: S.No 1. 2. 3. 4. Raw materials Molasses H2SO4 (NH4)2SO4 Yeast Culture Total Cost ($) 3,216,889 16,088.79 185,725.33 638,400 4,057,103
Table 11.4 Cost of Raw Materials Cost of utilities: S.No 1. 2. Utility Cooling Water Steam Total Cost ($) 123.09 1,032,485 1,032,608 Table 11.5 Cost of Utilities Cost of Waste Treatment= 5% of CRM= $ 202,855 Cost of Operating labor NOL= (6.29+31.7 P2+0.23 Nnp) 0.5 Nnp=12, p=0 NOL=no. of operating labor/shift=3 COL=77,778 $/yr Therefore, COM= $ 8,335, 909 REVENUES: Market price of ethanol = 42/litre Annual Production= 1030.803 kg/hr *24*200*53.232=263,384,186=$4,877,485 The cash flow chart for our project is in Table 11.6
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Yr Inv. Depr. Revenue COMd Tax. Income Tax @32.45% Net profit Cash Flow Cumulative Cash flow Discounted Cash Flow Cumulative Discounted Cash Flow 0 1 2 -0.675 -3.446 -3.446 -1.216 3 4 5 6 7 8 9 10 11 12 1.216+ 0.675 1.419 1.127 0.895 0.711 0.564 0.448 0.356 0.283 0.224 0.178 5.871 5.871 5.871 5.871 5.871 5.871 5.871 5.871 5.871 5.871+ 0.6892 Table 11.6 Cash Flow Chart (all figures in 1*10^8) 11.2 CASH FLOW STATEMENT: 1. 2. Cost of land= 45 acres*15 lacs= 0.675*10^8 FCI= 6.892 *10^8 a. b. 3. 4. 3.446 *10^8 in first year 3.446 *10^8 in second year 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 -0.048 0.244 0.476 0.66 0.807 0.923 1.015 1.088 1.147 1.193 0.0792 0.154 0.214 0.262 0.299 0.329 0.353 0.372 0.387 -0.048 0.1648 0.322 0.446 0.545 0.624 0.686 0.735 0.775 0.806 -0.048 1.2918 1.217 1.157 1.109 1.072 1.042 1.018 0.999 2.8892 -8.831 -7.5392 -6.3222 -5.1652 -4.0562 -2.9842 -1.9422 -0.9242 0.0748 2.964 -0.036 1.108 0.9982 0.956 0.893 0.79 0.682 0.576 0.492 1.097 -6.648 -5.54 -4.54 -3.586 -2.693 -1.903 -1.221 -0.645 -0.153 0.944 -0.675 -3.446 -4.662 -0.675 -4.121 -8.783 -0.675 -2.983 -2.954 -0.675 -3.658 -6.612
Salvage Value= 10% of FCI = 0.6892 *10 ^8 Working Capital TCI=FCI+0.15 TCI TCI= (6.892 *10^8)/0.85 = 8.108*10^8 WC=15% of TCI = 1.216 *10^8
5.
Calculation of Revenues: a. b. Ethanol= $4,877,485 Biofertilizer=$5,994,462 Total= 5.871 *10^8
6.
Depreciation Calculation(by Written-down Value Method) VA=Vo (1-DWDV) n n=10, VA=6.892, Vo =6.892
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D=0.206=20.6% Similarly, other values of depreciation as shown in table 11.6 NON-DISCOUNTED PARAMETERS: 1. Payback Period: Land+WC=0.675+1.216=1.891 PBP=7+ (-1.9422+1.891) / (-1.9422+0.9242)=7+0.05=7.05years 2. 3. 4. Cumulative Cash Price=2.964*10^8 Cumulative Cash Ratio=11.795/8.831=1.336 ROROI=Avg. annual net profit/FCIL-S=0.0815=8.5%
DISCOUNTED PARAMETERS: 1. Discounted Payback Period(DBPB): Discounted value of land + WC=0.675+1.216/1.12 = 1.68*10^8 DBPB=6.33 years 2. 3. Net Present Value(NPV)= 0.994 *10^8 Present Value Ratio(PVR)= all positive cash flows/all negative cash flows =7.5922/6.648=1.142
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Chapter-12 HAZOP ANALYSIS AND PLANT LAYOUT

