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CONVERSION OF BIOMASS TO BIOFUELS

CONVERSION OF BIOMASS TO BIOFUELS . WSU ChE 481/581 & UI BAE 504. THERMOCHEMICAL CONVERSION SECTION. LECTURER: MANUEL GARCIA-PEREZ , Ph.D. Department of Biological Systems Engineering 205 L.J. Smith Hall, Phone number: 509-335-7758 e-mail: mgarcia-perez@wsu.edu. CREDIT HOURS: 3.

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CONVERSION OF BIOMASS TO BIOFUELS

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  1. CONVERSION OF BIOMASS TO BIOFUELS WSU ChE 481/581 & UI BAE 504 THERMOCHEMICAL CONVERSION SECTION LECTURER: MANUEL GARCIA-PEREZ , Ph.D. Department of Biological Systems Engineering 205 L.J. Smith Hall, Phone number: 509-335-7758 e-mail: mgarcia-perez@wsu.edu CREDIT HOURS: 3 MEEETING PLACE: EME B46, TUESDAY AND THURSDAY 1:25-2:40 AM

  2. OUTLINE OF OUR PREVIOUS LECTURE A.- OVERVIEW B.- BIOMASS RESOURCES (UNIQUE ROLE OF BIOMASS) C.- CONVERSION TECHNOLOGIES INTRODUCTION D.- INTRODUCTION TO THERMOCHEMICAL CONVERSION TECHNOLOGIES E.- CELLULOSE PRIMARY THERMOCHEMICAL REACTIONS F.- EFFECT OF ALKALINES, ACID AND OXYGEN THERMOCHEMICAL REACTIONS G.- INTERACTIONS BETWEEN THE CELLULOSE AND THE LIGNIN H.- SECONDARY THERMOCHEMICAL REACTIONS I.- CONCLUDING REMARKS

  3. OVERVIEW OF THE THERMOCHEMICAL SECTION LECTURE 1 INTRODUCTION TO BIOMASS THERMOCHEMICAL CONVERSION TECHNOLOGIES AND THERMO-CHEMICAL REACTIONS LECTURE 2 TORREFACTION AND PYROLYSIS (SLOW AND FAST) LECTURE 3 GASIFICATION, COMBUSTION AND HYDROTHERMAL CONVERSION LECTURE 4 CHARACTERIZATION AND USES OF THERMOCHEMICAL REACTION PRODUCTS

  4. SECOND LECTURE OUTLINE A.- TORREFACTION B.- SLOW PYROLYSIS (CARBONIZATION) C.- FAST PYROLYSIS D.- CONCLUSION

  5. A.-TORREFACTION (225-300 oC) TORREFACTION IS NOT YET COMMERCIALLY AVAILABLE TORREFACTION IS A THERMAL TREATMENT STEP IN THE RELATIVELY LOW TEMPERATURE RANGE OF 225 – 300 oC. THE AIM IS TO PRODUCE A FUEL WITH INCREASED ENERGY DENSITY BY DECOMPOSING THE REACTIVE HEMICELLULOSE. TORREFACTION ALSO INDUCES LARGE MODIFICATIONS IN THE STRUCTURE OF CELLULOSE AND LIGNIN. TORREFIED BIOMASS HAS LOWER MOISTURE CONTENT AND HIGHER CALORIFIC VALUE. TORREFIED BIOMASS CONTAINS 70 % OF ITS INITIAL WEIGHT AND 90 % OF THE ENERGY CONTENT. THE MOISTURE UP-TAKE OF TORREFIED BIOMASS IS VERY LIMITED FROM 1 TO 6 %. TORREFACTED BIOMASS HAS SEVERAL ADVANTAGES PRIOR TO GASIFICATION, ELECTRICITY CONSUMPTION FOR MILLING DECREASES SIGNIFICANTLY. THE FIBROUS STRUCTURE AND THE TENACY OF BIOMASS ARE REDUCED BY HEMICELLULOSE DECOMPOSITION TOGETHER WITH THE DEPOLYMERIZATION OF CELLULOSE DURING THE TORREFACTION REACTION. THE POWER CONSUMPTION IN SIZE REDUCTION IS DECREASED 85 % WHEN THE BIOMASS IS FIRST TORREFACTED. MOREOVER, THE CAPACITY OF THE MILL INCREASES IN PROPORTION TO THE PARTICLE SIZE. WHEN THE 0.2 mm PARTICLE SIZE IS CONSIDERED, THE CHIPPER CAPACITY FOR TORREFIED WILLOW IS UP TO 6.5 TIMES THE CAPACITY OF UNTREATED WILLOW. AIR UTILITY FUEL FLUE GAS TORREFACTION GASES Combustion TORREFIED BIOMASS BIOMASS Cooling Torrefaction Drying Heat exchange FLUE GAS FLUE GAS GENERAL FLOW DIAGRAM OF A TORREFACTION PROCESS

  6. A.-TORREFACTION (225-300 oC) MAIN REACTIONS HAPPENING DURING BIOMASS TORREFACTION CO2, H2O, CO, FORMIC ACID, ACETIC ACID, GLYOXAL, ACETOL, METHYL GLYOXAL CROSS LINKED DIMER, .... CELLOTRIOSAN CELLOBIOSAN LEVOGLUCOSAN HAA Depolymerization and Fragmentation 3’ 2 3 6 Fragmentation Depolymerization Fragmentation HIGH TEMPERATURE REACTIONS (320 – 600 oC) Intermolecular dehydratation Polycondensation 290 oC CRYSTALLINE CELLULOSE OF LOW DP (200-400) (ACTIVE CELLULOSE) MOLTEN CELLULOSE (INTERMEDIARY CELLULOSE) 1 4 7 5 CROSSLINKED CELLULOSE CHARCOAL + CO + CO2 CELLULOSE + H2O MAIN TORREFACTION REACTIONS LOW TEMPERATURE REACTIONS (180-320 oC) Varhegyi G, Jakab E: Is the Broido-Shafizadeh Model for Cellulose Pyrolysis True? Energy & Fuels 1994, 8, 1345-1352 Haas T.J., Nimlos M.R., Donohoe B.S.: Real-Time and Post-reaction Microscopic Structural Analysis of Biomass Undergoing Pyrolysis. Energy & Fuels 2009, 23, 3810-3817.

