1. Biomass The future source of energy and chemicalsJanardhan.H.L Material science Division PPISR, Bidlur,Devanhalli Bengaluru - 562110

2. Present sources of Energy Global Scenario: Petroleum 33% Coal 24% Natural gas 19% Nuclear power5%Hydropower6%Biomass13% 3. Time for energy concernPeak oil is defined as the point in time when the rate of global petroleum extraction is reached maximum, after which the rate of production enters terminal decline. 4. Time for energy concern India ranks among the top 10 largest oilconsuming countries. Oil accounts for about 30% of India's total energy consumption. Presently, India imports about 70% of its total oil consumption and makes no exports. This naturally would create a supply deficit, as domestic oil production is unlikely to keep pace with demand. India's rough production is only 0.8 million barrels per day. 5. Traditional Idea Modern Approach Energy and Chemicals from Biomass 6. Fuelwood Demand in India in 1996 Consumption of FuelwoodMillion Tons1. Household (a) Forested Rural (b) Non Forested Rural (c) Urban Areas Sub Total78 74 10 1622. Cottage Industry 3. Rituals 4. Hotels etc. Total25 4 10 201 7. Bio-Digester as fuel sourcePlant, kitchen, animal and human waste is used as feed and methanogenic bacteria converts organic molecule into methane 8. Fuel from Agricultural products Enzymatic breakdown of sugars present in sugarcane, maize, sugar-beet, etc; to get Ethanol, Mild acid hydrolysis of agricultural waste, including wood, followed by enzymatic breakdown to get Methanol/Ethanol. Transesterification of oils and fats to produce biodiesel Gasification of biomass to produce syngas, used in the manufacture of liquid by Fischer-Tropsh synthesis 9. Better option? The daily input of dung and urine from a single cow produces 12 kilowatt-hours of electricity or 89 kilowatt-hours of heat, from biogas plant. Dilute acid hydrolysis of wood followed by fermentation produces 11% of ethanol, and generates 40.2 kg of waste per kg of ethanol, If the starting material of the biodiesel is edible oil/fodder it may compete with the agricultural land for food/fodder. 10. Big challenge! 70.6% of crude oil as fuel generates US$ 385 billion a year, but 3.4% 0f crude oil consumed for petrochemicals and specialties generate roughly same amount of money 11. Role of biomass conversion in CO2 cycle 12. Composition of wood based biomass Cellulose40% Hemicellulose 25% Lignin 30% Oil,fats,proteins and other substances 5% 13. Second generation biofuelsBagasseFirst generation biofuelsSteam splitting Heat powerBurnJuice LigninExtraction and trans esternCelluloseHemi celluloseHydrolysis , pt-catayst (e.g: PtUSY)Glucose Thermal cracking 250-600C, base cat.Low mol wt feedstocks (phenols) Hydro processingAlkyl benzenes (Biofuel)Bio-OilGasificationSyngasBioethanol Water Pt catalystseparationPhenolic fractionHydrogenFlow-chart of Biomass conversionMethanolFischerTropsch productsBiodiesel++GlycerolCarbohydrate fraction Catalytic steam reformPhenolic resinsFermentationComplete gasification 800-1000C ( 2 bar)Catalyst 500 CMTO MTG MTPGlycerolBiological gasificationHydrogen 14. Generations of Bio-Fuels At present the production of first generation bio ethanol mainly utilizes plants rich in carbohydrates. First generation biodiesel produced by transesterification of vegetable oils, or animal fats. Second generation biofuels are still under development, and the focus lies on the utilization of wood-based biomass. 15. Bio-Refinery Lignocellulosic biomass is converted through a number of different processes into a mixture of products, including biofuels, valuable chemicals, heat and electricity. Lignocellulosic biorefinary attempts to parallel the working of crude-oil refinery. An abundant raw material, consisting mainly lignin, cellulose, and hemicellulose, enters biorefinery. 16. Bio-Refining process Wood is converted into bio oil by fast pyrolysis, subsequently it is refined or/and gasification of bio mass, followed by catalytic upgrading of the productsor/andseparationofsugarswithsubsequent catalytic upgrading of the products. 17. Characteristics of bio-oil High water and oxygen content Corrosive Lower stability Immiscibility with crude-oil-based fuels High acidity High viscosity Low calorific value 18. Bio-Refining process Highly oxygenated raw material is functionalized or controllably defunctionalized as the energy liberated by the compound decreases with the increase in the O/C molar ratio, as compared with its analogue. Methanol on combustion yields 727kJ/mol Methane on combustion yields 891kJ/mol Ethanol on combustion yields 1367kJ/mol Ethane on combustion yields 1560kJ/mol 19. Bio-Refining process using solid Acid/Base Pyrolysis of cellulose and hemicellulose results in many simultaneous reactions such as hydrolysis, oxidation, depolymerization, dehydration and decarboxylation. Pyrolysis of lignin between 250 and 600C yields valuable low molecular weight feedstocks. Application of shape selective cracking catalysts would allow the process to be run at low temperatures and improved product distribution. 