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315 devendra


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315 devendra

  1. 1. Biofuel from wastes an economic and environmentally feasible resource DevendraPratap Singh Department Of Applied Chemistry Dr. Ambedkar Institute Of Technology for Handicapped Kanpur 1
  2. 2. CONTENTS 1.Introduction 2.Need of Biofuel 3.Steps for Production of Biofuel from Biomass (a)Pretreatment (Comparative study) (b)Enzymatic hydrolysis & Fermentation (c)Kinetic study of production of ethanol 4.Advantage of bioethanol 5.Conclusion & Effective parameters 6.Major concerns/problems in bio ethanol cellulosic materials 7.Future Prospectus 8.Case Study of total biofuel production Lignocellulosic production from 2
  3. 3. (1) Introduction (a) BIOMASS Biomass is a renewable energy resource derived from the carbonaceous waste of various human and natural activities. It is derived from numerous sources, including the byproducts from the timber industry, agricultural crops, raw material from the forest, major parts of household waste and wood. Barley Straw, Rice Straw, Wheat Straw and Rape Straw before Pre-treatment 3
  4. 4. (b) Biomass Resources Untapped Natural Resource Agriculture: Rice husk, Rice straw, Wheat straw, Vegetable residue, etc Livestock: Animal waste, Butchery waste, etc. Agriculture, Livestock, Forestry and Fishery group Other Waste group Forestry: Forest residue, Thinned wood, Processing waste, Sawdust, etc. Fishery: Processing waste, Bowel, Dead fish, etc. Industry: Sewage sludge, Organic processing waste, etc. Household: Garbage, Human waste, etc. Plantation (Production group) Continental area: Grain, Plant, Vegetable, Fat and oil, etc. Water area: Algae, Photosynthetic bacteria, etc. 4
  5. 5. (c) BIOFUEL A fuel that is produced using biological feedstock's. It is a renewable energy source derived from biomass, such as plants, agricultural or forestry waste, animal wastes, or food waste. Common biofuels include ethanol and biodiesel. First generation Biofuels : Corn and sugar to ethanol, Chemical transesterification of vegetable oils Second Generation Biofuels : Lignocellulose to ethanol Enzymatic bioconversion of Vegetable oil Third generation Biofuels: Energy crops for bio-alcohol, Algal Ethanol /Biodiesel 5
  6. 6. (d)ETHANOL Produced from hydrolysis of sugar crops, Lignocellulosic biomasses, and fruit and vegetable waste by suitable enzymes or acid followed by fermentation of sugars, starch, cellulose and hemicelluloses using yeast or bacterium. It is used primarily as a supplement to gasoline. Fermentation is the process by which cells release energy under anaerobic conditions . (C6H10O5)n Acid Pretreatment C12H22O11 + H2O C6H12O6 zymase(Yeast) invertase n C6H12O6 C6H12O6 + C6H12O6 2C2H5OH + 2CO2 6
  7. 7. (e) BIODISEL It is Defined as the mono alkyl ester of long chain fatty acids derived from renewable lipid sources by Transesterification. It is produced from virgin or used vegetable oils (both edible & non edible) and animal fats through various chemical process. Transesterification: Transesterification is the process of reacting a triglyceride molecule with an excess of alcohol in presence of catalyst to produce glycerin and fatty aids. Triglyceride + Methanol NaOH or KOH Methyl ester + Glycerol 7
  8. 8. 2. Need of Biofuels It provides a market for excess production of vegetable oils and animal fats. It decreases the country's dependence on imported petroleum. It is renewable and does not contribute to global warming due to its closed carbon cycle. 8
  9. 9. 3. Steps for Production of Biofuel from Lignocellulosic Biomass (a) Pretreatment A pretreatment step is necessary for the enzymatic hydrolysis process. It is able to remove the lignin layer and to decristallize cellulose so that the hydrolytic enzymes can easily access the biopolymers. Need of lignocellulose pretreatment Tight multi-polymeric complex of cellulose, hemicelluloses and lignin Protective action of lignin Crystalline structure of cellulose Limited surface area for hydrolysis The purpose of physical pretreatments is the increase of the accessible surface area and the size of pores of cellulose and the decrease of its crystallinity and its polymerization degree. 9
