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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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2018 Impact Factor: 2.809

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Front. Chem. Sci. Eng.    2018, Vol. 12 Issue (4) : 708-717    https://doi.org/10.1007/s11705-018-1767-y
RESEARCH ARTICLE
Kinetic-compartmental modelling of potassium-containing cellulose feedstock gasification
Attila Egedy1(), Lívia Gyurik1, Tamás Varga1, Jun Zou2, Norbert Miskolczi1, Haiping Yang2
1. Institute of Chemical and Process Engineering, University of Pannonia, Veszprém 8200, Hungary
2. State Key Laboratory of Coal Combustion, Huazhong University of Science and Technolgy, Wuhan 430074, China
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Abstract

Biomass is of growing interest as a secondary energy source and can be converted to fuels with higher energy density especially by pyrolysis or gasification. Understanding the mechanism and the kinetics of biomass pyrolysis (thermal decomposition) and gasification (conversion of organic material to gases) could be the key to the design of industrial devices capable of processing vast amounts of biomass feedstock. In our work real product components obtained in pyrolysis were took into consideration as well as char and oil as lumped components, and the kinetic constants for a biomass model compound (cellulose) pyrolysis and gasification were identified based on a proposed simplified reaction mechanism within a compartment model structure. A laboratory scale reactor was used for the physical experiments containing consecutive fast pyrolysis and gasification stages using alkali metal (K) containing feedstock, which has a significant effect on the cellulose pyrolysis and gasification. The detailed model was implemented in MATLAB/Simulink environment, and the unknown kinetic parameters were identified based on experimental data. The model was validated based on measurement data, and a good agreement was found. Based on the validated first principle model the optimal parameters were determined as 0.15 mL/min steam flow rate, and 4% K content.
Keywords biomass pyrolysis      kinetic parameter identification      compartment modelling      optimisation     
Corresponding Author(s): Attila Egedy   
Just Accepted Date: 27 July 2018   Online First Date: 17 December 2018    Issue Date: 03 January 2019
 Cite this article:   
Attila Egedy,Lívia Gyurik,Tamás Varga, et al. Kinetic-compartmental modelling of potassium-containing cellulose feedstock gasification[J]. Front. Chem. Sci. Eng., 2018, 12(4): 708-717.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-018-1767-y
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I4/708
Fig.1  The schematic figure of two-stage pyrolysis/gasification system with steam inlet flow rate 0.05 mL/min
C1 C2 C3 C4 C5 C6
Model CSTR PFR Mixer PFR CSTR PFR
Volume /cm3 22.5 225 0 225 2.9 225
Reactions r1,r2,r3,r7,r8 r3,r4,r5,r6 None r3,r4,r5,r6 r3,r4,r5,r6,r9 r3,r4,r5,r6
Valid phases Solid, gas Liquid, gas Liquid, gas Liquid, gas Solid (catalyst), liquid, gas Liquid, gas
Tab.1  The structure of the compartment model
Case number Steam flow rate /(mL?min?1) Potassium content /(wt?wt?1)% Catalyst age /1
1 0.01 2.5 0 (without catalyst)
2 0.01 2.5 1
3 0.02 2.5 1
4 0.05 2.5 1
5 0.10 2.5 1
6 0.20 2.5 1
7 0.10 5 1
8 0.10 10 1
9 0.10 15 1
10 0.10 2.5 2
11 0.10 2.5 3
12 0.10 2.5 4
13 0.10 2.5 5
Tab.2  The experimental cases
Fig.2  Experimental gas yields for the four gas components for all cases
Fig.3  Measured and simulated gas yields in case 1
Fig.4  Measured and simulated gas yields in case 3 and 5
k1 k2 k3 k4 k5 k6 f1 f2 f3 f4
1.23e?2 9.71e?2 1.19e?2 4.98 6.13e?1 4.91 2.96e4 1.00 5.33e2 4.27e2
Tab.3  The identified model parameters for cases 1?6
Fig.5  Model validation based on case 2 (blue), 4 (magenta) and 6 (green)
Fig.6  Gas yields with different potassium content: case 7 (blue), 8 (magenta) and 9 (green)
Fig.7  Solid phase results with different potassium content: cases 7?9
Fig.8  Gas yields with different catalyst age: cases 10 (blue), 11 (magenta), 12 (green), 13 (black)
k7 k8 k9 p q1 q2 q3 q4
12.87 2.793 0.112 0.727 3.49e?2 0.660 2.64e4 0.279
Tab.4  Identified model parameters for cases 7?13
Fig.9  K weight fraction on catalyst: cases 10?13
Equilibrium constant type Value
Keq thermal 0.123
Keq catalytic 65.61
Keq [30] Eq. (14) 1.033
Keq [30] Eq. (16) 1.089
Keq [30] Eq. (17) 0.938
Tab.5  Comparison of equilibrium constants of water gas shift reaction
Fig.10  Normalized product yields [1] at different parameter values
Parameter Parameter value Lower limit Upper limit
k1 1.23E?02 8.00E?03 1.50E?02
k2 9.71E?02 7.00E?02 1.20E?01
k3 1.19E?02 1.00E?04 1.00E?01
k4 4.98E+00 1.00E?07 5.00E+00
k5 6.13E?01 1.00E?07 5.00E+00
k6 4.91E+00 1.00E?07 5.00E+00
k7 1.29E+01 1.00E?05 1.00E+01
k8 2.79E+00 1.00E?05 1.00E+01
k9 1.12E?01 5.00E?03 7.00E?01
f1 2.96E+04 1.00E+02 5.00E+04
f2 1.00E+00 1.00E+00 1.00E+01
f3 5.33E+02 1.00E+00 1.00E+03
f4 4.27E+02 1.00E+01 1.00E+03
p 7.27E?01 1.00E?05 1.00E+01
q1 3.49E?02 1.00E?03 5.00E?01
q2 6.60E?01 1.00E?03 1.00E+00
q3 2.64E?04 1.00E?04 5.00E?01
q4 2.79E?01 1.00E?03 5.00E?01
  
Variable Unit Description
ci kg/m3 gas mass concentration
fcat_activity 1 catalyst activity factor (K dependent)
fchar_K 1 char production factor (K dependent)
fi 1 dimensionless multiplication factor
ki variable reaction rate constant for gasification
mcatalyst % mass of the catalyst (0.5 g)
mcellulose kg initial cellulose mass (1.5 g)
mK_actual % actual potassium content in cellulose
mK_cat kg potassium mass deposited on catalyst
mK_ref % reference potassium content (2.5%)
mchar kg char mass
mK_s kg solid K in char
ni mmol gas yields
p 1 char production factor exponent
qi 1 catalyst activity factor exponent
ri 1/s reaction constant for gasification
t s time
  
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