Thermochemical Conversion of Biomass to Fuel.cenusa brown 5-25-12
5 likes3,208 views
The document discusses renewable energy production through thermochemical processes such as gasification and pyrolysis, focusing on biomass as a feedstock. It outlines the characteristics and advantages of different biomass types, production methods, and the conversion of biomass to biofuels. Additionally, it emphasizes the potential applications of biochar and bio-oil, including their roles in soil enhancement and carbon sequestration.
More Related Content
Similar to Thermochemical Conversion of Biomass to Fuel.cenusa brown 5-25-12 (20)
![Biochar root growth_and_rhizosphere_communities[linkedi]](https://cdn.slidesharecdn.com/ss_thumbnails/biocharrootgrowthandrhizospherecommunitieslinkedi-120402092601-phpapp02-thumbnail.jpg?width=560&fit=bounds)
Thermochemical Conversion of Biomass to Fuel.cenusa brown 5-25-12
- 1. Center for Sustainable Environmental Technologies The Thermochemical Option Robert C. Brown Robert C. Brown Center for Sustainable Environmental Technologies Iowa State University Iowa State University CenUSA Webinar May 25, 2012
- 2. Center for Sustainable Environmental Technologies What is the Perfect Energy Carrier for Transportation Fuel? What is the Perfect Energy Carrier for Transportation Fuel? • Liquid at ambient conditions d b d • Immiscible in water • Low toxicity • High energy density • Cold weather operability • Stable during long‐term storage • Efficient production from a primary energy source
- 3. Center for Sustainable Environmental Technologies Drop‐In Fuels Drop‐In Fuels • Fully compatible with existing fuel infrastructure – Hydrocarbons (alkanes and aromatics) – Possibly butanol • Are drop in fuels also the “perfect fuel?” – Close enough
- 4. Center for Sustainable Environmental Technologies Three Kinds of Biomass Three Kinds of Biomass • Lipid‐rich biomass Lipid‐rich biomass • Lignocellulosic biomass • Waste biomass
- 5. Center for Sustainable Environmental Technologies Lignocellulosic Feedstock • Lignocellulose a three- three dimensional polymeric composites formed by plants as structural material • Constituents include: – Cellulose: main source of glucose (C6 sugar) – Lignin: source of xylose (C5 sugar) g ) Glycosidic • Simple sugars can be bonds liberated from carbohydrate either enzymatically or Cellulose is a polymer of monosaccharides thermally (glucose)
- 6. Center for Sustainable Environmental Technologies Lipid Feedstocks: Nearly hydrocarbons Lipid Feedstocks: Nearly hydrocarbons • Triglycerides: Three fatty acids attached to glycerol backbone found in oil seeds and microalgae b kb f d i il d d i l • Readily converted to pure hydrocarbons via hydrogenation h d ti H2 H2 H2 H2 H2 H2 H2 H2 O H3C C C C C C C C C C O CH2 C C C C C C C C H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 O H3C C C C C C C C C C O CH C C C C C C C C H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 O H3C C C C C C C C C C O CH2 C C C C C C C C H2 H2 H2 H2 H2 H2 H2 H2
- 7. Center for Sustainable Environmental Technologies Lipids vs Lipids vs Lignocellulose Which Kind of Plant Should Deoxygenate Carbohydrate? Glucose Unit Glycosidic Bonds OH CH2OH OH CH2OH OH CH2OH OH O O O O O O OH OH OH OH OH Plant No. 2 OH OH O O O O O O O CH2OH OH CH2OH OH CH2OH OH CH2OH Plant No. 1 CO2 H2O Lipid biosynthesis Lipid involves biological deoxygenation of yg carbohydrates, too! CO2 Cellulose to hydrocarbons Cellulose to hydrocarbons involves deoxygenation of CO2 Source: Nature Medicine carbohydrate 11, 599 – 600, 2005.