  7. A.-TORREFACTION (225-300 oC) Volatiles (0.128 kg, 632 kJ) Volatiles (0.332 kg, 3541 kJ) Wood (1 kg, 17630 kJ) Wood (1 kg, 17630 kJ) TORREFACTION REACTOR (250 oC, 30 min) TORREFACTION REACTOR (300 oC, 10 min) Torrefied Wood (0.872 kg, 17085 kJ) Torrefied Wood (0.668 kg, 14213 kJ) 0 AIR Heat (124 kJ) Heat (87 kJ) FLUE GAS 14.7 TORREFACTION GASES 1.7 Combustion 21.4 7.97 27.7 142.2 135.6 BIOMASS Cooling Torrefaction Drying 156.1 134.7 5.5 22.2 4.1 Heat exchange FLUE GAS FLUE GAS OVERALL MASS AND ENERGY BALANCES FOR TORREFACTION AT TWO DIFFERENT TEMPERATURES NET ENERGY FLOWS (IN MW) CORRESPONDING WITH TORREFACTION OF WOODCUTTINGS AT 280 oC . DURING TORREFACTION, BIOMASS LOSES RELATIVELY MORE OXYGEN AND HYDROGEN COMPARED TO CARBON. SUBSEQUENTLY, THE CALORIFIC VALUE OF PRODUCTS INCREASES. THE NET CALORIFIC VALUE OF TORREFIED BIOMASS IS ON THE RANGE OF 18-23 MJ/KG (LHV) OR 20-24 MJ/KG (HHV). THE TORREFIED BIOMASS ALSO BECOMES MORE POROUS WITH THE VOLUMETRIC DENSITY OF 180-300 KG/M3.

  8. A.- TORREFACTION (200-300 oC) COMPOSITION OF WOOD AND TORREFIED WOOD (WILLOW) TORREFIED WOOD (250 oC, 30 min) TORREFIED WOOD (300 oC, 10 min) WOOD Carbon 47.2 % 51.3 % 55.8 % Hydrogen 6.1 % 5.9 % 5.6 % 40.9 % 36.2 % Oxygen 45.1 % 0.4 % 0.5 % Nitrogen 0.3 % 1.5 % 1.9 % Ash 1.3 % LHV (MJ/kg) 17.6 19.4 21.0 THE NET EFFICIENCY OF TORREFACTION IS AROUND 91 % WHEN THE UTILITY CONSUMPTION IS INCLUDED. THE MASS YIELD OF THE TORREFACTION PROCESS IS AROUND 70 %

  9. B.- SLOW PYROLYSIS (350-600 oC) THE HISTORICAL DEVELOPMENT OF PYROLYSIS RELATED INDUSTRIES IS ONE OF THE MOST INTERESTING IN THE ANNALS OF INDUSTRIAL CHEMISTRY. VERY OFTEN THE BY-PRODUCT OF TODAY BECOMES THE MAIN PRODUCT OF TOMORROW. JAMES WITHROW, 19151 SINCE THE CHEMICAL INDUSTRY TODAY CAN PRODUCE THE BY-PRODUCTSOBTAINED FROM THE PYROLYSIS OF WOOD, WITH THE EXCEPTION OF CHARCOAL, MORE CHEAPLY THAN THE PYROLYSIS PROCESS, THE MAIN EMPHASIS IN THE LATTER IS ON THE PRODUCTION OF CHARCOAL. FOR THIS REASON SIMPLE CARBONIZATION METHODS, SIMILAR TO THE ORIGINAL CHARCOAL PILES BUT IN AN IMPROVED FORM ARE LIKELY TO BE MORE ECONOMICAL THAN MORE COMPLICATED PLANTS THAT PLACE EMPHASIS ON THE ISOLATION AND PROCESSING OF BY-PRODUCTS. HERMAN F.J. WENZL, 19702,3 1James, R, Withrow: The Chemical Engineering of the Hardwood Distillation Industry. Ind. Eng. Chem. Res. Vol. 7, No. II, p. 912 (1915) 2Wenzl H.F.J. The Chemical Technology of Wood, Academic Press, 1923. 3Antal MJ, Gronli M: The Art, Science and Technology of Charcoal Production. Ind. Eng. Chem. Res. 2003, 42, 1619-1640.

  10. O O OH O H OH O Oligo-sugars OH H HO H H H HO HO B.- SLOW PYROLYSIS (350-600 oC) CELLULOSE PRIMARY THERMOCHEMICAL REACTIONS CO2 CO CHAR (Polyaromatics) CH4 H2O CO O H2O CH4 H HO H2 O (II) HIGH TEMPERATURE REACTIONS (300-600 oC) 4 5 FAST PYROLYSIS 6 2 3 1 Cellulose of Low DP (Active Cellulose) Molten Cellulose Cross-linked Cellulose Cellulose H2O + SLOW PYROLYSIS (I) LOW TEMPERATURE REACTIONS (180-300 oC) (PRE-TREATMENT)