12.1 HAZOP Analysis: In our biorefinery, the major process is the production of first generation bioethanol from molasses. We have considered the HAZOP Analysis of one of our major equipment i.e. DISTILLATION COLUMN. Distillation units are one of the most important parts in any chemical plant. In our biorefinery also it plays an important role. The qualities of a distillation units products are directly affected by feeds properties. The HAZOP study of the column is summarized in the Table 12.1 HAZOP Analysis: Unit: Distillation Unit Study Node: Tower Process Parameters: Level, Concentration, Temperature, Pressure Guide words: Too high, Too low The guide words are applied to the study node of the tank, pressure vessel, closed pipe section and standpipe with the designated process parameters. [28] Hazards and Operability Review Project Name: Design of Integrated Sugarcane based biorefinery Process: Production of first generation bioethanol from Molasses Section: Distillation Column Item Study node Process Guide Possible causes parameter Words Tower Too High Too high inflow 1A Level Too low outflow Temp expansion Vessel contraction depressurization 1B Too Low Too high outflow Too low inflow evaporation Too high inflow Too low outflow Long storage Wrong substance dipped, impurity Azeotrope formation Poisoning on cleaning Evaporation Date:25/04/13 Page: 1of 2
Possible consequences Flammable, Corrosives, High pressure at outflow
Action required Level control alarm Trip, shutdown Dump valve Overflow, drain Level control alarm Trip, shutdown controller
1C
Concentration
Too High
Check valve Alarm
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Reverse flow Wrong burst in flow Too high heating flow Too low cooling flow Too high electrical heat Fire Low pressure Too high cooling flow Too low heating flow Too low inflow temp Too high temp Too high inflow Too low outflow Pressure reduction fails Full of liquid Too low temp Too low inflow Too high outflow Cooling Table 12.1 HAZOP Analysis applied to the Distillation Column [29] The potential process modifications resulting from this study are the following: install a high-temperature alarm to alert the operator in the event of cooling function loss install a high-temperature shutdown system (this system would automatically shut down the process in the event of a high temperature; the shutdown temperature would be higher than the alarm temperature to provide the operator with the opportunity to re- store cooling before the unit is shutdown) install a check valve in the cooling line to prevent reverse Study the cooling water source to consider possible contamination and interruption of supply, install a cooling water flow meter and low-flow alarm (which will provide an immediate indication of cooling loss). Advantages of HAZOP Analysis: The advantage to this approach is that it provides a more complete identification of the hazards, including information on how hazards can develop as a result of operating procedures and operational upsets in the process. Dump Tank Cleaning, Steam Temp control Alarms Trips, shutdown Relief valve Temp control Alarms Trips shutdown Safety valve Relief valve Trip, Shutdown Cooling Burst disc Trip, Shutdown Alarm Vacuum breaker Pressure control
1D
Temperature
Too high
Overpressure, metal stress, metal weakening, fire, loss of reflux flow Low pressure
1E
Too Low
1F
Pressure
Too High
1G
Too Low
12.2 PLANT LAYOUT: Site Selection: For our biorefinery, we have selected the Indapur region of Solapur, Maharashtra.
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Raw material Supply: Many sugar mills are located in the nearby region of Solapur like Siddhanath Sugar Mills, Shri Siddheshwar Sugar Factory and many more. So the raw material availability is quite easy from these mills. Transport Facilities: Majorly, we are relying on the Transport by road. Northern Hihgway-9 i.e. Mumbai Highway passes through Indapur and we will transport our products via road and also receive our raw materials via road network. Availability of Utilities: a) Power: We are taking power from the local grid and we are also producing power by burning of bagasse in our biorefinery plant. b) Water: We are getting the water supply for our plant from Ujani dam on Bhima River. The plant layout of our Biorefinery is shown in fig 12.1
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CONCLUSION
Our project emphasizes on the need of bio-refinery in the present scenario. It is essential to establish solutions which reduce the rapid consumption of fossil resources, which are not renewable (petroleum, natural gas, coal, minerals). A forward looking approach is the stepwise conversion of large parts of the global economy into a sustainable bio-based economy with bioenergy, biofuels, and bio-based products as its main pillars. Biorefinery concept, being the solution to the problem, supports this approach. The importance of Bioethanol as an additive to regular fuel is increasing continuously. Ethanol is a high octane fuel and has replaced lead as an octane enhancer in petrol. In India, the most common blend is 5% ethanol and 95% petrol .Vehicle engines require no modifications to run on it and vehicle warranties are unaffected also. The Cabinet Committee on Economic Affairs (CCEA) has made it mandatory for oil marketing companies (OMCs)
Bharat Petroleum, Hindustan Petroleum and Indian Oil Corporation - to blend 5% ethanol with petrol from December 2012. This is likely to reduce the fuel import bill and lower India's dependence on fossil fuel as the ethanol prices are lower than petrol. Thus bio-ethanol, being the main product of our integrated sugar based bio-refinery, justifies our project. The location of our plant is Solapur, Maharashtra on account of the availability of raw material at a cheaper, subsidized rate with sound transport and electricity facilities. Thus we have designed a plant of 30 ton/day with techno-economic feasibility report which is stated with the need, demand and supply analysis by going through a process of mass, energy balance with detailed equipment design in the process. We have discussed in detail, the properties, traditional applications, current uses of our product and also discussed how we can make the manufacturing process more energy efficient by producing 2 nd generation bioethanol as well. We have worked on the control strategy of the distillation column, major equipment in our process flow diagram. The economic evaluation of the plant shows a total capital investment requirement of Rs 8.108*10^ 8 with an acceptable payback period of 7 years. In the development of the plant various practical considerations regarding safety, pollution and environmental concerns are taken care of. A detailed plant layout of the plant is also prepared.
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REFERENCES
1. 2. Biorefinery at http://en.wikipedia.org/wiki/Biorefinery as of 2nd Sep, 2012 Birgit Kamm, Patrick R. Gruber and Michael Kamm, Biorefineries-Industrial Processes and Products Status quo and future directions Vol-1 Wiley-VCH Verlag GmbH & Co. KGaA, pg.3 3. Ethanol at http://petrofedwinwinhosting.net/upload/1920%20April%202012/Presentations/Session%201/2_Abhay%20Chau dhari.pdf as of 2nd Sep, 2012 4. 5. 6. 7. 8. Traditional applications at http://www.ryssen.com/en/Products/Traditional-applications/ as of 7 Dec 2012 Godavari Biorefinery at http://www.somaiya.com/pages/home.html as of 4 Sep 2012 Alternative fuels at http://www.doe.gov.ph/AF/BioethanolFAQ.htm as of 25 Nov 2012 Sugar at http://en.wikipedia.org/wiki/Sugar#Forms_and_uses as of 6 Dec 2012 Ethanol a renewable energy source at http://www.extraordinaryroadtrip.org/research-library/technology/ethanol/current-uses.asp as of 5 Dec 2012 9. 12. Molasses at http://en.wikipedia.org/wiki/Molasses as of 5 Sep 2012
10. Grades of ethanol at http://www.grainprocessing.com/alcohol/alcohol-grades.htm as of 5 Sep 2012 11. Types of molasses at http://whatscookingamerica.net/Q-A/Molassas.htm as of 5 Sep 2012 12. Demand supply for ethanol at http://www.ethanolindia.net/ethanol_demand.htm as of 5 Sep 2012 13. Alain.A.vertes, John Wiley and sons, Biomass to biofuels-strategies for global industries- pg 71-88 14. Safety evaluation of ethanol at http://www.occup-med.com/content/3/1/26 as of 8 Dec 2012 15. Simulation of ethanol production from sugarcane at http://www.aidic.it/escape20/webpapers/549Dias.pdf as of 8 Dec 2012 16. Ethanol at http://www.scribd.com/doc/53596201/Final-Project as of 8 Dec 2012 17. Trends in bioconversion of lignocellulose: Biofuels, platform chemicals & biorefinery concept, Vishnu Menon, Mala Rao, Division of Biochemical Sciences, National Chemical Laboratory, Pune 411-008, India 18. 2nd generation bioethanol at http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA436469 as of 8 Dec 2012 19. Ethyl alcohol at http://www.authorstream.com/Presentation/shaktibhardwaj-1381152-ethyl-alcohol-me/ as of 2 Nov 2012 20. Production of ethyl alcohol from molasses using aspen plus at http://www.scribd.com/doc/53596201/Final-Project as of 2 Nov 2012 21. Lignocellulosic ethanol in Brazil at http://edepot.wur.nl/9629 as of 6 Dec 2012 22. Richard.M.Felder, Ronald.W.Rousseau, Elementary principles of Chemical processes, 3rd edition, Appendix B 23. Distillation Control and Strategy at http://xa.yimg.com/kq/groups/18125250/1751783716/name/liptak_distillation_ebook.pdf as of 7 Dec 2012 24. http://www.scribd.com/doc/24314779/Fermenter-Design 25. http://www.engr.usask.ca/departments/chebio/students/current-undergrad/projects/2008/Group%20I%20%20Final%20Report.pdf 26. http://hengyeusa.com/community/modern-molecular-sieve-dehydration-technology-for-fuel-ethanol
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27. Turton Richard, C.Bailei Richard, B. Whiting Wallace, A. Shaeiwitz Joseph, Analysis, Synthesis and Design of Chemical Processes, second ed., pg 143-180,266-272 28. Daniel. A. Crowl, Joseph.F.Louvar, Chemical Process Safety-Fundamentals with applications, second edition, Pg-448-453 29. HAZOP Analysis at http://www.risoe.dtu.dk/rispubl/reports/ris-m-2319.pdf as of 25th April 2013
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APPENDIX MATERIAL SAFETY AND DATA SHEET
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0 0
Material Safety Data Sheet
Water MSDS
Section 1: Chemical Product and Company Identification
Product Name: Water Catalog Codes: SLW1063 CAS#: 7732-18-5 RTECS: ZC0110000 TSCA: TSCA 8(b) inventory: Water CI#: Not available. Synonym: Dihydrogen oxide Chemical Name: Water Chemical Formula: H2O Contact Information: Sciencelab.com, Inc. 14025 Smith Rd. Houston, Texas 77396 US Sales: 1-800-901-7247 International Sales: 1-281-441-4400 Order Online: ScienceLab.com
He a lt h
0 0 0 A
Fire Re a c t iv it y P e rs o n a l P ro t e c t io n
CHEMTREC (24HR Emergency Telephone), call: 1-800-424-9300 International CHEMTREC, call: 1-703-527-3887 For non-emergency assistance, call: 1-281-441-4400
Section 2: Composition and Information on Ingredients