  10. 10. Effect of Pretreatment Pretreatment gives enzyme accessible substrate 10
  11. 11. Wheat bran, sugarcane bagasse, Rice bran and rape straw were used for the treatment process. Before pretreatment these biomasses are reduced in to smaller particles after milling and crushing (particle size <180 μm). (b) Dilute Acid pre-treatment For the comparative result equal amount of biomasses were pretreated in two ways one is acid trement where 2-3% acid (H2SO4) was used for the pre-treatment method. In this content acid soaked biomass slurry was autoclaved at 1210C for 30 minutes. To separate the solid and liquid fraction centrifuge method was used. The dilution and pH was maintained at 5 by adding alkali of centrifuged biomass before fermentation process. 11
  12. 12. Different raw materials and their contains after pretreatment Raw Material Cellulose Hexosans (H) % 45 Hemicelluloses Pentosans (P)% 35 30 50 15 Rice straw 32.1 24 18 Rape straw 33.4 30 17 Rice bran 30.4 22 16 Wheat bran 31.3 23 17.5 Sugarcane bagasse Wheat straw Lignin % 15 12
  13. 13. Effect of acid pretreatment on carbohydrate content of sugarcane baggase Sample Sample-Acid used for Cellulose Available Pre-treatment (%) Conversion (%) Substrate (%) S1 0.5 11.8 88.2 S2 1.0 12.8 87.2 S3 1.5 13.6 86.4 S4 2.0 14.2 85.8 S5 2.5 15.2 84.8 S6 3.0 16.0 84 13
  14. 14. (c) Enzyme pre-treatment 150 g of each biomass were suspended in 500 mL H2O in ratio of 3:10 (w/v) sugarcane bagasse and added of 0.1 mL of α-amylase enzyme. The pH of sample was adjusted at pH 5, 5.5, and 6. The sample was incubated in water bath 100°C for 30 minutes, after that the mixture was applied for second enzymatic treatment (0.2 ml of glucoamylase). Finally, hydrolzsate was pressed through cheese cloth. The amount of reducing sugar in juice was measured. pH 5 5.5 6 5 5.5 6 Temperature (°C) 30 30 30 40 40 40 Glucose (%) 23.35 22.80 22.00 21.05 19.43 18.95 Effect of enzyme pre-treatment methods on glucose content of sugarcane baggase From the Table, it is clear that, increasing pH at 400C showed reverse effect on glucose concentration . 14
  15. 15. (d) Fermentation The pre-treated samples were carried out for fermentation experiments. The yeast S. cerevisiae was used for fermentation. After 3 fermentation days the ethanol content was measured by gas chromatography. S. cerevisiae was also used with Pitchia stipititis for both the fermentation of pentose and hexose. Equal amount of both the yeast and P. Stipititis were taken for the efficient hydrolysis and fermentation of both Pentose's and hexoses sugar present in the hydrolyzed. Fermentation Medium:- One litre of production medium was prepared according to the requirement of S. cerevisiae, containing 50.0 gL -1glucose, 1.0 gL-1yeast extract, 5.0 gL-1KH2PO4, 2.0 gL-1(NH4)2SO4 and 0.4 gL1 MgSO4.7H2O. The medium was sterilized and the pH was adjusted to 5.0. The Preparation of Inoculums:- The micro-organism was cultured in 250 mL Erlenmeyer flasks, containing 100 mL of the (PDA) medium, which has the same composition as the fermentation medium. The Erlenmeyer flask was incubated at 280C for 6 hours on a rotary shaker at 200 rpm. 15
  16. 16. Production of Ethanol % (v/v) at 300C and pH 5,from enzyme treated biomass Biomass (150g) Sugar (%) Ethanol (%) by Sugarcane bagasse Wheat Bran 23.35 20.74 S.cerevisiae 19.25 17.47 S.cerevisiae & P. stipititis 26.75 21.17 Rape Straw 22.75 18.09 25.48 Rice bran 21.03 17.95 24.28 40 Ethanol (%) 35 30 26.75 Glucose (% ) 25.48 25 24.28 21.17 Ethanol (% by S. cerevisie ) Ethanol (% by P.Stitipititis and ) S. cerevisie 20 15 10 Sugercane bagasse Rape straw Wheat bran Typpes of biomass Rice bran 16
  17. 17. SN. 1 2 3 4 Types of biomass samples Ethanol %(v/v) by S.cerevisiae S.cerevisiae & P. stipititis Sugarcane baggase Wheat Bran Rape Straw Rice bran 24.25 21.47 23.95 23.05 35.38 31.25 34.37 33.98 Production of Ethanol % (v/v) at 300C and pH 5 of acid treated biomass 40 35.38 35 34.37 33.98 31.25 Glucose (% ) 30 Ethanol (% by S. cerevisie ) 25 Ethanol (% by P.Stitipititis and ) S. cerevisie 20 15 10 Sugercane bagasse Rape straw Wheat bran Rice bran T y p p e s o f b io mas s 17