  11. B.- SLOW PYROLYSIS (350-600 oC) SLOW PYROLYSIS AND PRODUCTION OF CHARCOAL SLOW PYROLYSIS: BIOMASS IS PYROLYSED AT SLOW HEATING RATES (5-100 oC/MIN). THIS LEADS TO LESS LIQUID AND MORE CHAR PRODUCTION. USERS PREFER CHARCOAL OVER OTHER BIOMASS FUELS SUCH AS WOOD. CHARCOALHAS A HIGHER ENERGY DENSITY THAN OTHER BIOMASS FUELS AND CAN BE STORED WITHOUT FEAR OF INSECT PROBLEMS. CHARCOAL IS ALSO DESIRED FOR THE FLAVORS WHICH IT IMPACTS TO GRILLED FOOD. AS USERS BECOME MORE AFFLUENT, THEY TYPICALLY SWITCH FROM WOOD FUELS TO CHARCOAL AND THEN TO PETROLEUM FUELS SUCH AS KEROSENE OR LPG. THE FOOD AND AGRICULTURE ORGANIZATION (FAO) HAS ESTIMATED THAT TOTAL CHARCOAL PRODUCTION IS AROUND 24 MILLION TONNES . ABOUT HALF OF THE WORLD CHARCOAL USE IS IN AFRICA, WHERE TRADITIONAL PRODUCTION TECHNIQUES LEAD TO A LOW CONVERSION EFFICIENCY (23 %). IT MEANS THAT 100 MILLION TONNES OF WOOD ARE ANNUALLY CUT FOR CHARCOAL PRODUCTION. THE FACT THAT CHARCOAL CONSUMPTION IS DOMINATED BY URBAN USERS FUELS THE ACCUSATION THAT RURAL AREAS SUBSIDIZE AND BEAR THE BURNT OF URBAN ENERGY USE, AS THE SUPPLIES TAKEN FROM RURAL AREAS DIRECTLY AFFECT LOCAL AVAILABILITY OF WOODFUELS. THE IMPACT OF CHARCOAL PRODUCTION ON FOREST IS LARGE FOR TWO REASONS: (1) THE WOODFUEL EQUIVALENT IS 4-6 TIMES LARGER, DUE TO THE INEFFICIENCY OF THE PRODUCTION PROCESS. (2) THE PRODUCTION OF CHARCOAL IS CONCENTRATED IN SMALL AREAS OVER A SHORT PERIOD OF TIME.

  12. B.- SLOW PYROLYSIS (350-600 oC) EVOLUTION OF PYROLYSIS RESEARCH ANCIENT TIMES THE RELATIONSHIP BETWEEN HUMANKINDAND FIRE HAS BEEN DOCUMENTED IN THE MUTH OF PROMETHEUS, WHO STOLE FIRE FROM THE GODS TO GIVE IT TO MAN. MAGNIFICENT CHARCOAL DRAWINGIN THE GROTTE CHAUVET (OVER 38,000 YEARS OLD) SUGGEST THAT CHARCOAL WAS THE FIRST SYNTHETIC MATERIAL PRODUCED MY MAN. SHALLOW PITS OF CHARCOAL WERE NEEDED TO MELT TIN FOR THE MANUFACTURE OF BRONZE TOOLS1. ANCIENT WORLD PRODUCED CHARCOAL AND MASTERED THE RECOVERY OF DISTILLATION PRODUCTS. MACEDONIANS PRACTICED CHARCOAL BURNING IN PITS FOR THE PURPOSE OF OBTAINING TARS. CHARCOAL BURNING IS AS OLD AS THE USE OF METALS. Antal MJ, Gronli M: The Art, Science and Technology of Charcoal Production. Ind. Eng. Chem. Res. 2003, 42, 1619-1640.

  13. B.- SLOW PYROLYSIS (350-600 oC) EVOLUTION OF PYROLYSIS RESEARCH WITHOUT TAR RECOVERY Early charcoal production in earth kilns WITH TAR RECOVERY

  14. B.- SLOW PYROLYSIS (350-600 oC) WOOD DISTILLATION INDUSTRIES1 1658 - GLAUBER IDENTIFIED THE PYROLIGNEOUS ACID WITH THE ACID CONTAINED IN VINAGER. 1661 - BOYLE DESCRIBED THE SEPARATION OF A SPIRITUOUS LIQUID FROM THE VOLATILE PRODUCT OF WOOD DISTILLATION 1792 - ILLUMINATING GAS MANUFACTURED FROM WOOD WAS COMMERCIALIZED IN ENGLAND. 1819 - REICHNBACH DESIGNED THE FIRST OVEN IN WHICH THE HEAT REQUIRED FOR INITIATING AND CARRYING OUT THE PROCESS WAS TRANSFERRED THROUGH METAL WALLS. 1856 - SR. WILLIAM H PERKIN PATENTED ANILINE PURPLE INCREASING THE DEMAND FOR METHYL ALCOHOL. 1864 - INCREASE IN DEMAND OF WOOD SPIRITSDUE TO THE DISCOVERY OF IODINE. 1870 - CHEMICALLY PURE ACETIC ACIDWAS OBTAINED AS A RESULT OF THE EARLY INVESTIGATION OF LOWITZ. 1870 - INCREASE IN THE DEMAND OF ACETONEDUE TO RISE OF THE CELLULOID INDUSTRY AND THE MANUFACTURE OF SMOKELEESS POWDER. 1 Klar M, Rule A: The technology of Wood Distillation. Chapman & Hall, LTD, 1925

  15. B.- SLOW PYROLYSIS (350-600 oC) Hardwood by product recovery plant including carbonization and refining factories to produce acetic acid, methanol and charcoal BIO-OIL REFINERIES? Toole A, Lane PH, Arbogast C, Smith WR, Peter R, Locke EG, Beglinger E, Erickson: Charcoal Production, marketing and uses, Forest Product Laboratory. Madison Wisconsin. US Department of Agriculture, 1961 Brown NC: The Hardwood distillation Industry in New York. The New York State College of Forestry at Syracuse University, 1917.