20. Bio-Refining process using solid Acid/Base Micro or Mesoporous hybrid materials doped with noble and transition metals, and base catalysts are used to selective decarboxylation, to produce high quality bio oil with less amount oxygen and water. Ex: AlMCM-41, MSU, ZSM-5,etc. 21. Catalyst testing for biorefining The catalyst is placed in the reactor and the biomass is placed in the piston cylinder. The reactor and piston cylinder are connected. Experiment is started when the temperature reaches 500C, biomass enters the reactor and the reaction starts.Fixed-bed unit for the catalytic conversion of wood based biomass 22. Catalyst activity comparisionAlMCM-41 is a promising catalyst in biorefining 23. ContinuedMSU type molecular sieve is next to MCM type, but lower organic phase in biooil and higher coke and char yields compared to Al-MCM-41 and non catalytic pyrolysis.Non-catalytic MSU-S/HNon-catalytic MSU-S/HMSU-S/WMSU-S/WAl-MCM-41Al-MCM-41 24. Chemicals from Biomass Acid hydrolysis and crackingHemicellulose + water at 170C, 5MpaN2 for 3hrsDhepe et.al, DOI: 10.1039/c004128a 25. Cellulose hydrolysis by solid acidsA. Onda,et.al. Green Chem., 2008, 10, 1033Hydrolysis of cellulose over various solid acid catalysts at 423 K. Reaction conditions: milled cellulose 45 mg, catalyst 50 mg, distilled water 5.0 mL, 24 h. 26. Energy and chemicals from bagasse Bagasse waste production in sugar plant 27. What cane variety for bio-energy ?Current varietySugar Bagasse for electricity & ethanolHigh quality High qualityMore Sugar More bagasse for electricity & ethanolHigh fibreLess Sugar Much more bagasse for electricity & ethanolEnergy caneSmall amount of sugar for ethanol Much more bagasse for electricity & ethanolFibre 10 12 % -Fibre 17 - 22 % Fibre 17 - 22 % Fibre 20 - 30 % Fibre > 30 % 28. Ethanol and Bioplastic from Bagasse 3 Steps 1. Lignin removal from bagasse 2. Convert hemicellulose and cellulose into simple sugars 3. Convert simple sugars into ethanol and bioplasticLignin 19.6Ash 6.3Hemicellulose 28.4Cellulose 40.6Sugar 3.1 29. Bio-diesel First generation Bio-diesel is manufactured by the tansesterification of the oils / Fat NaOHTriglycerideMethanolBio-Diesel (Methyl Ester)GlycerolRecent development is catalytic cracking of non edible oils to get mixture of hydrocarbons that are present in various fractions of gasoline, kerosene, and diesel. 30. Comparison of production Oil CropGallons of Oil per AcreSoybeans48Rapeseed127Jatropha435-2000Algae5000-15,000 31. Bio-fuel from algae Algal strains with high oil content can be used as feed stock for biodiesel production. Several species of algae with high starch content are now being tested to produce ethanol. Algae produces a lot more oil per acre than all the other oil crops put together. And this is why algae biodiesel is gaining more and more interest. Ex: Botryococcus braunii, Chlorella, Dunalielle tertiolecta, Gracilaria, Pleurochrysis carterae, sargassum(10 times more out put volume of Gracilaria)Contd 32. Advantages of Bio-fuel from algae Compared to other feedstock's, algae can provide a highyield source of bio-diesel, ethanol and aviation fuels . It does not effect food supplies, rainforests or arable land. Algae are the fastest growing plants in the world. They use photosynthesis to harness sunlight and carbon di oxide. 33. Pilot units India have 20+ years of application of gasification technology for thermal, motive power and electrification. Over 1600 gasifier systems, having 16 MW total capacity, have generated 42 million Kilo Watt hour (KWh) of electricity, replacing 8.8million liters of oil annually (CMIE, 1996)Contd 34. ContdFour gasifier Action Research Centers (ARCs) located within different national institutions and supported by the MNES have developed twelve gasifier models, ranging from 3.5 to 100 KW. Two co-generation projects (3 MW surplus power capacity) in sugar mills and one rice paddy straw based power project (10 MW) were commissioned.Contd 35. ContdBTL process for the production of bio-fuels are under development, and several pilot units are under construction or already running. The most advanced unit is the pilot plant from Choren Industries in Freiberg (Germany) in cooperation with shell. Petroalgae a USA based company want to launch its fuel from algae by next year. IOC R&D centre in association with NTPC to scale up algal growth by utilizing CO2 rich flue gas from thermal stacks. Contd 36. ContdPraj a pune based company, has established a pilot plant of 2 ton/day capacity for converting ligno-cellulosic materials to ethanol and are planing to put up a much larger capacity plant next year. The lignocellulosic biomass fractionation technology developed by NCL, Pune, has been scaled up by Godavari Biorefineries. ExxonMobil invested $300 million in Synthetic Genomics to develop algae biofuel. 