  18. 18. (e) Observation of Kinetic study of 100 gm sugar SN. Raw Materials Sugarcane from Bagasse Rape Straw Rice bran Wheat bran 1 Biomass yield YX/S (gg-1) 0.015 0.014 0.040 0.010 2 Ethanol yield YP/S (gg-1) 0.36 0.29 0.33 0.26 3 Final biomass, (gl-1) 1.49 1.32 1.28 0.92 4 Final ethanol (gl-1) 34.6 26.5 31.5 22.9 5 Substrate utilized, (%) 95.90 90.80 93.52 85.42 6 Fermentation efficiency (% of theoretical) 99.01 96.5 89.2 84.6 7 Fermentation time, (h) 24 24 24 24 * Theoretical yield based on total sugars is 0.511 gg-1 18
  19. 19. Fermentation of 100 gl­-1 sugar by yeast (temp 30°C, pH5) (•) total reducing sugars, () ethanol, () biomass. 19
  20. 20. Formula used Specific growth rate (µ) h-1 = Specific Ethanol productivity (qp) gg-1h-1 = Specific substrate uptake rate (qs) gg-1h-1 = Cell Yield, YX/S (gg-1) = Ethanol Yield, YP/S (gg-1) = Fermentation Efficiency (%) = 20
  21. 21. Enzymes that are able to hydrolyze the cellulose (C6 Sugar) and hemicelluloses (C5 sugars) These are:Yeast (Saccharomyces cerevisiae ): is able to utilize only hexose. Z. mobilis: has the ability to decompose both hexose and pentose Trichoderma resei: produces cellulase enzymes needed to convert cellulose and hemicellulose in to sugars . Clostridium thermocellum (C. thermocellum): this bacterium will convert cellulose directly to ethanol, but has some other byproducts that can reduce efficiency during fermentation. Pitchia stipititis : also able to decompose both hexose and pentose Aspergillus Niger: For saccharification of algal biomass. Aspergillus Niger is cellulolytic and amylolytic in nature as it produces cellulases and amylases.  Fungi- Saccharomyces cerevisiae (Strain 1), Kluyveromyces marxianus (Strain 2), Candida tropicalis (Strain 3), , a strain of Pitchia (Strain 4) and Candida krusei (Strain 5).  Saccharomyces cerevisiae simultaneously combination with Pitchia stipititis and Pitchia tenofiller for the complete fermentation of sugars. 21
  22. 22. (f) Complete process of production of ethanol BIOMASS SUGAR & NUTRIENTS Handling Enzyme Production Grinding Pretreatment CELLULOSE LIGNIN Inoculation Enzymatic Hydrolysis Fermentation XYLOSE Distillation Acid Pretreatment ETHANOL 22
  23. 23. (4) ADVANTAGES OF BIOETHANOL Environmental feasibility: Befouled are biodegradable and far less toxic that fossil fuels, Benefit over fossil fuels is the greenhouse gas emissions reduced. As motor fuel: The principle fuel used as a petrol substitute is bioethanol in terms of E85, E10. The most common blend is 10% ethanol and 90% petrol .Blending bioethanol with petrol will ensure greater fuel security, avoiding heavy reliance on oil producing nations. Calorific value: Although the Gross calorific value of ethanol is (29,700kj/kg) lower than petrol (48,000kj/kg) and diesel (44,800 kj/kg), yet is less toxic than bothers. Ethanol is a high octane fuel and has replaced lead as an octane enhancer in petrol , also it has low tendency to create knocking in spark engines. Minimum expenses: The cost of Ethanol production from lignocelluloses is approx Rs.55/- per liter at this time but in a large scale and using modern, techniques it will be minimized. 23
  24. 24. Fuel properties of anhydrous ethanol and comparison with petrol and diesel fuel Property Composition, weight % C H O Density, kg/m3 Lower heating value, MJ/kg Octane number Cetane number / n-Heptane Rapid vapour pressure (kPa) Stoichiometric air/fuel ratio, weight Boiling temperature, °C Flash point, closed cup, °C Ethanol 52.2 13.1 34.7 794 26.7 100 8 15.6 9:1 78 13 Petrol Diesel 85-88 12-15 0 750 42.9 85-90 5-15 55-103 14:1 80-225 -42 84-87 13-16 0 825 43 30-40 1.4 16:1 188-343 74 Sources: JEC, 2005; Joseph, 2007 24
  25. 25. Effects of Blend on Octane Rating 120 115 Octane Number 110 105 100 95 90 85 80 75 0 20 40 60 80 100 Volume % Ethanol Research Octane No. Motor Octaane No. As the ethanol blending (% of ethanol) increases in the gasoline, Octane rating becomes slightly higher. From the figure the Motor Octane number was found maximum for 100% blend, 112. While Research Octane number was found 118 on 100% blending (Bailey 25 and John Russell ).