Composition: Name Water CAS # 7732-18-5 % by Weight 100
Toxicological Data on Ingredients: Not applicable.
Section 3: Hazards Identification

Potential Acute Health Effects: Non-corrosive for skin. Non-irritant for skin. Non-sensitizer for skin. Non-permeator by skin. Non-irritating to the eyes. Nonhazardous in case of ingestion. Non-hazardous in case of inhalation. Non-irritant for lungs. Non-sensitizer for lungs. Noncorrosive to the eyes. Non-corrosive for lungs. Potential Chronic Health Effects: Non-corrosive for skin. Non-irritant for skin. Non-sensitizer for skin. Non-permeator by skin. Non-irritating to the eyes. Non-hazardous in case of ingestion. Non-hazardous in case of inhalation. Non-irritant for lungs. Non-sensitizer for lungs. CARCINOGENIC EFFECTS: Not available. MUTAGENIC EFFECTS: Not available. TERATOGENIC EFFECTS: Not available. DEVELOPMENTAL TOXICITY: Not available.
Section 4: First Aid Measures

Eye Contact: Not applicable. p. 1
Skin Contact: Not applicable. Serious Skin Contact: Not available. Inhalation: Not applicable. Serious Inhalation: Not available. Ingestion: Not Applicable Serious Ingestion: Not available.
Section 5: Fire and Explosion Data

Flammability of the Product: Non-flammable. Auto-Ignition Temperature: Not applicable. Flash Points: Not applicable. Flammable Limits: Not applicable. Products of Combustion: Not available. Fire Hazards in Presence of Various Substances: Not applicable. Explosion Hazards in Presence of Various Substances: Not Applicable Fire Fighting Media and Instructions: Not applicable. Special Remarks on Fire Hazards: Not available. Special Remarks on Explosion Hazards: Not available.
Section 6: Accidental Release Measures

Small Spill: Mop up, or absorb with an inert dry material and place in an appropriate waste disposal container. Large Spill: Absorb with an inert material and put the spilled material in an appropriate waste disposal.
Section 7: Handling and Storage

Precautions: No specific safety phrase has been found applicable for this product. Storage: Not applicable.
Section 8: Exposure Controls/Personal Protection

Engineering Controls: Not Applicable Personal Protection: Safety glasses. Lab coat. Personal Protection in Case of a Large Spill: Not Applicable Exposure Limits: Not available.
Section 9: Physical and Chemical Properties

Physical state and appearance: Liquid. p. 2
Odor: Odorless. Taste: Not available. Molecular Weight: 18.02 g/mole Color: Colorless. pH (1% soln/water): 7 [Neutral.] Boiling Point: 100C (212F) Melting Point: Not available. Critical Temperature: Not available. Specific Gravity: 1 (Water = 1) Vapor Pressure: 2.3 kPa (@ 20C) Vapor Density: 0.62 (Air = 1) Volatility: Not available. Odor Threshold: Not available. Water/Oil Dist. Coeff.: Not available. Ionicity (in Water): Not available. Dispersion Properties: Not applicable Solubility: Not Applicable
Section 10: Stability and Reactivity Data

Stability: The product is stable. Instability Temperature: Not available. Conditions of Instability: Not available. Incompatibility with various substances: Not available. Corrosivity: Not available. Special Remarks on Reactivity: Not available. Special Remarks on Corrosivity: Not available. Polymerization: Will not occur.
Section 11: Toxicological Information