- 8. Center for Sustainable Environmental Technologies Renewable Fuels Technologies Renewable Fuels Technologies FEEDSTOCKS TECHNOLOGY BIOFUELS OILSEED CROPS Transesterification FAME ALGAE Pyrolysis Gasification AG WASTES CELLULOSIC Catalysis BIOMASS FUEL HYDROCARBONS TREES Chemical GRASSES Catalysis GRAINS STARCH ALCOHOLS Biochemical SUGAR Conversion C i SUGARCANE
- 9. Center for Sustainable Environmental Technologies Thermochemical Biofuels Thermochemical Biofuels • The other cellulosic biofuels… • Syngas to biofuels (via gasification) • Bi il t bi f l Bio‐oil to biofuels (via fast pyrolysis) • Builds upon core competencies at Builds upon core competencies at ½ tpd oxygen-blown gasifier at ISU’s BioCentury Research Farm ISU • Gasification and pyrolysis • Catalysis • Novel fermentations • Techno‐economic and life cycle analysis l i 1/4 tpd fast pyrolyzer at ISU’s BioCentury Research Farm USDA REE E S it
- 10. Center for Sustainable Environmental Technologies Generalized Thermochemical Process Generalized Thermochemical Process Feedstock Depolymerization/ Decomposition Depolymerization/ Decomposition Thermolytic Thermolytic Substrate Upgrading Biofuel
- 11. Center for Sustainable Environmental Technologies Gasification • Gasification is the thermal decomposition of organic matter into flammable gases g Heating and Drying Pyrolysis Gas-Solid Reactions Gas-phase Reactions Volatile gases: CO, CO + H2O CO2 + H2 CO2, H2, H2O light O, hydrocarbons, tar CO + 3H2 CH4 + H2O H 2O Heat CO 2 CO ½ O2 CO2 char 2H2 Porosity increases CO CH4 Thermal front H2O H2 penetrates particle Endothermic Exothermic reactions reactions 11
- 12. Center for Sustainable Environmental Technologies Two Major Gasification Options Two Major Gasification Options Low Temperature Gasification High Temperature Gasification (Bubbling Fluidized Bed) (Entrained Flow Gasifier) oxygen Syngas biomass Biomass 1300 °C Ash Fluidized Bed Water cooled radiation screen Steam/ Oxygen O raw syngas and molten slag
- 13. Center for Sustainable Environmental Technologies Syngas • Syngas consists mostly of CO, H2, CO2, CH4 Composition of syngas (volume percent) Hydrogen Carbon Carbon Methane Nitrogen HHV Monoxide Dioxide (MJ/m3) 32 488 15 2 3 10.4 0 • Syngas also contains small amounts of tar, alkali metals, sulfur, nitrogen, and chlorine that must be removed before it can be nitrogen and chlorine that m st be remo ed before it can be catalytically upgraded to transportation fuels Raw Syngas Gasifier Particulate Removal Biofuel Biomass Tar Alkali Sulfur Nitrogen Catalytic Oxygen/Steam Removal Removal Removal Removal Synthesis
- 14. Center for Sustainable Environmental Technologies Gasification Efficiency • Thermal efficiency - conversion of chemical energy of solid fuel to chemical energy and sensible heat of gaseous product – High temperature, high-pressure gasifiers: >95% – Typical biomass gasifiers: 70 - 90% • Cold gas efficiency – conversion of chemical energy of solid fuel to chemical energy of gaseous product – T i l bi Typical biomass gasifiers: 50 75% ifi 50-75% 14
- 15. Center for Sustainable Environmental Technologies Gasification Opportunities and Challenges Gasification Opportunities and Challenges • Advantages – Tolerates relatively dirty biomass feedstock – Produces uniform intermediate product (syngas) – Proven method for “cracking the lignocellulosic nut” – Allows energy integration in biorefinery • Disadvantages g – Gas cleaning technologies still under development – Synfuel processing occurs at high processing occurs at high ½ tpd gasification plant at ISU’s pressures BioCentury Research Farm
- 16. Center for Sustainable Environmental Technologies Syngas Upgrading to Fuels Syngas Upgrading to Fuels • Catalytic – performed at moderate temperatures and high pressures temperatures and high pressures using metal catalysts – Fischer‐Tropsch synthesis to hydrocarbons suitable for fuels – Methanol synthesis followed by upgrading to gasoline upgrading to gasoline – Ethanol synthesis • S Syngas fermentation – performed f t ti f d at ambient temperature and p pressure using biocatalysts g y
- 17. Center for Sustainable Environmental Technologies Pyrolysis Definition – thermal decomposition of Definition thermal decomposition of carbonaceous material in the absence of oxygen of oxygen
- 18. Center for Sustainable Environmental Technologies Py Products • Gas – non‐condensable gases like carbon dioxide, carbon monoxide, hydrogen • Solid – mixture of inorganic compounds (ash) and carbonaceous materials (charcoal) • Liquid – mixture of water and organic Bio- Bio-oil compounds known as bio‐oil recovered from bio oil recovered from pyrolysis vapors and aerosols (smoke) aerosols (smoke)
