Modelling & experimental validation of biomass-steam gasification in bubbling fluidized bed reactor

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1 Modelling & experimental validation of biomass-steam gasification in bubbling fluidized bed reactor Prasanth Gopalakrishnan Supervisor: Professor Shusheng Pang Co-supervisor: Dr Chris Williamson Department of Chemical and Process Engineering

2 Objective: To develop a mathematical model to simulate the gas composition of biomass gasification in the bubbling fluidised gasifier. Unsteady state non isothermal model based on reaction kinetics of produced combustible gases. Investigation of the effects of operating parameters such as temperature and steam to biomass ratio on the gas compositions. Validate the model with experimental data

3 Fluidised Bed- Gasification Technology with Steam as Gasification Agent Flue gas Hot Sand Combustible Gases CFB Combustor BFB Gasifier CO,CO, H, H O, CH 4 Biomass Air Char & Sand Steam Biomass - Pinus radiata Ultimate Analysis C H O N Wt % dry basis

4 Leads a programme on Wood IGCC for wood industry. Has built a 1 kwth laboratory-scale Fast Internal Circulating Fluidised Bed (FICFB) Gasifier for tests and evaluation of radiata pine residues. Developing producer gas cleaning technologies. Biofuels projects (Pyrolysis, Fischer-Tropsch process). Gasifier at UoC

5 Biomass gasification There are two stages of physical and chemical changes in the biomass gasification: Decomposition of the biomass under high temperature. This is a similar process to biomass fast pyrolysis. Secondary reactions involving the evolved volatiles. Char reaction with gasification agent.

6 Instantaneous Overall Pyrolysis Reactions N wood CH 1.44 O.66 + N moist H O Heat at very high Temp N N H tar N H CO + N Tar+ N CO+ N CH char CO CH 4 Char CO + N + N C H H O C H H O+ For reaction above (fast pyrolysis in fluidized bed) a product distribution, instead of a typical kinetic equation, was defined by Gonza lez-saiz, in his PhD Thesis Advances in biomass gasification in fluidized bed, with the same type of biomass as the one considered in our research (small pine wood chips) and in a fluidized bed working under similar experimental conditions (Sadaka et al., ) y i = Function (Temperature) i corresponds to volatile gases & tar and char can be used as initial condition

7 Secondary Reactions Involved in the evolved volatiles and Gasification of char reactions Steam Gasification Reactions C + H C + H O K 1 O CO + H K5 CO + H Equilibrium temperature[k] ~948 ~93 o ΔG [J/mol] o ΔH [J/mol] Bouduard Reaction Steam Methane Reforming Reaction C + CO CH K 4 CO K 6 4 H O CO + 3 ~ H ~ Water gas - shift Reaction Methanation Reaction CO + H C + H K O CO K 3 CH 4 + H ~198 ~

8 Hydrodynamic model of Fluidization Producer Gas Mixing & distribution of solids & fluid Emulsion Region Bubble Region U b A b T bed Emulsion Region U e A e D 1 D Formation of motion of bubbles through the bed Bubble Region H b F be Gasification Zone Fast Pyrolysis Zone Inlet Steam at velocity of U o Biomass Feed Interphase mass transfer of particles and gases between the regions F be Emulsion phase plug flow and all reactions occurs in this region Fig.1 Two phase model for fluidised bed gasifier. Bubble phase no solids, only water gas reaction and methane reforming reaction occurs.