Routes of Entry: Absorbed through skin. Eye contact. Toxicity to Animals: LD50: [Rat] - Route: oral; Dose: > 90 ml/kg LC50: Not available. Chronic Effects on Humans: Not available. Other Toxic Effects on Humans: Non-corrosive for skin. Non-irritant for skin. Non-sensitizer for skin. Non-permeator by skin. Non-hazardous in case of ingestion. Non-hazardous in case of inhalation. Non-irritant for lungs. Non-sensitizer for lungs. Non-corrosive to the eyes. Noncorrosive for lungs. Special Remarks on Toxicity to Animals: Not available. p. 3
Special Remarks on Chronic Effects on Humans: Not available. Special Remarks on other Toxic Effects on Humans: Not available.
Section 12: Ecological Information

Ecotoxicity: Not available. BOD5 and COD: Not available. Products of Biodegradation: Possibly hazardous short term degradation products are not likely. However, long term degradation products may arise. Toxicity of the Products of Biodegradation: The product itself and its products of degradation are not toxic. Special Remarks on the Products of Biodegradation: Not available.
Section 13: Disposal Considerations

Waste Disposal: Waste must be disposed of in accordance with federal, state and local environmental control regulations.
Section 14: Transport Information

DOT Classification: Not a DOT controlled material (United States). Identification: Not applicable. Special Provisions for Transport: Not applicable.
Section 15: Other Regulatory Information

Federal and State Regulations: TSCA 8(b) inventory: Water Other Regulations: EINECS: This product is on the European Inventory of Existing Commercial Chemical Substances. Other Classifications: WHMIS (Canada): Not controlled under WHMIS (Canada). DSCL (EEC): This product is not classified according to the EU regulations. Not applicable. HMIS (U.S.A.): Health Hazard: 0 Fire Hazard: 0 Reactivity: 0 Personal Protection: a National Fire Protection Association (U.S.A.): Health: 0 Flammability: 0 Reactivity: 0 Specific hazard: p. 4
Protective Equipment: Not applicable. Lab coat. Not applicable. Safety glasses.
Section 16: Other Information

References: Not available. Other Special Considerations: Not available. Created: 10/10/2005 08:33 PM Last Updated: 06/09/2012 12:00 PM The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no event shall ScienceLab.com be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if ScienceLab.com has been advised of the possibility of such damages.
p. 5
3 2
Material Safety Data Sheet
Ethyl Alcohol 190 Proof MSDS
Section 1: Chemical Product and Company Identification
Product Name: Ethyl Alcohol 190 Proof Catalog Codes: SLE1036, SLE1609, SLE1288 CAS#: Mixture. RTECS: Not applicable. TSCA: TSCA 8(b) inventory: Water; Ethyl alcohol 200 Proof CI#: Not applicable. Synonym: Ethyl Alcohol 190 Proof Chemical Formula: Not applicable. Contact Information: Sciencelab.com, Inc. 14025 Smith Rd. Houston, Texas 77396 US Sales: 1-800-901-7247 International Sales: 1-281-441-4400 Order Online: ScienceLab.com
He a lt h
2 3 0 H
Fire Re a c t iv it y P e rs o n a l P ro t e c t io n
CHEMTREC (24HR Emergency Telephone), call: 1-800-424-9300 International CHEMTREC, call: 1-703-527-3887 For non-emergency assistance, call: 1-281-441-4400
Section 2: Composition and Information on Ingredients

Composition: Name Water Ethyl alcohol 200 Proof CAS # 7732-18-5 64-17-5 % by Weight 5 95
Toxicological Data on Ingredients: Ethyl alcohol 200 Proof: ORAL (LD50): Acute: 7060 mg/kg [Rat]. 3450 mg/kg [Mouse]. VAPOR (LC50): Acute: 20000 ppm 8 hours [Rat]. 39000 mg/m 4 hours [Mouse].
Section 3: Hazards Identification

Potential Acute Health Effects: Hazardous in case of skin contact (irritant), of eye contact (irritant), . Slightly hazardous in case of skin contact (permeator), of ingestion. Non-corrosive for skin. Non-corrosive to the eyes. Non-corrosive for lungs. Potential Chronic Health Effects: Slightly hazardous in case of skin contact (sensitizer) CARCINOGENIC EFFECTS: Classified PROVEN by State of California Proposition 65 [Ethyl alcohol 200 Proof]. Classified A4 (Not classifiable for human or animal.) by ACGIH [Ethyl alcohol 200 Proof]. MUTAGENIC EFFECTS: Mutagenic for mammalian somatic cells. [Ethyl alcohol 200 Proof]. Mutagenic for bacteria and/or yeast. [Ethyl alcohol 200 Proof]. TERATOGENIC EFFECTS: Classified PROVEN for human [Ethyl alcohol 200 Proof]. DEVELOPMENTAL TOXICITY: Classified Development toxin [PROVEN] [Ethyl alcohol 200 Proof]. Classified Reproductive system/toxin/female, Reproductive system/toxin/male [POSSIBLE] [Ethyl alcohol 200 Proof]. The substance is toxic to blood, the reproductive system, liver, upper respiratory tract, skin, central nervous
p. 1
Section 4: First Aid Measures

Eye Contact: Check for and remove any contact lenses. Immediately flush eyes with running water for at least 15 minutes, keeping eyelids open. Cold water may be used. Get medical attention. Skin Contact: In case of contact, immediately flush skin with plenty of water. Cover the irritated skin with an emollient. Remove contaminated clothing and shoes. Cold water may be used.Wash clothing before reuse. Thoroughly clean shoes before reuse. Get medical attention. Serious Skin Contact: Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream. Seek medical attention. Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention if symptoms appear. Serious Inhalation: Evacuate the victim to a safe area as soon as possible. Loosen tight clothing such as a collar, tie, belt or waistband. If breathing is difficult, administer oxygen. If the victim is not breathing, perform mouth-to-mouth resuscitation. Seek medical attention. Ingestion: Do NOT induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Loosen tight clothing such as a collar, tie, belt or waistband. Get medical attention if symptoms appear. Serious Ingestion: Not available.
Section 5: Fire and Explosion Data