  16. B.- SLOW PYROLYSIS (350-600 oC) WOOD DISTILLATION INDUSTRY (FIRST BIO-OIL REFINERY) GASES BIOMASS SLOW PYROLYSIS (CARBONIZATION) CONDENSER SETTLED TAR (DECANTED OIL) PYROLYGNEOUS WATER CHARCOAL EVAPORATION DISSOLVED TAR DISTILLATE CONTAINING ACETIC ACID ACETONE CALCIUM ACETATE DESTRUCTIVE DISTILLATION MILK OF LIME NEUTRALIZATION CRUDE WOOD NAPHTA CRUDE WOOD SPIRIT Acetone: 12-14 % Methyl alcoho: 50-55 % Another organics: 5-10 % Water: 26-28 % RECTIFICATION WATER 1 Klar M, Rule A: The technology of Wood Distillation. Chapman & Hall, LTD, 1925

  17. B.- SLOW PYROLYSIS (350-600 oC) WOOD DISTILLATION INDUSTRIES1 1870-1900 GREAT DEVELOPMENT OF WOOD DISTILLATION INDUSTRY. CONDENSER TUBES 15 m3 RETORT CONDENSER TANK FURNACE PORTABLE RETORT CONDENSER RETORT COLLECTING VAT 1 Klar M, Rule A: The technology of Wood Distillation. Chapman & Hall, LTD, 1925

  18. B.- SLOW PYROLYSIS (350-600 oC) SWEDISH CARBO-OVEN (CAPACITY 300-400 m3) BOSNIAN MEILER OVEN (50 m3) MODIFIED FORM OF THE SCHWARTZ KILN AMERICAN KILN 1 Klar M, Rule A: The technology of Wood Distillation. Chapman & Hall, LTD, 1925

  19. B.- SLOW PYROLYSIS (350-600 oC) 1870-1900GREAT DEVELOPMENT OF WOOD DISTILLATION INDUSTRY. GAS LIQUID SEPARATOR CONDENSER WATER-TANK DEVICES FOR SEPARATING WOOD GAS AND PYROLYGNEOUS ACID CONTINUOUS NEUTRALIZATION OF MILK OF LIME BIO-REFINERIES BASED ON SLOW PYROLYSIS SCRUBBING THE NON-CONDENSABLE WOOD-GAS 1 Klar M, Rule A: The technology of Wood Distillation. Chapman & Hall, LTD, 1925

  20. B.- SLOW PYROLYSIS (350-600 oC) 1870-1900GREAT DEVELOPMENT OF WOOD DISTILLATION INDUSTRY. MULTIPLE EVAPORATOR FOR THE CONTINUOUS EVAPORATION OF ACETATE LIQUOR BY EXHAUST STEAM APPARATUS FOR THE CONTINUOUS DISTILLATION OF PYROLYGNEOUS ACID CONTINUOUS DISTILLATION OF PYROLYGNEOUS ACID APPARATUS FOR THE MANUFACTURE OF ACETIC ACID MECHANICAL DRUM-DRIER FOR THE PRODUCTION OF SOLID ACETATE OF LIME 1 Klar M, Rule A: The technology of Wood Distillation. Chapman & Hall, LTD, 1925

  21. B.- SLOW PYROLYSIS (350-600 oC) Bates J.S. Distillation of hardwood in Canada. Department of the Interior, Canada, 1922.

  22. B.- SLOW PYROLYSIS (350-600 oC) IN THE LAST 80 YEARS SLOW PYROLYSIS HAS RECEIVED LITTLE ATTENTION. NO CHARCOAL PRODUCTION TECHNOLOGY ABLE TO COMPLY WITH NORTH AMERICA ENVIRONMENTAL STANDARDS IS CURRENTLY AVAILABLE . Brick beehive-large scale conversion low grade wood Concrete kiln

  23. 3.- SLOW PYROLYSIS (350-600 oC) NEED FOR MORE RESEARCH ON SLOW PYROLYSIS. DEVELOPMENT OF NEW PROTOTYPES 1961 Toole A, Lane PH, Arbogast C, Smith WR, Peter R, Locke EG, Beglinger E, Erickson: Charcoal Production, marketing and uses, Forest Product Laboratory. Madison Wisconsin. US Department of Agriculture, 1961

  24. 3.- SLOW PYROLYSIS SLOW PYROLYSIS IN DEVELOPING NATIONS

  25. B.- SLOW PYROLYSIS (350-600 oC) The current trend in charcoal production aims at improving the environmental performance while maintaining and/or improving charcoal yield and quality. Steel vessels or retorts are filled with pre-dried wood and placed in a ceramic brick-lined carbonization furnace heated to 600°C. The tars and gases produced as the wood heats up are led to a separate high-temperature combustion chamber. The flue gas from this combustion chamber is used to heat the carbonization furnace, and the remaining heat from the furnace is used to pre-dry the wood. The very good heat management of this type of equipment makes it possible to produce 1 kg of charcoal from 3 to 4 kg of wood. Because of the very high temperature of the combustion chamber, all particles, tars and gases are completely combusted. These equipments have been certified to meet strict emission standards for combustion installations. Emissions of tars, carbon monoxide and nitrogen oxide as well as smell components are well within the legal limits.

  26. B.- SLOW PYROLYSIS (350-600 oC) SLOW PYROLYSIS FOR THE PRODUCTION OF HEAT SCHEMATIC DIAGRAM SHOWING PROCESSES AND THE FLOW OF MATERIAL IN A CONTINUOUS, AUGER BASES, SLOW PYROLYZER. BIOCHAR, ELECTRICITY AND HEAT ARE PRIMARY PRODUCTS OF THIS CONCEPT Laid DA, Brown RC, Amonette JE, Lehmann J: Review of the Pyrolysis Platform for coproducing bio-oil and bio-char. Bio-fuels, Bioproducts & Biorefining. 2009, 547-561

  27. C.- FAST PYROLYSIS (350 – 600 oC) 1970s- OIL CRISIS (FLUIDIZED BED REACTORS) 1980s- FUNDAMENTALS OF BIOMASS PYROLYSIS AND DEVELOPMENT OF NEW PYROLYSIS REACTORS. 1980s- PROGRESS IN BIO-OIL CHARACTERIZATION 1990s- SEVERAL FAST PYROLYSIS TECHNOLOGIES REACH COMMERCIAL OR NEAR COMMERCIAL STATUS 1990s- COMBUSTION OF CRUDE BIO-OILS AT ATMOSPHERIC PRESSURE IN FLAME TUNNELS AND BOILERS. 1990s- COMBUSTION OF BIO-OILS IN GAS TURBINES AND DIESEL ENGINES AND UNDERSTANDING BIO-OIL COMBUSTION PHENOMENA 1990s- PROPOSED SPECIFICATIONS FOR FUEL APPLICATIONS 1990s- BIO-OILS UPGRADING: (DEVELOPMENT OF BIO-OILS MICRO-EMULSIONS), HOT VAPOR FILTRATION,USE OF ADITIVES.