9 Mass Balance Accumulation rate of i in rate of i out convection rate of i out by exchange with of species (i) = + the emulsion - phase rate of production of i by chemical reaction Bubble phase Mass balance C t ib Accumulation of species (i) = U b C x ib + D ib C x ib {rate of i in rate of i out } convection F be ( C ) ib Cie + Rib rate of i out by exchange with the emulsion phase Chemical Reaction term

10 Emulsion phase Mass balance Conc. of i th species [Kgmol/m 3 ] Emulsion phase gas velocity [m/s] Diffusion coefficient of Component i [m /s] Gas Exchange Coefficient b/n Bubble & emulsion phase [1/s] C t ie = Accumulation of species (i) U ε e C ib x + D ie C x {rate of i in rate of i out } convection ie + F ε be A A b e rate of i into the emulsion phase by exchange with bubble phase ( C ) ib Cie + Rie Chemical Reaction term involved in emulsion phase + rate of production of species by devolatilization of feed

11 Energy Balance Rate of heat accumulation in the emulsion phase = heat in by gas flow in the emulsion phase heat generated by reactions in the emulsion phase - heat out by gas flow in the emulsion phase + Heat input by bed material in - + Net heat exchange b/n the bubble & Emulsion phase Heat removed by bed material char out +/- * Similarly for the bubble phase except all the terms applies except the last two terms

12 Bubble phase Energy balance C ib C t pb T b = x Sensible heat [kj/kmol] Heat interchange coefficient b/n bubble & emulsion phase [kw/m 3 K] ( U ) ( ) bcibδhib + δbhbe Te Tb + δbribδhr Rate of heat accumulation in the bubble phase heat in by gas flow in the emulsion phase - heat out by gas flow in the emulsion phase Net heat exchange b/n the bubble & Emulsion phase heat generated by reactions in the emulsion phase

13 Emulsion phase Energy balance C C ie t pe T e = x ( U C ΔH ) + ( 1 δ) H ( T T ) e ie ie be b e + ( 1 δ) R ie ΔH r + m sandcpsand x T Heat input by bed material in - Heat removed by bed material char out

14 Boundary Conditions x=h C ib C = ie = x x T b T = e = x x ; x= D C C = D C C = C 1 ib ie ib Ci ; ie i Ub x Ue x T = T = b e T in

15 Hydrodynamics of Fluidized Bed At minimum Fluidization, bed starts lifting. At this point the frictional upward lift force just exceeds the gravitational force. Gravitational force : ( ΔP) Ac = gw = gρb, appv = g( ρ p ρ f )( 1 ε ) L Ac Pressure drop given by Ergun s Correlation of fixed bed u ( ΔP) = 1.75 ( 1 ε ) u ρ L ( 1 ε ) ε 3 d f ' p + 15 ( ε ) μ g( ρ ρ ) ρ d f ' p f u p f 1.75ρ ε f 3 d ε ' p 3 = μ u f ' p d L

16 Hydrodynamics of Fluidized Bed (Continues ) Some variables involved in the model are closely interrelated through hydrodynamics derived from (Mori and Wen, 1975) and (Davidson et al., 1985) Bubble diameter: Db = DbM ( DbM Db ) exp(.3x / D) Maximum Bubble diameter: D [ ( )]. 4 bm = 1.64 A U U Initial bubble diameter: D =.871 A( U U ) N. Bubble velocity: Volume fraction of bubble: Emulsion velocity: Gas exchange co efficient b/n bubble & emulsion phase [1/s] [ ] 4 b / U = U U b ( U U ) Ub DEL = / Ue = U 1 ( DEL) Fbe =. 11 D b ( gd ). 5 b

17 Operating Conditions Arrhenius reaction type is used Temperature : 76 Deg C Feed rate : kg/hr Steam/Biomass:.3 Initial volatiles after instant fast pyrolysis C H, =.51 kmol/m 3 (9.81 mol %) C CO, =.67 kmol/m 3 (39. mol %) C CO, =.3 kmol/m 3 (13.6 mol%) C CH4, =.1 kmol/m 3 (1. mol %) Initial concentration of steam, C HO, =.15 kmol/m 3 Mass of Tar formed during Initial pyrolysis =1.41 kg Mass of char formed during Initial pyrolysis =.99 kg