Flammability of the Product: Flammable. Auto-Ignition Temperature: The lowest known value is 363C (685.4F) (Ethyl alcohol 200 Proof). Flash Points: CLOSED CUP: 18.5C (65.3F).(estimated) Flammable Limits: The greatest known range is LOWER: 3.3% UPPER: 19% (Ethyl alcohol 200 Proof) Products of Combustion: These products are carbon oxides (CO, CO2). Fire Hazards in Presence of Various Substances: Highly flammable in presence of open flames and sparks, of heat. Slightly flammable to flammable in presence of oxidizing materials. Non-flammable in presence of shocks, of reducing materials, of combustible materials, of organic materials, of metals, of acids, of alkalis. Explosion Hazards in Presence of Various Substances: Slightly explosive in presence of open flames and sparks, of heat, of oxidizing materials, of acids. Non-explosive in presence of shocks. Fire Fighting Media and Instructions: Flammable liquid, soluble or dispersed in water. SMALL FIRE: Use DRY chemical powder. LARGE FIRE: Use alcohol foam, water spray or fog. Special Remarks on Fire Hazards: Containers should be grounded. CAUTION: MAY BURN WITH NEAR INVISIBLE FLAME Vapor may travel considerable distance to source of ignition and flash back. May form explosive mixtures with air. Contact with Bromine pentafluoride is likely to cause fire or explosion. Ethanol ignites on contact with chromyl chloride. Ethanol ignites on contact with iodine heptafluoride gas. It ignites than explodes upon contact with nitrosyl perchlorate. Additon of platinum black catalyst caused ignition. (Ethyl alcohol 200 Proof) Special Remarks on Explosion Hazards: Ethanol has an explosive reaction with the oxidized coating around potassium metal. Ethanol ignites and then explodes on contact with acetic anhydride + sodium hydrosulfate (ignites and may explode), disulfuric acid + nitric acid, phosphorous(III) p. 2
oxide platinum, potassium-tert-butoxide+ acids. Ethanol forms explosive products in reaction with the following compound : ammonia + silver nitrate (forms silver nitride and silver fulminate), iodine + phosphorus (forms ethane iodide), magnesium perchlorate (forms ethyl perchlorate), mercuric nitrate, nitric acid + silver (forms silver fulminate) silver nitrate (forms ethyl nitrate) silver(I) oxide + ammonia or hydrazine (forms silver nitride and silver fulminate), sodium (evolves hydrogen gas). Sodium Hydrazide + alcohol can produce an explosion. Alcohols should not be mixed with mercuric nitrate, as explosive mercuric fulminate may be formed. May form explosive mixture with manganese perchlorate + 2,2-dimethoxypropane. Addition of alcohols to highly concentrate hydrogen peroxide forms powerful explosives. Explodes on contact with calcium hypochlorite Vapor may explode if ignited in an enclosed area. Containers may explode when heated or involved in a fire. (Ethyl alcohol 200 Proof)
Section 6: Accidental Release Measures

Small Spill: Dilute with water and mop up, or absorb with an inert dry material and place in an appropriate waste disposal container. Large Spill: Flammable liquid. Keep away from heat. Keep away from sources of ignition. Stop leak if without risk. Absorb with DRY earth, sand or other non-combustible material. Do not touch spilled material. Prevent entry into sewers, basements or confined areas; dike if needed. Be careful that the product is not present at a concentration level above TLV. Check TLV on the MSDS and with local authorities.
Section 7: Handling and Storage

Precautions: Keep locked up.. Keep away from heat. Keep away from sources of ignition. Ground all equipment containing material. Do not ingest. Do not breathe gas/fumes/ vapor/spray. Wear suitable protective clothing. In case of insufficient ventilation, wear suitable respiratory equipment. If ingested, seek medical advice immediately and show the container or the label. Avoid contact with skin and eyes. Keep away from incompatibles such as oxidizing agents, acids, alkalis, moisture. Storage: Store in a segregated and approved area. Keep container in a cool, well-ventilated area. Keep container tightly closed and sealed until ready for use. Avoid all possible sources of ignition (spark or flame). Do not store above 23C (73.4F).
Section 8: Exposure Controls/Personal Protection

Engineering Controls: Provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapors below their respective threshold limit value. Ensure that eyewash stations and safety showers are proximal to the work-station location. Personal Protection: Splash goggles. Lab coat. Vapor respirator. Be sure to use an approved/certified respirator or equivalent. Gloves. Personal Protection in Case of a Large Spill: Splash goggles. Full suit. Vapor respirator. Boots. Gloves. A self contained breathing apparatus should be used to avoid inhalation of the product. Suggested protective clothing might not be sufficient; consult a specialist BEFORE handling this product. Exposure Limits: Ethyl alcohol 200 Proof TWA: 1900 (mg/m3) from OSHA (PEL) [United States] TWA: 1000 (ppm) from OSHA (PEL) [United States] TWA: 1900 (mg/m3) from NIOSH [United States] TWA: 1000 (ppm) from NIOSH [United States] TWA: 1000 (ppm) [United Kingdom (UK)] TWA: 1920 (mg/m3) [United Kingdom (UK)] TWA: 1000 STEL: 1250 (ppm) [Canada] Consult local authorities for acceptable exposure limits.
Section 9: Physical and Chemical Properties

Physical state and appearance: Liquid. p. 3
Odor: Alcohol like. Mild to strong. Like wine or whiskey; Ethereal, vinous. Pleasant. Taste: Burning. Pungent. Molecular Weight: Not applicable. Color: Clear Colorless. pH (1% soln/water): Neutral. Boiling Point: The lowest known value is 78.5C (173.3F) (Ethyl alcohol 200 Proof). Weighted average: 79.58C (175.2F) Melting Point: May start to solidify at -114.1C (-173.4F) based on data for: Ethyl alcohol 200 Proof. Critical Temperature: The lowest known value is 243C (469.4F) (Ethyl alcohol 200 Proof). Specific Gravity: Weighted average: 0.8 (Water = 1) Vapor Pressure: The highest known value is 5.7 kPa (@ 20C) (Ethyl alcohol 200 Proof). Weighted average: 5.53 kPa (@ 20C) Vapor Density: The highest known value is 1.59 (Air = 1) (Ethyl alcohol 200 Proof). Weighted average: 1.54 (Air = 1) Volatility: Not available. Odor Threshold: 100 ppm Water/Oil Dist. Coeff.: Not available. Ionicity (in Water): Not available. Dispersion Properties: See solubility in water, methanol, diethyl ether, acetone. Solubility: Easily soluble in cold water, hot water, methanol, diethyl ether. Soluble in acetone.
Section 10: Stability and Reactivity Data