37. Major Obstacles High investment costsLow volumetric energy density of bio massLack of infrastructureLimitations to the productivity of photosynthesisAvailable of cultivable land areas for the production of bio energy plants, which are in competition with food production 38. Present challenge Understanding the mechanism of the catalytic conversion of lignocellulosic biomass into bio-oil, including structure-property relationships and product distribution. Catalyst development, regarding porosity, acidity, basicity, metal support interactions, controlled formation of catalyst particles, improved hydrothermal stability, resistance to catalyst deactivation Process condition and large scale production 39. Recent Bioenergy news updates from India March 22, 2011: The country is aiming to generate about 10,000MW of energy from biomass over the next decade said Deepak Gupta, Secretary of the Ministry of New and Renewable Energy (MNRE), in Bangalore. K. Verma, MD, Karnataka State Forest Industries Corporation Limited, highlighted the importance of plantation, especially bamboo, to provide sustainable supply of feedstock for power generation Jan 25, 2011: International Finance Corporation (IFC), a member of the World Bank, has guaranteed $300 million, for renewable energy projects in India. Jan 24, 2011: Reliance Venture Asset Management has completed the Series A funding for AllGreen Energy Ltd for its biomass project in Perundurai. Tamil Nadu. AllGreen is one of the leading players in the Indian renewable energy marketplace, through the usage of its biomass gasification power plants that use agricultural waste to generate power Nov. 18, 2010: Clenergen Corporation is to join forces with Yuken India Limited to install a 4 MW/h Gasification Biomass Power Plant operating on gas engines at their manufacturing facility in Bangalore, India. August 27, 2010: Orient Green Power Company, Chennai set a target of 200MW of biomass power generation and at present is generating 40MW from biomass plants. 40. List of Companies working on Biomass to Energy Reliance Venture Asset Management Abellon Clean Energy Ltd, India - Gujarat , India BioEnergy Consult - Uttar Pradesh, India Deep Industries - Gujarat, India Saltmarch Media - Karnataka, India Yuken India Orient Green Power Company etc 41. Conclusive Remarks In 20th and early 21st century the development of countries were designed around crude oil, due to high availability and low prices. But today, scenario based on crude oil is unsustainable at long term. The conversion of wood based biomass to energy and chemicals is an attractive area since the raw material is available in plenty and at cheaper rate. Wood based biomass contains cellulose, hemicellulose and lignin. All these can be converted into energy with suitable treatment. Heterogeneous solid catalysts play a major role in gasification, acid hydrolysis, cracking steps in biomass conversion. So far the drawbacks of reported catalysts are their low hydrothermal stability, lower activity and poor recyclability. Hydrothermally stable zeolites or carbon based catalysts may be a future for hydrolysis and cracking of biomass. Contd 42. Continued A race to develop a better catalyst is still on. R&D is necessary in this field for the complete utilization of biomass into fuel and specialty chemicals. Next century development will be limited by the supply of crude oil. As the biomass composition varies from species to species catalyst development is challenging. Global energy may not be fulfilled by biomass only, hybrid with other renewable energy source may be utilized. 43. References: 1) Biofuels and Biomass-To-Liquid Fuels in the Biorefinery: Catalytic Conversion of Lignocellulosic Biomass using Porous Materials -Michael Stcker, Angew.Chem. Int. Ed. 2008, 47, 9200 9211 DOI: 10.1002/anie.200801476 2) A solid-acid-based process for the conversion of hemicellulose -Paresh Laxmikant Dhepe and Ramakanta Sahu Green, Chem., 2010, 12, 21532156 | 2153, DOI: 10.1039/c004128a 3) Design of solid catalysts for the conversion of biomass -Roberto Rinaldi and Ferdi Schuth, Energy Environ. Sci., 2009, 2, 610626, DOI: 10.1039/b902668a 4) Selective hydrolysis of cellulose into glucose over solid acid catalysts -Ayumu Onda, Takafumi Ochi and Kazumichi Yanagisawa, DOI: 10.1039/b808471h 5) Sustainable biomass power for rural India : Case study of biomass gasifier for village electrification -N. H. Ravindranath, H. I. Somashekar, S. Dasappa and C. N. Jayasheela Reddy, CURRENT SCIENCE, VOL. 87, NO. 7, 10 OCTOBER 2004 6) BIOMASS ENERGY IN INDIA : TRANSITION FROM TRADITIONAL TO MODERN - P.R. Shukla, http://www.e2analytics.com, The Social Engineer, Vol. 6, No. 2 7) Fixed Bed Catalytic Cracking Of Non-Edible Oils Using Zeolites For The Production Of the Bio-Fuel. G. Ramya & T. Sivakumar, Bulletin Of the Catalysis Society Of India, Vol.9, Issue 3 & 4 (2010) 83-90. 44. Thank you