Engineering Conferences International ECI Digital Archives Biochar: Production, Characterization and Applications Proceedings 8-20-2017 Thermal evolution of biochar and its physicochemical properties during hydrothermal gasification Sonil Nanda York University, Canada Ajay K. Dalai University of Saskatchewan, Canada Franco Berruti ICFAR, Western University, Canada Janusz A. Kozinski York University, Canada Follow this and additional works at: http://dc.engconfintl.org/biochar Part of the Engineering Commons Recommended Citation Sonil Nanda, Ajay K. Dalai, Franco Berruti, and Janusz A. Kozinski, "Thermal evolution of biochar and its physicochemical properties during hydrothermal gasification" in "Biochar: Production, Characterization and Applications", Franco Berruti, Western University, London, Ontario, Canada Raffaella Ocone, Heriot-Watt University, Edinburgh, UK Ondrej Masek, University of Edinburgh, Edinburgh, UK Eds, ECI Symposium Series, (2017). http://dc.engconfintl.org/biochar/25 This Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion in Biochar: Production, Characterization and Applications by an authorized administrator of ECI Digital Archives. For more information, please contact franco@bepress.com.
Thermal Evolution of Biochar and its Physicochemical Properties during Hydrothermal Gasification of Biomass Sonil Nanda 1, Ajay K. Dalai 2, Franco Berruti 3 & Janusz A. Kozinski 1 1 Lassonde School of Engineering, York University, Canada 2 Dept. of Chemical & Biological Engineering, University of Saskatchewan, Canada 3 Institute for Chemical and Fuels from Alternative Resources (ICFAR), Western University, Canada ECI Biochar: Production, Characterization and Applications
Introduction Dependence on fossil fuels as the main energy sources has led to serious energy crisis and environmental problems. Waste biomass is a potential renewable energy source to meet the increasing energy demands. Biomass can be converted to biofuels by BTL (pyrolysis, liquefaction and fermentation) and BTG (gasification) technologies. Hydrogen is renewable, non-toxic, clean fuel and highly energy efficient source. 2
Energy crops Definition: Any plant grown as a low-cost and low-maintenance harvest used for making biofuels or combusted for its energy content to generate heat or electricity. Ideal traits of an energy crop: Fast growing, short rotation and high yield Be able to grow in marginal or degraded lands Low requirement of intensive agricultural practices No competition with food crops for land and nutrients Examples: Wood-based energy crops: Willow and poplar Grasses: switch grass, elephant grass and timothy grass 3
Supercritical water gasification Water at temperature > 374 C and pressure > 22.1 MPa is called supercritical water. Physical and chemical characteristics such as ion product, density, dielectric constant and viscosity of supercritical water are greatly different from either extreme state of the gas phase or the liquid phase. Advantages: No biomass drying required Better solvation of organics Negligible or no toxic byproducts Hydrogen-rich synthesis gas products 4
Timothy grass: Biochemical characterization 34.2 30.1 Weight % 18.1 16.5 1.1 High cellulose and hemicellulose (~64.3 wt.%) indicates high sugar content. Good for bioconversion Extractives include tannin, terpens, terpenoids, lipids, fatty components etc. 5
Timothy grass: Thermogravimetric analysis Moisture and volatiles evolution Char production 6
Experimental Objectives To study the gasification potentials of timothy grass as a model biomass for energy crops. To study the effects of different gasification parameters: o Temperature (450-650 C) o Feed concentration (1:4 and 1:8 biomass-to-water ratio) o Reaction time (15-45 min) To enhance H 2 yields by the application of homogeneous alkali catalysts and study the effect of their concentrations (1-3 wt%) o KOH o NaOH o K 2 CO 3 o Na 2 CO 3 Characterize the biochar generated at different temperatures to determine their thermal and physicochemical properties. 7
Supercritical water gasification Add Sample Thermocouple Relief valve Pressurizing Heating Filter Gas drying filter Gas-liquid separator Reactor N 2 Gas sampling Furnace Separation Gas sample Liquid product Char CONTROL SYSTEM
Effects of temperature and feed concentration (45 min) 1:4 Biomass-to-water ratio 1:8 Biomass-to-water ratio 7.00 9.00 GAS YIELD (MMOL/G) 6.00 5.00 4.00 3.00 2.00 1.00 GAS YIELD (MMOL/G) 8.00 7.00 6.00 5.00 4.00 3.00 2.00 1.00 0.00 450 550 650 0.00 450 550 650 TEMPERATURE ( O C) TEMPERATURE ( O C) H2 CO CO2 CH4 C2H6 H2 CO CO2 CH4 C2H6 Better free radical mechanism H 2 yield: 1:4 BTW (1.04-4.08 mmol/g) < 1:8 BTW (1.14-5.15 mmol/g). Higher gas yields at 650 C than at 450 C. CO yield decreased at 650 C due to water-gas shift reaction.