Stability: The product is stable. Instability Temperature: Not available. Conditions of Instability: Incompatible materials, heat, sources of ignition. Incompatibility with various substances: Reactive with oxidizing agents, acids, alkalis. Corrosivity: Non-corrosive in presence of glass. Special Remarks on Reactivity: Ethanol rapidly absorbs moisture from the air. Can react vigorously with oxiders. The following oxidants have been demonstrated to undergo vigorous/explosive reaction with ethanol: barium perchlorate, bromine pentafluoride, calcium hypochlorite, chloryl perchlorate, chromium trioxide, chromyl chloride, dioxygen difluoride, disulfuryl difluoride, fluorine nitrate, hydrogen peroxide, iodine heptafluoride, nitric acid nitrosyl perchlorate, perchloric acid permanganic acid, peroxodisulfuric acid, potassium dioxide, potassium perchlorate, potassium permanganate, ruthenium(VIII) oxide, silver perchlorate, silver peroxide, uranium hexafluoride, uranyl perchlorate. Ethanol reacts violently/expodes with the following compounds: acetyl bromide (evolves hydrogen bromide) acetyl chloride, aluminum, sesquibromide ethylate, ammonium hydroxide & silver oxide, chlorate, chromic anhydride, cyanuric acid + water, dichloromethane + sulfuric acid + nitrate (or) nitrite, hydrogen peroxide + sulfuric acid, iodine + methanol + mercuric oxide, manganese perchlorate + 2,2-dimethoxy propane, perchlorates, permanganates + sulfuric acid, potassium superoxide, potassium tert-butoxide, silver & nitric acid, silver perchlorate, sodium hydrazide, sulfuric acid + sodium dichromate, tetrachlorisilane + water. Ethanol is also incompatible with platinium, and sodium. No really safe conditions exist under which ethyl alcohol and chlorine oxides can be handled. Reacts vigorously with acetyl chloride (Ethyl alcohol 200 Proof) Special Remarks on Corrosivity: Not available. Polymerization: Will not occur.
p. 4
Section 11: Toxicological Information

Routes of Entry: Absorbed through skin. Eye contact. Inhalation. Ingestion. Toxicity to Animals: Acute oral toxicity (LD50): 3632 mg/kg (Mouse) (Calculated value for the mixture). Chronic Effects on Humans: CARCINOGENIC EFFECTS: Classified PROVEN by State of California Proposition 65 [Ethyl alcohol 200 Proof]. Classified A4 (Not classifiable for human or animal.) by ACGIH [Ethyl alcohol 200 Proof]. MUTAGENIC EFFECTS: Mutagenic for mammalian somatic cells. [Ethyl alcohol 200 Proof]. Mutagenic for bacteria and/or yeast. [Ethyl alcohol 200 Proof]. TERATOGENIC EFFECTS: Classified PROVEN for human [Ethyl alcohol 200 Proof]. DEVELOPMENTAL TOXICITY: Classified Development toxin [PROVEN] [Ethyl alcohol 200 Proof]. Classified Reproductive system/toxin/female, Reproductive system/toxin/male [POSSIBLE] [Ethyl alcohol 200 Proof]. Other Toxic Effects on Humans: Hazardous in case of skin contact (irritant), of inhalation. Slightly hazardous in case of skin contact (permeator), of ingestion. Special Remarks on Toxicity to Animals: Lowest Published Dose/Conc: LDL[Human] - Route: Oral; Dose: 1400 mg/kg LDL[Human child] - Route: Oral; Dose: 2000 mg/ kg LDL[Rabbit] - Route: Skin; Dose: 20000 mg/kg (Ethyl alcohol 200 Proof) Special Remarks on Chronic Effects on Humans: May affect genetic material (mutagenic) Causes adverse reproductive effects and birth defects (teratogenic) , based on moderate to heavy consumption. May cause cancer based on animal data. Human: passes through the placenta, excreted in maternal milk. (Ethyl alcohol 200 Proof) Special Remarks on other Toxic Effects on Humans: Acute potential health effects: Skin: causes skin irritation Eyes: causes eye irritation Ingestion: May cause gastrointestinal tract irritation with nausea, vomiting, diarrhea, and alterations in gastric secretions. May affect behavior/central nervous system (central nervous system depression - amnesia, headache, muscular incoordination, excitation, mild euphoria, slurred speech, drowsiness, staggaring gait, fatigue, changes in mood/personality, excessive talking, dizziness, ataxia, somnolence, coma/ narcosis, hallucinations, distorted perceptions, general anesthetic), peripherial nervous system (spastic paralysis)vision (diplopia). Moderately toxic and narcotic in high concentrations. May also affect metabolism, blood, liver, respiration (dyspnea), and endocrine system. May affect respiratory tract, cardiovascular(cardiac arrhythmias, hypotension), and urinary systems. Inhalation: May cause irritation of the respiratory tract and affect behavior/central nervous system with symptoms similar to ingestion. Chronic Potential Health Effects: Skin: Prolonged or repeated skin contact may casue dermatitis, an allergic reaction. Ingestion: Prolonged or repeated ingestion will have similiar effects as acute ingestion. It may also affect the brain. (Ethyl alcohol 200 Proof)
Section 12: Ecological Information

Ecotoxicity: Not available. BOD5 and COD: Not available. Products of Biodegradation: Possibly hazardous short term degradation products are not likely. However, long term degradation products may arise. Toxicity of the Products of Biodegradation: The product itself and its products of degradation are not toxic. Special Remarks on the Products of Biodegradation: Not available.
Section 13: Disposal Considerations

Waste Disposal: Waste must be disposed of in accordance with federal, state and local environmental control regulations.
Section 14: Transport Information

p. 5
DOT Classification: CLASS 3: Flammable liquid. Identification: : Ethanol (Ethyl alcohol 200 Proof) UNNA: 1170 PG: II Special Provisions for Transport: Not available.
Section 15: Other Regulatory Information