- 19. Center for Sustainable Environmental Technologies The many faces of pyrolysis The many faces of pyrolysis Technology Residence Heating Rate Temperature Predominate Time (C) Products carbonization days very low 400 charcoal conventional 5‐30 min low 600 oil, gas, char gasification 0.5‐5 min moderate >700 gas Fast pyrolysis 0.5‐5 s very high 650 oil flash‐liquid <1 s high <650 oil flash‐gas <1 s high <650 chemicals, gas ultra <0.5 s very high 1000 chemicals, gas vacuum 2‐30s 2 30s high <500 oil hydro‐pyrolysis <10s high <500 oil methano‐pyrolysis <10s high <700 chemicals Mohan D., Pittman C. U. Jr., and Steele P. H. “Pyrolysis of Wood/Biomass for Bio‐oil: A Critical Review” Energy & Fuels, 20, 848‐889 (2006)
- 20. Center for Sustainable Environmental Technologies Carbonization (slow pyrolysis) Carbonization (slow pyrolysis) • Charcoal is the carbonaceous residue obtained from heating biomass under oxygen‐starved bi d d conditions. • Charcoal word origin ‐ “the making of coal. of coal ” • Geological processes that make coal are quite different from those that produce charcoal and properties are Charcoal yields (dry weight basis) y ( y g ) quite different. for different kinds of batch kilns • Charcoal contains 65% to 90% Kiln Type Charcoal Yield carbon with the balance being Pit 12.5‐30 volatile matter and mineral matter l til tt d i l tt Mound Mound 2‐42 2 42 (ash). Brick 12.5‐33 • Antal, Jr., M. J. and Gronli, M. (2003) Portable Steel (TPI) 18.9‐31.4 The Art, Science, and Technology of The Art, Science, and Technology of Concrete (Missouri) 33 Kammen, D. M., and Lew, D. J. (2005) Review of technologies for the production and use Charcoal Production, Ind. Eng. of charcoal, Renewable and Appropriate Energy Laboratory, Berkeley University, March 1, http://rael.berkeley.edu/files/2005/Kammen‐Lew‐Charcoal‐2005.pdf, accessed Chem. Res. 42, 1619‐1640 November 17, 2007.
- 21. Center for Sustainable Environmental Technologies The many faces of pyrolysis The many faces of pyrolysis Technology Residence Heating Rate Temperature Predominate Time (C) Products carbonization days very low 400 charcoal conventional 5‐30 min low 600 oil, gas, char gasification 0.5‐5 min moderate >700 gas fast pyrolysis 0.5‐5 s very high 650 oil flash‐liquid <1 s high <650 oil flash‐gas <1 s high <650 chemicals, gas ultra <0.5 s very high 1000 chemicals, gas vacuum 2‐30s 2 30s high <500 oil hydro‐pyrolysis <10s high <500 oil methano‐pyrolysis <10s high <700 chemicals Mohan D., Pittman C. U. Jr., and Steele P. H. “Pyrolysis of Wood/Biomass for Bio‐oil: A Critical Review” Energy & Fuels, 20, 848‐889 (2006)
- 22. Center for Sustainable Environmental Technologies Fast Pyrolysis y y Fast pyrolysis - rapid thermal decomposition of organic compounds in the absence of oxygen to produce predominately liquid product Biochar
- 23. Center for Sustainable Environmental Technologies Fast Pyrolysis Fast Pyrolysis • Dry feedstock: <10% • Small particles: <3 mm • Moderate temperatures (400‐500 oC) • Short residence times: 0.5 ‐ 2 s • Rapid quenching at the end of the process • Typical yields Oil: 60 ‐ 70% Char: 12 ‐15% Gas: 13 ‐ 25%
- 24. Center for Sustainable Environmental Technologies Bio‐Oil Bio Oil Source: Piskorz, J., et al. (1988) White Poplar Pyrolysis liquid (bio‐oil) Spruce from flash pyrolysis is a from flash pyrolysis is a Moisture content, wt% 7.0 3.3 low viscosity, dark‐ Particle size, m (max) 1000 590 brown fluid with up to Temperature 500 497 15 to 20% ater 15 to 20% water Apparent residence time Apparent residence time 0 65 0.65 0 48 0.48 Bio‐oil composition, wt %, m.f. Saccharides 3.3 2.4 Anhydrosugars 6.5 6.8 Aldehydes 10.1 14.0 Furans 0.35 ‐‐ Ketones 1.24 1.4 Alcohols 2.0 1.2 Carboxylic acids 11.0 8.5 Water‐Soluble – Total Above 34.5 34.3 Pyrolytic Lignin 20.6 16.2 Unaccounted fraction 11.4 15.2
- 25. Center for Sustainable Environmental Technologies Energy Efficiency Energy Efficiency • Conversion to 75 wt‐% bio‐oil translates to energy efficiency of 70% ffi i f 70% • If carbon used for energy source (process heat or slurried with liquid) then efficiency approaches 94% slurried with liquid) then efficiency approaches 94% Source: http://www.ensyn.com/info/23102000.htm