Effect of temperature (45 min, 1:8 BTW ratio) Total gas yield Lower heating value 18.0 17.2 2500 2207 16.0 Gas yield (mmol/g) 14.0 12.0 10.0 8.0 6.0 4.0 7.0 11.3 LHV (kj/nm3) 2000 1500 1000 500 541 1528 2.0 0.0 0 450 550 650 450 550 650 Temperature ( o C) Temperature ( o C) Total gas yields increased from 7 mmol/g at 450 C to 17.2 mmol/g at 650 C LHV increased from 541 kj/nm 3 at 450 C to 2207 kj/nm 3 at 650 C
Effect of reaction time and feed concentration (650 C) 1:4 Biomass-to-water ratio 1:8 Biomass-to-water ratio 7.00 9.00 GAS YIELD (MMOL/G) 6.00 5.00 4.00 3.00 2.00 1.00 GAS YIELD (MMOL/G) 8.00 7.00 6.00 5.00 4.00 3.00 2.00 1.00 0.00 15 30 45 0.00 15 30 45 REACTION TIME (MIN) REACTION TIME (MIN) H2 CO CO2 CH4 C2H6 H2 CO CO2 CH4 C2H6 Better water-gas shift reaction H 2 yield: 1:4 BTW (1.75-4.08 mmol/g) < 1:8 BTW (2.7-5.15 mmol/g) H 2 yield increased at 45 min than 15 min due to hydrogenation reaction. Better water-gas shift reaction at 45 min.
Effect of reaction time (650 C, 1:8 BTW ratio) Total gas yields Lower heating value 18.0 17.2 2500 2207 Gas yields (mmol/g) 16.0 14.0 12.0 10.0 8.0 6.0 4.0 11.6 13.0 Gas yields (mmol/g) 2000 1500 1000 500 1451 1744 2.0 0.0 0 15 30 45 15 30 45 Reaction time (min) Reaction time (min) Total gas yields increased from 11 mmol/g at 15 min to 17.2 mmol/g at 45 min LHV increased from 1451 kj/nm 3 at 15 min to 2207 kj/nm 3 at 45 min
Effect of catalysts (650 o C, 45 min, 1:8 BTW ratio) KOH Better hydrogenation, water-gas shift reaction NaOH Better methanation reaction
Effect of catalyst (650 C, 45 min, 1:8 BTW ratio) TOTAL GAS YIELD (MMOL/G) LOWER HEATING VALUE (KJ/NM 3 ) 27.2 28.8 28.5 30.6 4083 4137 4677 4315 17.2 2207 No catalyst Na2CO3 K2CO3 NaOH KOH No catalyst Na2CO3 K2CO3 NaOH KOH Total gas yield: KOH > K 2 CO 3 > NaOH > Na 2 CO 3 LHV: NaOH > KOH > K 2 CO 3 > Na 2 CO 3
Proximate and ultimate analysis of timothy grass biomass and biochars (45 min, 1:8 BTW ratio) Parameter Timothy grass Biochar-450 C Biochar-550 C Biochar-650 C Proximate analysis (wt%) Moisture 6.2 3.5 2.9 2.0 Ash 4.1 8.6 10.1 13.2 Volatile matter 71.4 58.4 46.6 37.4 Fixed carbon 18.3 29.5 40.4 47.4 Ultimate analysis (wt%) C 47.4 61.2 69.7 75.1 H 6.8 5.4 4.1 3.7 N 1.4 1.2 1.0 0.7 S 0.1 0.05 0.04 0.04 O b 40.4 23.6 15.1 7.3 HHV (MJ/kg) 18.6 24.9 26.2 28.9 15
SEM analysis of biochars (45 min, 1:8 BTW ratio) More cracked surface 16
FTIR analysis of biochars (45 min, 1:8 BTW ratio) Aromatics Alcohols, esters, ethers Carbonyls Alkanes Alkynes High gasification temperature led to the removal of alkanes, alkynes, alcohols, esters, ethers and carbonyls from biomass in biochars due to dehydration of organic functional groups (C O, C=O and C H). Biochar at 650 C become more aromatic with the increase in C C and C H groups. High temperature led to formation of aromatic biochars due to dehydration, dehydrogenation, demethanation, decarboxylation and decarbonylation of organic components. 17
Raman spectroscopy of biochars (45 min, 1:8 BTW ratio) Biochar-450 C Band S S L D V L G R G Assignment C H Hydroaromatic rings C C Aromatic rings C C Highly ordered carbon C H Methylene or methyl Amorphous carbon structure C=C Alkenes, Crystalline carbon structures Biochar-650 C Biochar at 650 C showed the removal of hydroaromatic rings (S band), and methylene groups (V L band). Thermal cracking and dehydrogenation caused aromatization of biochar with the increase in crystalline carbon structures, e.g. C-C (D band), C=C (G band). 18
Conclusions Temperature played a major role leading to hydrothermal cracking of timothy grass with highest gas yields at 650 C. The carbon content in the biochar and heating value increased with the rise in temperature. Lower feed concentration (1:8 BTW ratio) resulted in higher H 2 yields due to free-radical mechanism and water-gas shift reaction. Reaction time of 45 min was optimal for higher H 2 yields, total gas yields with greater LHV of the gas products. 3 wt% KOH resulted in highest yields of H 2 due to higher water-gas shift reaction, while 3 wt% NaOH enhanced methanation reaction with higher CH 4 yields. As the temperature increased from 450 to 650 C, extreme thermal denaturation of biochar through dehydration, bond breakages and formation of transformational products resulted in their aromatization. 19
Acknowledgements Funding sources NSERC Canada Research Chair program Research facilities Lassonde School of Engineering, York University Saskatchewan Structural Sciences Centre, University of Saskatchewan 20