Federal and State Regulations: California prop. 65: This product contains the following ingredients for which the State of California has found to cause cancer, birth defects or other reproductive harm, which would require a warning under the statute: Ethyl alcohol 200 Proof (in alcoholic beverage) California prop. 65: This product contains the following ingredients for which the State of California has found to cause birth defects which would require a warning under the statute: Ethyl alcohol 200 Proof (in alcoholic beverage) Connecticut hazardous material survey.: Ethyl alcohol 200 Proof Illinois toxic substances disclosure to employee act: Ethyl alcohol 200 Proof Rhode Island RTK hazardous substances: Ethyl alcohol 200 Proof Pennsylvania RTK: Ethyl alcohol 200 Proof Florida: Ethyl alcohol 200 Proof Minnesota: Ethyl alcohol 200 Proof Massachusetts RTK: Ethyl alcohol 200 Proof Massachusetts spill list: Ethyl alcohol 200 Proof New Jersey: Ethyl alcohol 200 Proof TSCA 8(b) inventory: Water; Ethyl alcohol 200 Proof Other Regulations: OSHA: Hazardous by definition of Hazard Communication Standard (29 CFR 1910.1200). Other Classifications: WHMIS (Canada): CLASS B-2: Flammable liquid with a flash point lower than 37.8C (100F). CLASS D-2B: Material causing other toxic effects (TOXIC). DSCL (EEC): R11- Highly flammable. S7- Keep container tightly closed. S16- Keep away from sources of ignition - No smoking. HMIS (U.S.A.): Health Hazard: 2 Fire Hazard: 3 Reactivity: 0 Personal Protection: h National Fire Protection Association (U.S.A.): Health: 2 Flammability: 3 Reactivity: 0 Specific hazard: Protective Equipment: Gloves. Lab coat. Vapor respirator. Be sure to use an approved/certified respirator or equivalent. Wear appropriate respirator when ventilation is inadequate. Splash goggles.
Section 16: Other Information

References: Not available. Other Special Considerations: Not available. Created: 10/09/2005 05:28 PM Last Updated: 06/09/2012 12:00 PM p. 6
The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no event shall ScienceLab.com be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if ScienceLab.com has been advised of the possibility of such damages.
p. 7
MATERIAL SAFETY DATA SHEET

1.1 Product Name: Common Name: Chemical Description: 1.2 Manufactured For:
Blackstrap Molasses
SECTION 1: CHEMICAL PRODUCT AND COMPANY IDENTIFICATION
Blackstrap Molasses
Molasses Inverted syrup from the juice of sugar cane Plant Food Company, Inc. 38 Hightstown-Cranbury Station Road Cranbury, NJ 08512 Emergency Telephone Number Telephone Number for Information Date Prepared 11/1/2011 609-448-0935 609-448-0935
SECTION 2: COMPOSITION/INFORMATION ON INGREDIENTS

Hazardous Components (Specific Chemical) Identity: Common Name
This product is a mixture--no specific CAS number
(CAS #) #REF!
OSHA PEL N/A
ACGIH TLV N/A
Other Limits Recommended N/A
SECTION 3: HAZARDS IDENTIFICATION

Black/brown liquid with typical odor. NEPA: Health:0 Reactivity:0 Flammability:1 Environment:0 (0=Insignificant=1 Slight 2=Moderate 3=High 4=Extreme) EMERGENCY OVERVIEW This material is not a 'health hazard' or a "physical hazard" as determined when reviewed according to the requirements of the Occupational Safety and Health Administration Hazard Communication Standard, 20 CFR 1910.1200
SECTION 4: FIRST AID MEASURES

4.1 EYES: Flush immediately with plenty of water for at least 15 minutes while holding eyelids apart to ensure complete irrigation of all eye and lid tissue. If irritation occurs, seek medical attention. 4.2 SKIN: Wash with plenty of soap and water. Remove contaminated clothing and shoes. Get medical attention if irritation persists. 4.3 INGESTION: If conscious and alert, administer water or milk to dilute, then induce vomiting. Call Poison Control Center or physician immediately. Do not give anything by mouth to an unconscious person. 4.4 INHALATION: Remove victim to fresh air. If not breathing, give artificial respiration, preferably mouth-to-mouth and get medical attention.
SECTION 5: FIREFIGHTING MEASURES

5.1 FLAMMABLE PROPERTIES FLASHPOINT: Not flammable METHOD USED: Closed Cup/NONCOMBUSTIBLE
5.2 FLAMMABLE LIMITS: LFL: NA UFL: NA 5.3 EXTINGUISHING MEDIA: Foam, carbon dioxide, dry chemical, or water fog. 5.4 FIRE & EXPLOSIVE HAZARDS: Not Combustible 5.5 FIRE FIGHTING EQUIPMENT: As in any fire, wear self-contained breathing apparatus, pressure demand, MSHA/NIOSH (approved or equivalent) and full protective gear. Avoid smoke inhalation. Contain any liquid runoff.
SECTION 6: ACCIDENTAL RELEASE MEASURES

6.1 SMALL RELEASES: Confine and absorb small releases on sand earth or other inert absorbent. Use water spray to dilute . 6.2 LARGE RELEASES: Shut off release if safe to do so. Dike spill area to prevent runoff into sewers, rains or surface waterways. Recover as much of the solution as possible. Treat remaining material as a small release (above).
SECTION 7: HANDLING AND STORAGE

7.1 HANDLING: Avoid contact with eyes. Use only in a well ventilated area. Wash thoroughly after handling. Avoid prolonged or repeated breathing of vapors. Avoid prolonged or repeated contact with the skin. 7.2 STORAGE: Store in original container only in a cool, well-ventilated, dry place at temperatures between 40 and 95F. Do not store near food or feeds. 7.3 TRANSER EQUIPMENT: Transfer product using chemical-resistant plastic or stainless steel tanks, pumps, valves, etc.
SECTION 8: EXPOSURE CONTROLS, PERSONAL PROTECTION

