APCAT Poster
- 1. Renewable energy Carbon Deposition on Bimetallic Co-Ni/Al2O3 Catalyst during Steam Reforming of Glycerol Chin Kui Cheng, Say Yei Foo, Adesoji A. Adesina Reactor Engineering & Technology Group, School of Chemical Engineering, The University of New South Wales Sydney NSW 2052, Australia INTRODUCTION AND MOTIVATION Aqueous Glycerol Solution • Climate change effects and sustainability Syringe considerations have necessitated the development of Pump new production technologies for energy and base Heating zone chemicals from renewable resources Steam reformed H2, CO2, CO • Syngas - a major base chemical and clean energy fuel Flow can be produced from biowastes rather than fossil feed Controller F F Electric • Glycerol (C3H8O3), the by-product of biodiesel Furnace Vent • For down-stream P = 101.3 kPa production is cheaply available and may be used as chemical processes feed to a syngas process Map showing biodiesel plants in Australia T = 773 – 823 K H Argon GC 2 Tubular Manometer Source: Biofuels Association of Australia ‡ • However, due to its high carbon content (40wt%), Reactor • As fuel for engine control and minimisation of carbon deposition during Excess glycerol is readily available Drierite bed Condenser • Fuel cell application catalytic steam reforming is vital to process efficiency from biodiesel industry as waste Schematic diagram illustrating the steam reforming set-up Catalyst preparation Chemistry of glycerol steam reforming Post-reaction analysEs Co-Ni/Al2O3 (b) TGA for gasification +3H2O 4H2 studies (2) + 7H2 3CO (c) TOC for carbon content analysis (1) Al2O3 support (d) FTIR analysis 3CO2 +3H2O (3) Precursors C3H8O3 (Glycerol) (b) (e) XRD analysis 3CO2 (c) (d) Drying/calcination Titration 3H2 (a) Autosorb for BET area and pore volume Sieving Deposition of carbon -2.2 Power-law modelling (823 K) Arrhenius plot Catalyst regeneration -2.8 Glycerol Steam TOC profile at 823 K -2.4 Slope = -0.2213 -2.9 TPR-TPO on used Al2O3 TPR-TPO on used Co-Ni/Al2O3 Slope = 0.5513 R2 = 0.934 EA = 40.9 kJ mol-1 R2 = 0.9532 R2 = 0.999 -2.6 ln(rcoking) -3.0 ln (rcoking) -2.8 -3.1 -3.0 -3.2 -3.2 -3.3 1 2 3 4 0.00120 0.00122 0.00124 0.00126 0.00128 0.00130 ln (Pressure) 1/T (K-1) •The carbon deposition behaviour may be modelled by the power-law expression: MS of gas-(used Al2O3) rxn MS of gas-(used Co-Ni/Al2O3) rxn 4920 T 0.56 0.22 •Total carbon content (TOC) profile shows rcarbon A exp Pglycerol Psteam strong dependency of carbon deposition with • The inhibition effect of steam towards carbon deposition was Pglycerol shown by the negative global power-order (-0.22) •TOC shows relatively mild inhibition by the • Carbon deposition increased with reaction temperature. The presence of steam, as shown by Psteam activation energy EA estimated as 40.9 kJ mol-1 Solid-state analysIs FTIR spectra XRD pattern Effect of TOC on physical properties Conclusions • Carbon deposition is strongly influenced by Pglycerol but weakly inhibited by Psteam • Most of the carbon was deposited on the Al2O3 • The presence of at least two types of carbon •Sample A: calcined fresh catalyst, B: •Carbon peak was detected at 2θ = species was evident from TPR-TPO studies Al2O3 employed in blank run, C: used 26o for used Al2O3 and Co-Ni/Al2O3 catalyst, D: regenerated catalyst • Complete gasification was achieved (TPR-TPO) • Carbon deposition resulted Regenerated catalyst did not have • in reduced BET area and pore • The spectrum band at 1015 cm-1 due to carbon peak, consistent with FTIR Acknowledgements volume of used catalysts C-O and C-C stretch mode. The band at spectra 1650 cm-1 represents C=C mode. The CKC is grateful for UIPA scholarship from UNSW -1 due to O-H mode • Wider peaks for used and band at 3500 cm regenerated catalysts indicates while SYF is a recipient of APA • A and D showed similar band possible sintering effect Corresponding author: TOCAT6/APCAT5 Prof. Adesoji A. Adesina a.adesina@unsw.edu.au JULY 18 – 23 , 2010 SAPPORO CONVENTION CENTER, SAPPORO JAPAN Tel.: +61 2 9385 5268; Fax: +61 2 9385 5966