  28. C.- FAST PYROLYSIS (350 – 600 oC) 1990s- BIO-OIL PHYSICO CHEMICAL STRUCTURE 1990s- STUDY OF FUEL PROPERTIES OF BIO-OIL BLENDS 1990s- DEVELOPMENT OF NEW BIO-OIL SEPARATION METHODS 1990s- NEW PRODUCTS FROM CRUDE BIO-OILS (Bio-Lime, Slow Release Fertilizers, Road de-icers, Wood Preservatives, Glues, Sealing materials, bio-pitches, Hydrogen, Meat Browning Agents, Hydroxyacetaldehyde, Phenol-formaldehyde resins) 2000s- DEVELOPMENT OF NEW BIO-OIL BASED REFINERY CONCEPTS

  29. C.- FAST PYROLYSIS (350 – 600 oC) FAST PYROLYSIS: IS A HIGH TEMPERATURE PROCESS IN WHICH BIOMASS IS RAPIDLY HEATED (AROUND 300 oC PER SECOND) IN THE ABSENCE OF OXYGEN. LIQUID PRODUCTION REQUIERES VERY LOW VAPOR RESIDENCE TIME TO MINIMIZE SECONDARY REACTIONS OF TYPICALLY 1 SECOND (BUT 5 SECONDS ARE ACCEPTABLE). IT INVOLVES RAPID HEATING OF BIOMASS. GENERALLY FAST PYROLYSIS IS USED TO OBTAIN HIGH-YIELD OF BIO-OIL. RESEARCHER HAS SHOWN THAT MAXIMUM LIQUID YIELDS ARE OBTAINED WITH HIGH HEATING RATES AT TEMPERATURES AROUND 500 oC THE GROUP AT THE UNIVERSITY OF WATERLOO, CANADA DEVELOPED THE FLASH PYROLYSIS PROCESS WHICH IS BASED ON THE ADIABATIC FLUIDIZED BED PYROLYSIS OF LIGNOCELLULOSIC MATERIALS. UNIVERSITY OF WATERLOO PILOT PLANT DIAGRAM Meier D, Faix O: State of the art of applied fast pyrolysis of lignocellulosic materials- a review. Bioresource Technology 68 (1999) 71-77

  30. C.- FAST PYROLYSIS (350 – 600 oC) BUBBLING FLUIDIZED BED DYNAMOTIVE: (http://www.dynamotive.com) HEAT SUPPLIED EXTERNALLY TO BED GOOD MASS & HEAT TRANSFER REQUIRES SMALL BIOMASS PARTICLES (2-3 mm) Brown R, Holmgren J: Fast Pyrolysis and Bio-Oil Upgrading . http://www.ars.usda.gov/sp2UserFiles/Program/307/biomasstoDiesel/RobertBrown& JenniferHolmgren presentationslides.pdf

  31. C.- FAST PYROLYSIS (350-600 oC) YIELD OF PRODUCTS SOLID (BIO-CHAR) GAS (SYNGAS) LIQUID (BIO-OIL) PROCESS 60-75 % (10-25 % WATER) FAST PYROLYSIS 13-20 % 12-20 % 30-45 % (25-70 % WATER) SLOW PYROLYSIS 20-35 % 20-35 % 5-10 % (5 % WATER) 10 % 85 % GASIFICATION

  32. C.- FAST PYROLYSIS (350 – 600 oC) EFFECT OF PARTICLE SIZE Time taken for a particle of a given size to reach a mean temperature of half that of the heat transfer environment Properties of wood Particle size and heating rates in wood

  33. C.- FAST PYROLYSIS (350 – 600 oC) EFFECT OF EXTERNAL HEAT TRANSFER COEFICIENT Effect of external heat transfer coefficient on the conversion time

  34. C.- FAST PYROLYSIS (350 – 600 oC) THE EFFECT OF VAPOUR RESIDENCE TIME ON ORGANIC LIQUID YIELD IS RELATIVELY WELL UNDERSTOOD ALTHOUGH THE INTERACTIONS OF TEMPERATURE AND RESIDENCE TIME IS LESS UNDERSTOOD. THE WINDOW FOR FUEL PRODUCTION REQUIERES MORE R & D TO BETTER UNDERSTAND THE PROCESSES AND MATCH THE PRODUCT QUALITY REQUIREMENT TO PROCESS PARAMETERS. THE PRODUCT VAPORS ARE NOT TRUE VAPORS BUT RATHER A MIST OR FUME AND ARE TYPICALLY PRESENT IN AN INERT GAS AT RELATIVELY LOW CONCENTRATIONS WHICH INCREASES COOLING AND CONDENSATION PROBLEMS. THIS CONTRIBUTES TO THE COLLECTION PROBLEMS AS THE AEROSOLS NEED TO BE IMPINGED ONTO SURFACE TO PERMIT COLLECTION, EVEN AFTER COOLING TO BELLOW THE DREW POINT TEMPERATURE. ELECTRICTATIC PRECIPITATORS ARE EFFECTIVE BUT CAN CREATE PROBLEMS FROM THE POLAR NATURE OF THE PRODUCT AND ARCHING OF THE LIQUIDS AND THEY FLOW, CAUSING ELECTROSTATIC PRECIPITATOR TO SHORT OUT. LARGE SCALE PROCESSING UNITS EMPLOYS QUENCHING SYSTEMS (SCRUBBERS). CAREFULL DESIGN IS NEEDED TO AVOID BLOCKAGE FROM DIFFERENTIAL CONDENSATION OF HEAVY ENDS. THE RATE OF COOLING SEEMS TO BE IMPORTANT. TRANSFER LINES FROM THE REACTOR TO THROUGH THE CYCLONE(S) TO THE LIQUID COLLECTION SYSTEM SHOULD BE MAINTAINED AT TEMPERATURES OVER 400 oC TO MINIMIZE LIQUID DEPOSITION.