8.1 RESPIRATORY PROTECTION: Not normally needed. If use generates an aerosol mist or respiratory irritation, use NIOSH-approved dust/moist respirator (such as 3M#8710).Ventilation: Where air contaminants can exceed acceptable criteria, use NIOSH/MSHA approved respiratory protection equipment. Respirators should be selected based on the form and concentration of contaminate. 8.2 SKIN PROTECTION: Neoprene rubber groves and apron should be worn to prevent repeated or prolonged contact with the liquid. Wash contaminated clothing prior to reuse. 8.3 EYE PROTECTION: Chemical goggles and a full face shield. DO NOT WEAR CONTACT LENSES. 8.4 EXPOSURE GUIDELINES: OSHA TWA N/A STEL N/A
N/A N/A ACGIH 8.5 ENGINEERING CONTROLS: Use adequate exhaust ventilation to prevent inhalation of product vapors.
1 of 2
MATERIAL SAFETY DATA SHEET

SECTION 9: PHYSICAL AND CHEMICAL PROPERTIES
9.1 APPEARANCE 9.2 ODOR: 9.3 VAPOR PRESSURE: 9.4 VAPOR DENSITY: 9.5 SOLUBILITY IN WATER: 9.6 SPECIFIC GRAVITY (H 0 = 1): 9.7 MELTING POINT: 9.8 pH: 9.9 VOLATILE: 9.10 COLOR: 9.11 WEIGHT PER GALLON: 9.12 STORAGE LIFE AT 70 F: 9.13 PH-21C: 9.15 VISCOSITY: 9.16 FREEZING POINT: 9.17 EVAPORATION RATE: 9.18 BOILING POINT:
Blackstrap Molasses
Black/brown, clear viscous liquid Fruity sweet None Not available Highly soluble 1.4 N/A 5.1 Not available Black/brown, clear viscous liquid 11.7 lbs (5.3 kg) > 1 Year N/A Not available < 32F Not determined 224F
SECTION 10: STABILITY AND REACTIVITY

10.1 STABILITY: Stable 10.2 HAZARDOUS POLYMERIZATION: Will not occur. 10.3 HAZARDOUS DECOMPOSITION PRODUCTS: None Known 10.4 INCOMPATIBILITY: None. Avoid heat over 140F. Keep container vented to allow release of CO produced by natural yeast in product
SECTION 11: TOXICOLOGICAL INFORMATION

11.1 ORAL: May cause stomach cramps and/or nausea. 11.2 DERMAL: May cause slight irritation, especially from prolonged exposure. May cause redness. 11.3 INHALATION: None expected but inhalation may cause mild irritation of nasal mucous membranes. 11.4 CHORNIC/CARCINOGENICTY: Data not available 11.5 TERATOLOGY: Data not available 11.6 REPRODUCTION: Data not available 11.7 MUTAGENICITY: Data not available 11.8 EYES: May cause temporary eye irritation.
SECTION 12: ECOLOGICAL INFORMATION

12.1 Alga/Lemna Growth Inhibition: Not known. 12.2 Toxicity to Fish and Invertebrates: Not known 12.3 Toxicity to Plants: Not known 12.4 Toxicity in Birds: Not known
SECTION 13: DISPOSAL CONSIDERATIONS

Do not contaminate lakes, streams, ponds, estuaries, oceans or other waters by discharge of waste effluents or equipment washwaters. Dispose of waste effluents in accordance with state and local waste disposal regulations. Also, chemical additions or other alterations of this product may invalidate any disposal information in this MSDS. Therefore, consult local waste regulators for proper disposal.
SECTION 14: TRANSPORTATION INFORMATION

D.O.T. Other Shipping Description: Not D.O.T. Regulated Fertilizing Compounds (Manufactured), Liquid. NMFC Item 6810 Sub 6, LTL Class 70
SECTION 15: REGULATORY INFORMATION

15.1 CERCLA: None 15.2 SARA TITLE III, Section 313 Toxic Chemicals: None
SECTION 16: OTHER INFORMATION

This information was developed from information on the constituent materials. No warranty is expressed or implied regarding the completeness or continuing accuracy of the information contained herein, and Plant Food Company, Inc. disclaims all liability for reliance thereon. The user should satisfy himself that he has all current data relevant to his particular use.
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DESIGN OF INTEGRATED SUGARCANE BASED BIOREFINERY

Priya Garg-091420 Ritu Lavania-091422

Submitted in partial fulfillment of the Degree of Bachelor of Technology

JAYPEE UNIVERSITY OF ENGINEERING AND TECHNOLOGY

Signature of Supervisor Name of Supervisor Designation Date

.............................................. Priya Garg (091420)

............................................... Ritu Lavania (091422)

Chapter 6: Selected Process

6.1 Process Flowsheet 6.2 Process Description 6.3 Plant Capacity

LIST OF SYMBOLS AND ACRONYMS

Design of integrated sugarcane based biorefinery

Chapter -1 HISTORICAL PROFILE

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Chapter-2 APPLICATIONS AND GRADES

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Chapter-3 ECONOMIC SCENARIO

Design of integrated sugarcane based biorefinery

Portable sector demand 1.6 2 2.6 3.1

Industrial sector demand 0.6 0.8 1 1.2

2011 2013 2015 2017

Fuel ethanol demand @5% blending 0.9 1 1.2 1.4

Total ethanol demand 3.2 3.8 4.7 5.7

Ethanol demand growth rate (%) 10%

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Chapter - 4 PROPERTIES, HANDLING AND STORAGE

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Chapter - 5 MANUFACTURING PROCESSES

Fig 5.1 District wise Sugar Contribution % in Maharashtra

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Ethanol production 185,540 L/d

ENERGY EFFICIENCY HIGHEST

200,741 L/d 196,314 L/d 203,193 L/d

<1(HIGHEST) <1(LOWEST) <1

HIGHEST LOWEST MINIMUM LOWEST HIGHEST

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Chapter-6 SELECTED PROCESS

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Chapter-7 MATERIAL BALANCE

Overall Reaction: C12H22O11+H2O2C6H12O64C2H5OH+4CO2 Mol. Wt of sucrose= 342

Design of integrated sugarcane based biorefinery

Design of integrated sugarcane based biorefinery

Table 7.1 Material Balance across Fermenter

YEAST TREATMENT Assumptions:

Design of integrated sugarcane based biorefinery

Kg/hr (inlet) 2400.183 55.692 323.125 1292.5 4071.5