- 26. Center for Sustainable Environmental Technologies Fast Pyrolysis Opportunities and Challenges Fast Pyrolysis Opportunities and Challenges • Advantages of bio oil: Advantages of bio‐oil: – Can be upgraded to drop‐in ( y (hydrocarbon) fuels ) – Opportunities for distributed processing ¼ ton per day fast pyrolysis pilot plant at • Disadvantages of bio‐oil ISU BioCentury Research Farm – High oxygen and water content makes bio‐oil inferior to High oxygen and water content makes bio oil inferior to petroleum‐derived fuels – Phase‐separation and polymerization and corrosiveness make long‐term storage difficult
- 27. Center for Sustainable Environmental Technologies Applications of Bio‐Oil Applications of Bio‐Oil • Stationary Power Stationary Power • Commodity Chemicals • Transportation Fuels i l
- 28. Center for Sustainable Environmental Technologies And Sugar and Bioasphalt! And Sugar and Bioasphalt! Heavy Ends Sugar solution (>20 wt%) Water Wash Raffinate (mostly phenolic oligomers derived from lignin)
- 29. Center for Sustainable Environmental Technologies Biochar • Carbonaceous residue from pyrolysis of biomass pyrolysis of biomass • Yields range from 5‐40% of biomass depending upon process biomass depending upon process conditions • Fine, porous structure ,p • Several potential applications, the most intriguing being dual g g g use as soil amendment and carbon sequestration agent
- 30. Center for Sustainable Environmental Technologies Terra Preta: Anthropogenic Soils from Biochar Terra Preta: Anthropogenic Soils from Biochar • Created hundreds of years y Terra Preta Oxisol ago by pre‐Colombian inhabitants of Amazon Basin • Result of slash and char agriculture • Much higher levels of soil organic carbon • F Far more productive than d i h Applied to the land, biochar serves as undisturbed both soil amendment and carbon oxisol soils sequestration agent Glaser et al. 2001. Naturwissenschaften (2001) 88:37–41
- 31. Center for Sustainable Environmental Technologies Biochar s Biochar’s Impact • Biochar increases soil cation exchange Increases: capacity (CEC), holding ammonium ions capacity (CEC), holding ammonium ions g Cation Exchange (NH4+) and other cations in the soil Capacity Soil Organic Matter • Biochar adsorbs soil organic matter which g Drainage contains plant‐available organic nitrogen1 Aeration • Biochar’s low bulk density increases soil aeration and water drainage, lessening the g , g Decreases: D likelihood of denitrification (NO3‐ N2O N2) and associated N2O emissions2 Soil Bulk Density Denitrification • Addition of biochar has been shown to Addition of biochar has been shown to N2O Emissions decrease nutrient leaching (nitrate, phosphate, cations) from manure Nutrient Leaching amendments3 1. Laird, D. A., Agron J 2008, 100, (1), 178-181. 2. Rogovska, et al. North American Biochar Conference, Boulder, CO, Aug 2009. 3. Laird, et al. 2008 GSA-SSSA-ASA-CSA Joint Meeting, Houston, TX, Oct 2008.
- 32. Center for Sustainable Environmental Technologies GHG Impacts of Soil Application of Biochar GHG Impacts of Soil Application of Biochar Increased CO2 Competition emissions due between food to enhanced and biomass soil microbial crops may respiration increase land under cultivation. + 0 _ Increase C Increased Reduce CO2 Reduce N2O Increase C Reduce CO2 input to soil yields may emissions emissions sequestration emissions due due to decrease the due to bio-oil from soils in soils to decreased enhanced amount of displacing due to better (Biochar C is use of lime plant growth land needed fossil fuel soil aeration very stable) and fertilizer to grow food.
- 33. Center for Sustainable Environmental Technologies Proof‐of‐Concept: Terra Preta in Brazil Proof‐of‐Concept: Terra Preta in Brazil Terra Preta Oxisol
- 34. Center for Sustainable Environmental Technologies Lovelock on Biochar Lovelock on Biochar “There is one way we could save ourselves and that is through the massive burial of through the massive burial of charcoal. It would mean farmers turning all their farmers turning all their agricultural waste…into non‐ James Lovelock in an biodegradable charcoal, and otherwise pessimistic burying it in the soil.” interview with New Scientist Magazine (January 2009) on our prospects for halting global t f h lti l b l climate change
- 35. Center for Sustainable Environmental Technologies ISU Facilities to Support Thermochemical Research Lab-scale pyrolyzers Micropyrolyzers & Batch and fixed bed and gasifiers bio-oil analysis catalytic upgrading reactors ISU Biorenewables Laboratory Quarter-ton/day pilot plant fast pyrolyzer Half-ton/day p y pilot p plant oxygen-blown gasifier ISU BioCentury Research Farm