  35. C.- FAST PYROLYSIS (350 – 600 oC) HEAT TRANSFER • THERE ARE TWO IMPORTANT REQUIRMENETS FOR HEAT TRANSFER IN A PYROLYSIS REACTOR: • TO THE REACTOR HEAT TRANSFER MEDIUM (SOLID REACTOR WALL IN ABLATIVE REACTORS, GAS AND SOLID IN FLUID AND TRANSPORT BED REACTORS, AND GAS IN ENTRAINED FLOW REACTORS. • FROM THE HEAT TRANSFER MEDIUM TO THE PYROLYZING BIOMASS HEATING THE BIOMASS PARTICLE: GAS SOLID HEAT TRANSFER FROM THE HOT GAS TO THE PYROLYSING BIOMASS PARTICLE BY PRIMARY CONVECTION, AND SOLID-SOLID HEAT TRANSFER WITH MOSTLY CONVECTIVE HEAT TRANSFER IN ABLATIVE PYROLYSIS. FLUID BED PYROLYSIS UTILIZES THE INHERENTLY GOOD SOLIDS MIXING TON TRANSFER APROXIMATELY 90 % OF THE HEAT TO THE BIOMASS BY SOLID-SOLID HEAT TRANSFER WITH A PROBABLE SMALL CONTRIBUTION FROM GAS SOLID CONVECTION HEAT TRANSFER (UP TO 10 %). SOME RADIATION EFFECT OCCUR IN ALL REACTORS SINCE THE THERMAL CONDUCTIVITY OF BIOMASS IS VERY POOR (0.1 W/mKALONG THE GRAIN AND ONLY 0.05 W/mK CROSS GRAIN). RELIANCE ON GAS SOLID HEAT TRANSFER MEANS THAT BIOMASS PARTICLES HAVE TO BE VERY SMALL TO FULFIL THE REQUIREMENTS OF RAPID HEATING TO ACHIEVE HIGH LIQUID YIELDS. CLAIMED HEATING RATES OF 10,000 oC/s MAY BE ACHIEVED AT THE THIN REACTION LAYER BUT THE LOW THERMAL CONDUCTIVITY OF WOOD WILL PREVENT SUCH TEMPERATURE GRADIENTS THROUGHOUT THE WHOLE PARTICLE. AS PARTICLE SIZE INCREASES, LIQUID YIELDS REDUCE AS SECONDARY REACTIONS WITHIN THE PARTICLE BECOME INCREASINGLY SIGNIFICANT.

  36. C.- FAST PYROLYSIS (350-600 oC) PYROLYSIS OILS ARE DARK BROWN LOW VISCOSITY LIQUIDS WITH 75-80 mass % OF ORGANICS ; 15-20 % WATER Brown R, Holmgren J: Fast Pyrolysis and Bio-Oil Upgrading . http://www.ars.usda.gov/sp2UserFiles/Program/307/biomasstoDiesel/RobertBrown& JenniferHolmgren presentationslides.pdf

  37. C.- FAST PYROLYSIS (350 – 600 oC) ABLATIVE PYROLYSIS: WOOD IS PRESSED AGAINST A HEATED SURFACE AND RAPIDLY MOVED DURING WHICH THE WOOD MELTS AT THE HEATED SURFACE AND LEAVES AN OIL FILM BEHIND WHICH EVAPORATES. THIS PROCESS USES LARGER PARTICLES OF WOOD AND IS TYPICALLY LIMITED BY THE RATE OF HEAT SUPPLY TO THE REACTOR. IT LEADS TO COMPACT AND INTENSIVE REACTORS THAT DO NOT NEED CARRIER GAS BUT WITH THE PENALTY OF A SURFACE AREA CONTROLLED SYSTEM AND MOVING PARTS AT HIGH TEMPERATURE. FLUID BED AND CIRCULATING FLUID BED PYROLYSIS: THE HEAT IS TRANSFERRED BY A MIXTURE OF CONVECTION AND CONDUCTION. THE HEAT TRANSFER LIMITATION IS WITHIN THE PARTICLE, THUS REQUIERING VERY SMALL PARTICLES OF TYPICALLY NO MORE THAN 3 MM TO OBTAIN GOOD YIELDS. SUBSTANTIAL CARRIER GAS IS NEEDED FOR FLUIDIZATION OR TRANSPORT. VACUUM PYROLYSIS:SLOW HEATING RATES BUT THE VAPOURS ARE REMOVED FROM THE REACTOR IN THE PRESENCE OF VACUUM (a) Fluidized bed, (b) circulating bed (c) ablative pyrolysis (d) rotating cone reactor, (e) vortex reactor (f) vacuum pyrolysis. Meier D, Faix O: State of the art of applied fast pyrolysis of lignocellulosic materials- a review. Bioresource Technology 68 (1999) 71-77

  38. C.- FAST PYROLYSIS (350 – 600 oC) CIRCULATING FLUID BED/TRANSPORT REACTOR ENSYN (http://www.ensyn.com/index.htm) HOT SAND CIRCULATED BETWEEN COMBUSTOR AND PYROLYZER HEAT SUPPLIED FROM BURNING CHAR HIGH THROUGHPUTS BUT MORE CHAR ATTRITION Brown R, Holmgren J: Fast Pyrolysis and Bio-Oil Upgrading . http://www.ars.usda.gov/sp2UserFiles/Program/307/biomasstoDiesel/RobertBrown& JenniferHolmgren presentationslides.pdf