  26. 26. 5- Conclusion & Effective Parameters (a) Effect of sugar concentration: Ethanol Production slightly decreases with increase in sugar concentration . It can be concluded that it is possible to successively use sugarcane bagasse, wheat bran and rape straw for bioethanol. Enzyme treatment at 30ºC and pH 5 is an effective treatment method for converting biomass to glucose. (b) Effect of temperature: Ethanol production is significantly reduced by increasing the temperature . (c) Effect of Ph: In case of different pH ethanol fermentation is more favourable at pH 5-6. (d) Effect of nutrient supplementation on ethanol production: In order to improve the bio ethanol production nitrogen source in fermentation medium such as NaNO3 , KNO3 enhances the enzymatic growth as well as fermentation. (e) Effect of Inoculums size: Enzymatic growth and Ethanol production is significantly increases by greater inoculums size. 26
  27. 27. 6-Major concerns/problems in bio ethanol production from cellulosic materials  The ability to ferment pentose (five-carbon sugars), especially xylose and arabinose, into ethanol is important for the efficiency and economics of the process.  Recently, special microorganisms have been genetically engineered which can ferment these sugars into ethanol with relatively high efficiency.  Formation of inhibitors is also the effective parameter which decreases the ethanol productivity. Inhibitors decreases the enzymatic growth.  Some of the methods which are required to enhance the production of ethanol from biomass are: Evaporation, Extraction with organic solvents and Adsorption on activated charcoal, molecular sieves, Neutralization, Alkaline Detoxification . 27
  28. 28. Future Prospects 1. 2. 3. 4. 5. The production of ethanol from lignocellulosic materials can be made cost-effective and done in large scale provided the following conditions are satisfied: Raw materials can be produced insufficiently large amounts and costs of production and collection are acceptable. Pretreatment of lignocellulosic materials is cost-effective. High yields of ethanol from hexoses and pentose's are attainable. Environmental pollution due to the process is minimized. If bio fuels continue their rapid growth around the globe, the impact on the agricultural sector can be significant. Increased jobs and economic development for rural areas in both industrialised and developing countries is one possibility, if governments put the appropriate policies in place and enforce them. The more involved farmers are in the production, processing, and use of bio fuels, the more likely they are to benefit from them. 28
  29. 29. A Case Study Total Biomass (Agricultural Residue) and projected biofuel (Ethanol) production upon total Area (In thousand hect.) of main crops in Uttar Pradesh (2012-13). S.N Agricultural Residue Biomass (dry ton/acre/y ear) 1-3 EtOH Yield (liter/dry ton) 333 EtOH Yield (liter/acre/year) Wheat Straw Agricultural area (In Thousand Hect.) 9485 1. 2. Rice Straw 4372 3-4 335 1173 3. Barley Straw 58 3-5 345 1380 4. Sugar cane Bagasse Maize Straw 1970 5-6 360 1980 274 3-4 345 1208 Rape (Sarson) Straw 622 3-5 355 1180 5. 6. 666 Biomass data Source: U.P. all agricultural sankhyikiya spatrika 29
  30. 30. Benefits of Biofuels: Using alternative energy is better for the envoirment. Using homegrown energy is better for health. Using Biofuels is better for the (Rural) economy. It makes us less dependent on foreign imports.  Private Sector Investments  Rural Employment  Reduction in Petroleum Imports  Energy Security  Earnings from Carbon Credits 30
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