18 Experiment Results from published literature data (Lv, Chang et al. 4)

19 Simulation results Height X Height X

20 Simulation results y H.4.3 y CO Time t[hr] 1 Height x. 1.5 Time t[hr] 1 Height x.4. y CO. y CH Time t[hr] 1 Height x Time t[hr] 1 Height x

21 Experiment Results from published literature data (Gil et al., 1999)

22 Experimental results from the dual fluidized bed gasifier,uoc Gas Composition (vol %) Steady State Gasifier Test showing the Transition Process from Heat-up to Gasification at the Start. H % N % CO % CH4 % Ethene % Ethane % CO 1% He Lower Heating 16. Value (MJ Sampling Time Gasifier run on 3 March 8. Bed material: Sand (1.5kg) Wood feed rate: kg/hr ; Steam : 6 kg/hr ; S/B=.3; Bed Temperature: 75 Deg C Lower Heating Value (MJ/Nm^3)

23 Producer Gas Composition Changes with Different Fluidizing Gases to the Chute & Siphon H % N % CO % CH4 % Ethene % Ethane % CO % He % Lower CV (MJ/Nm3) 1 16 Gas Composition (vol %) Lower Heating Value (MJ/Nm 3 ) DryWood pellets feed rate (Kg dry /h) Gasifier run: Bed material: Sand (1.5kg); Wood feed rate: kg/hr; Steam : 6 kg/hr ; S/B=.8-.45; avg bed temperature: 8 Deg C

24 Gas Composition on Dry Basis Gas Composition on Dry Basis Mole Fraction H CO CO CH4 Mole Fraction H CO CO CH Biomass-Steam Ratio Biomass-Steam Ratio Effect of Steam to Biomass Ratio when pine is gratified at 8 Deg C

25 Gas Composition on Wet Basis Mole Fraction H CO CO CH4 HO Biomass-Steam Ratio

26 Experiment Results from published literature data (Franco et al., 3)

27 Effects of Temperature and Steam to Biomass Ratio Effects of Increase in Temperature I. H and CO increased II. CO and CH 4 decreased Effects of Increase in Steam to Biomass ratio. I. CO increased II. CO and H decreased III. CH 4 insignificant change ( remains unchanged)

28 Extension of the work Reaction kinetics of tar and higher hydrocarbon can be included. Parameters such as D1 and D are the axial dispersion co-efficient for the bubble to emulsion and Emulsion to bubble phase. The values are taken such as D1 constitutes to plug flow and D to mixed flow. It is recommended to use the diffusion co-efficient of the individual gas components. Finding the appropriate values for the dispersion co-efficient for individual gas components involved in the reactions between the phases, would improve the results. Both particle and gas phase void fractions are assumed to be constants. Hence continuity equation along with the momentum equation can be incorporated to the non isothermal reaction kinetics model to evaluate the changes in the void fraction along the length of the gasifier.

29 References DAVIDSON, J. F., CLIFT, R. & HARRISON, D. (1985) Fluidization, London Orlando: Academic Press. FRANCO, C., PINTO, F., GULYURTLU, I. & CABRITA, I. (3) The study of reactions influencing the biomass steam gasification process.fuel, 8, GIL, J., CORELLA, J., AZNAR, M. P. & CABALLERO, M. A. (1999) Biomass gasification in atmospheric and bubbling fluidized bed: Effect of the type of gasifying agent on the product distribution. Biomass and Bioenergy, 17, Lv, P. M., J. Chang, et al. (4). "A kinetic study on biomass fast catalytic pyrolysis." Energy & Fuels 18(6): MORI, S. & WEN, C. Y. (1975) Estimation of bubble diameter in gaseous fluidized beds. AIChE Journal, 1, SADAKA, S. S., GHALY, A. E. & SABBAH, M. A. () Two phase biomass airsteam gasification model for fluidized bed reactors: Part II--model sensitivity. Biomass and Bioenergy,,

30 Thank You! Any Questions???

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