  39. C.- FAST PYROLYSIS (350 – 600 oC) ROTATING CONE PYROLYZER BTG (http://www.btgworld.com/index.php?r=company) HIGH PRESSURE OF PARTICLE ON HOT REACTOR WALL ACHIEVED BY CENTRIFUGAL OR MECHANICAL MOTION. CAN USE LARGE PARTICLES AND DOES NOT REQUIRE CARRIER GAS COMPLEX AND DO NOT SCALE WELL SAND AND BIOMASS BROUGHT INTO CONTACT WITHIN ROTATING CONE COMPACT DESIGN AND DOES NOT NEED CARRIER GAS Brown R, Holmgren J: Fast Pyrolysis and Bio-Oil Upgrading . http://www.ars.usda.gov/sp2UserFiles/Program/307/biomasstoDiesel/RobertBrown& JenniferHolmgren presentationslides.pdf

  40. C.- FAST PYROLYSIS (350 – 600 oC) Brown R, Holmgren J: Fast Pyrolysis and Bio-Oil Upgrading . http://www.ars.usda.gov/sp2UserFiles/Program/307/biomasstoDiesel/RobertBrown& JenniferHolmgren presentationslides.pdf

  41. C.- FAST PYROLYSIS (350 – 600 oC) REACTOR TYPES AND HEAT TRANSFER SUGGESTED MODE OF HEAT TRANSFER REACTOR TYPE ADVANTAGES/DISADVANTAGES/FEATURES ABLATIVE 95 % CONDUCTION 4 % CONVECTION 1 % RADIATION ACCEPT LARGE SIZE FEEDSTOCKS, VERY HIGH MECHANICAL CHAR ABRASION, COMPACT DESIGN, HEAT SUPPLY PROBLEMATICAL, HEAT TRANSFER GAS NOT REQUIRED, PARTICLE TRANSPORT GAS NOT ALWAYS REQUIERED HIGH HEAT TRANSFER RATES, HIGH CHAR ABRASION , CHAR/SOLID HEAT CARRIER SEPARATION REQUIERED, SOLIDS RECYCLE REQUIRED, INCREASED COMPLEXITY OF THE SYSTEM, MAXIMUM PARTICLE SIZE UP TO 6 mm, POSSIBLE LIQUIDS CRACKING BY HOT SOLIDS, POSSIBLE CATALYTIC ACTIVITY FROM CHAR, GREATER REACTOR WEAR POSSIBLE 80 % CONDUCTION 19 % CONVECTION 1 % RADIATION CIRCULATING FLUID BED FLUID BED 90 % CONDUCTION 9 % CONVECTION 1 % RADIATION HIGH HEAT TRANSFER RATES, HEAT SUPPLY TO FLUIDIZING GASE OR TO BED DIRECTLY, LIMITED CHAR ABRASION, VERY GOOD SOLID MIXING, PARTICLE SIZE LIMIT < 2 mm IN SMALLEST DIMENSION, SIMPLE REACTOR CONFIGURATION ENTRAINED FLOW LOW HEAT TRANSFER RATES, PARTICLE SIZE LIMIT < 2mm, LIMITING GAS/SOLID MIXING 4 % CONDUCTION 95 % CONVECTION 1 % RADIATION

  42. C.- FAST PYROLYSIS (350 – 600 oC) PLANT ENGINEERS ACCOUNT FOR THE AMOUNT OF ENERGY CONSUMED WITHIN THE BOUNDARIES OF A PYROLYSIS PLANT. THIS ENERGY IS USUALLY COUNTED AGAINST THE MAJOR PRODUCT OF THE PLANT, ALTHOUGH IT CAN BE APPRORTIONED AMONG THE VARIOUS BYPRODUCTS. THE EFFICIENCY OF A MODERN FAST PYROLYSIS PLANT CONSIDERING THAT THE BIO-OIL IS THE ONLY PRODUCT OF THE PLANT IS ABOUT 70 %. HOWEVER, IF THE ENERGY CONTENT OF THE CHAR IS CONSIDERED, THE OVERALL EFFICIENCY IS MORE THAN 90 %. SCALABILITY PYROLYZERS RANGE IN SIZE FROM LABORATORY DEVICES THAT PROCESS AS LITTLE AS A FEW MILLIGRAMS OF MATERIALS PER TEST TO INDUSTRIAL EQUIPMENT PROCESSING MANY TONS PER HOUR. THE LARGEST FACILITY IN NORTH AMERICA ARE CAPABLE OF PROCESSING 250 AND 200 DRY TONS OF BIOMASS PER DAY. PYROLYSIS CAN BE SCALED FROM SMALL TO LARGE TO OPTIMIZE THE BALANCE BETWEEN ECONOMIES OF SCALE ASSOCIATED WITH PROCESSING BIOMASS AT A LARGE CENTRALIZED FACILITY AND REDUCED BIOMASS TRANSPORTATION, STORAGE AND HANDLING COST THAT ACCRRUE FROM PROCESSING BIOMASS THROUGH A DISTRIBUTED NETWORK OF SMALL FACILITIES LOCATED CLOSE TO BIOMASS RESOURCE. Laid DA, Brown RC, Amonette JE, Lehmann J: Review of the Pyrolysis Platform for coproducing bio-oil and bio-char. Bio-fuels, Bioproducts & Biorefining. 2009, 547-561

  43. C.- FAST PYROLYSIS (350 – 600 oC) Biomass Biomass PRETREATMENT PYROLYSIS PRETREATMENT CHARCOAL Biomass BIO-OIL PYROLYSIS CHARCOAL BIO-OIL PRETREATMENT PYROLYSIS BIO-REFINERY BIO-OIL CHARCOAL Biomass PYROLYSIS Main Products for Large Markets (Green Gasoline, Green Diesel, Ethanol) PRETREATMENT High Value Products (Chemicals, Polymers) CHARCOAL THE MAIN GOAL OF A BIO-REFINERY IS TO PRODUCE HIGH-VALUE LOW VOLUME (HVLV) AND LOW VALUE HIGH-VOLUME (LVHV) PRODUCTS USING A SERIES OF UNIT OPERATIONS -Pelaez-Samaniego MR, Garcia-Perez M, Cortez LB, Rosillo-Calle F, Mesa J: Improvements of Brazilian Carbonization Industry as Part of the Creation of a Global Biomass Economy. Accepted in: Renew. Sust. Energ. Rev., 2008, v. 12, n 4, p. 1063-1086 - Badger PC, Fransham P: Use of Mobile Fast Pyrolysis Plants to densify Biomass and Reduce Biomass Handling Costs - A Preliminary Assessment, Biomass and Bioenergy 30, 2006, 321–325

  44. C.- FAST PYROLYSIS (350 – 600 oC) BIOCHAR CAN RESULT IN A NET REMOVAL OF CARBON FROM THE ATMOSPHERE AND AT THE SAME TIME ENHANCE SOIL PRODUCTIVITY MULTI-FEEDSTOCK PRODUCTION OF BIO-CHAR AND MULTI-APPLICATION USE. Sohi S, Lopez-Capen E, Krull E, Bol R: Biochar climate change and soil: A review to guide future research, CSIRO, 2008.

  45. C.- FAST PYROLYSIS (350 – 600 oC) INDUSTRIAL UNITS (200-2,000 t/day) MOBILE UNITS (50-200 t/day) Ensyn (ABRI) BTG Dynamotive

  46. C.- FAST PYROLYSIS (350 – 600 oC) BIO-OIL REFINERIES (HYDROTREATMENT CONCEPT) THE USE OF BIOMASS RESOURCES TO PRODUCE INFRASTRUCTURE COMPATIBLE FUEL IS APPEALING. HYDROCARBON FUELS CAN BE USED WITHOUT SIGNIFICANT CHANGES TO CURRENT FUEL DISTRIBUTION INFRASTRUCTURE. Jones SB, Holladay JE, Valkenburg C, Stevens DJ, Walton C, Kinchin C, Elliott DC, Czernik S: Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case. US Department of Energy, February 2009, PNNL-18284 Rev. 1. DE-AC05-76RL01830

  47. C.- FAST PYROLYSIS (350 – 600 oC) FAST PYROLYSIS OIL UPGRADING UNTREATED BIO-OIL IS A DARK BROWN, FREE-FLOWING LIQUID WITH ABOUT 20 % WATER. BIO-OIL CAN BE STABILIZED AND CONVERTED TO A CONVENTIONAL HYDROCARBON FUEL BY REMOVING THE OXYGEN THROUGH HYDROTREATING. HYDROTREATING TO REMOVE NITROGEN AND SULFUR FROM HYDROCARBONS IS A COMMON AND WELL ESTABLISHED REFINERY PROCESS. OXYGEN REMOVAL ON THE SCALE NEEDED TO UPGRADE PYROLYSIS OILS IS RELATIVELY NEW AND IN THERESEARCH STAGES. THE UPGRADING STEP INCLUDES CONTACTING THE BIO-OIL WITH HYDROGEN UNDER PRESSURE AND AT MODERATE TEMPERATURE (< 400 oC) OVER FIXED BED REACTORS. SINGLE STAGE HYDROTREATING HAS PROVED TO BE DIFFICULT, PRODUCING A HEAVY, TAR LIKE PRODUCT. DUAL STAGE PROCESSING, WHERE MILD HYDROTREATING IS FOLLOWED BY MORE SEVERE HYDROTEATING HAS PROVED TO BE TECHNICALLY VIABLE. OVERALL THE PYROLYSIS OIL IS ALMOST COMPLETELY DEOXYGENATED BY A COMBINATION OF HYDRODEOXYGENATION AND DECARBOXYLATION: LESS THAN 2 % OXYGEN REMAINS IN THE TREATED STABLE OIL. WATER AND OFF-GAS ARE PRODUCED AS BYPRODUCTS. THE WATER PHASE CONTAINS SOME DISSOLVED ORGANICS, WHILE THE OFF GAS CONTAINS LIGHT HYDROCARBONS. ONCE STABILIZED THE OIL CAN BE FURTHER REFINED INTO CONVENTIONAL FUELS. Jones SB, Holladay JE, Valkenburg C, Stevens DJ, Walton C, Kinchin C, Elliott DC, Czernik S: Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case. US Department of Energy, February 2009, PNNL-18284 Rev. 1. DE-AC05-76RL01830

  48. C.- FAST PYROLYSIS (350 – 600 oC) FLOW DIAGRAM FOR PYROLYSIS OIL STABILIZATION (BIO-OIL REFINERIES) HYDROGEN PYROLYSIS OIL Cost of production: 1.74 $/gal gasoline/diesel FUEL GAS TO REFORMER UP-GRADED BIO-OIL TO DEBUTANIZER 2000 T/DAY OF HYBRID POPLAR UNIT TO PRODUCE 76 MILLION GALLONS/YEAR OF GASOLINE AND DIESEL (115 gal/t) WASTE WATER Jones SB, Holladay JE, Valkenburg C, Stevens DJ, Walton C, Kinchin C, Elliott DC, Czernik S: Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case. US Department of Energy, February 2009, PNNL-18284 Rev. 1. DE-AC05-76RL01830

  49. D.- CONCLUSIONS PYROLYSIS IS THE ONLY TECHNOLOGY AVAILABLE TO PRODUCE CHARCOAL. MOST OF CURRENT RESEARCH AND DEVELOPMENT IN PYROLYSIS AIMS AT PRODUCING HIGH YIELDS OF A BIO-OIL THAT WILL BE FURTHER REFINED TO PRODUCE TRANSPORTATION FUELS. YIELDS AS HIGH AS 28 % OF GREEN GASOLINE AND GREEN DIESEL FROM LIGNOCELLULOSIC MATERIALS HAVE BEEN REPORTED. THERE IS AN INCREASING INTEREST TO PRODUCE BIO-CHAR FOR CARBON SEQUESTRATION.

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