Finnish-Swedish Flame Days 2013,

Gasification Workshop, 2013-04-18, Jyvskyl

Particle scale char gasification models

for biomass fuels
Kentaro Umeki
Kentaro.umeki@ltu.se
Div. Energy Science
Dept. Engineering Sciences and Mathematics
Lule University of Technology, Sweden
 Agenda
Background
Particle scale biomass char gasification models
Phenomenological model for intrinsic reaction rate
Reaction mechanism
Surface area development
Catalytic activity of ash (K, Na, Ca, Mg, Fe, etc.)
Considering intra-particle diffusion
Considering external diffusion
Summary and future challenges
Red letters: Focus of this presentation
(especially important for biomass fuels)
 Solid-phase Gas-
phase

Raw biomass Drying

(100 C)

Dry biomass Devolatilization

(200-500 C)

Char
Gasification
(> 700 C)
Combustion
Ash
(>500 C)
Mass transfer
Heat transfer
 Char gasification

Rate controlling step

Slower than devolatilization by a few orders of magnitude
High heating value of char
Char yield from devolatilization: ~10% on weight basis, but
15-30% on energy basis
Target for energy balance in allothermal gasifiers
Endothermic reactions (with CO2/H2O)
Convert sensible heat to useful chemical energy
Reactor scale

Microscopic scale

Particle scale

Plant scale
 Partice scale (mass diffusion) models?

Important to predict char conversion accurately

hence, important for gas composition as well

Majority of current CFD models do NOT consider

particle-scale (diffusion) phenomena
1. Develop constitutive equations to implement?
2. Find (numerically) efficient ways for coupling particle
and reactor models?
This presentation focuses on approach 1.
 Important factors for char gasification

Catalytic activity of O2
inorganic matters CO2
H2O

External and
intra-particle
Surface area diffusion
 0,4
Definitions mini

Residual mass [g]

0,3 mini - m
Char conversion mini - mfin
mini m 0,2 m
X
mini m fin 0,1
mfin
Conversion rate 0
dX 0 500 1000 1500 2000
r Elapsed time [s]
dt
Apparent rate
Conversion rate observed as a lump of
chemical reaction and mass diffusion
Intrinsic rate
Conversion rate of pure chemical reaction
(when diffusion is negligible)
 Common strategy for modelling

Intrinsic reaction rate = ,

(1) reaction conditions dependent models based on
reaction mechanisms: (k(p,T))
(2) Char conversion dependent models describing reactive
surface area and catalytic activity: f(X)
Intra-particle diffusion
Effectiveness factor: =
External particle diffusion
Mass balance in gas film

[e.g. A. Gmez-Barea and B. Leckner,

Prog. Combust. Energy Sci. 2010]
Phenomenological models for intrinsic reaction rate
Reaction mechanism
Surface area development
Catalytic activity of ash (K, Na, Ca, Mg, Fe, etc.)
For more detail: K. Umeki, A. Moilanen, A. Gmez-Barea, J. Konttinen, A model
of biomass char gasification describing the change in catalytic activity,
Chemical Engineering Journal 207-208 (2012) 616-624.
 Single-step reaction model
C+O22(1-)CO+(2-1)CO2
C+H2OCO+H2
C+CO22CO

, = /

Arrhenius plots from the reference will be shown.here.

[C. Di Blasi, Prog. Energ. Comb. Sci. 35 (2009) 121-140]

 Detailed reaction model
C+O2 2(1-) CO+ (2-1) CO2 O2, H2O, H2, CO,
2C+O22C(O) CO2 CO2
C(O) CO
2C(O) CO2 + C
C+CO2C(O) + CO O H
C C C C C
C+H2OCO+H2
Char (carbon)
C+H2OC(O) + H2O
C(O) CO Examples (Langmuir-Hinshelwood model)
C+H2C(H)2 1 2 2
, =
C+1/2H2C(H) 1 2 + 2
1 2
C+CO22CO , =
1 + 1 /3 2 + 3 /3 2
C+CO2C(O) + CO 1 2
C(O) CO , =
1 + 1 /2 + 1 /2 2
Phenomenological models for surface area
Models Reaction
Overall reaction
Throughout particle

Shrinking core
Particle surface
[Yagi 1953]
Random pore
Pore surface
[Bhatia 1980]
Overlapped grain Overlapped grains
[Adschiri 1987] surface
Percolation Each carbon site in
[Reyes and Jensen 1986] lattice
 Function f(X) for different models
Models f(X) with f(X=0)=1
Overall reaction (1 X )
Shrinking core (1 X ) 2 3
Random pore (1 X ) 1 ln(1 X )

Overlapped grain [1 (1 0 1 ) X ]{1 (ln 0 ) 1 ln[1 (1 0 1 ) X ]}2 / 3

1
Percolation (1 X )[1 (1 0 ) 0 X ]
= 4Lo(1-o)/So
o: Initial porosity
Lo: Total length of pores per unit volume
So: Pore surface area per unit volume
 Models
1. Overall reaction
2.
1. 2. Shrinking core

3. Random pore
3.

4. Overlapped grain

5. Percolation

4. 5.
 Catalytic activity of inorganic content

K, Ca, Na, Mg and Fe known as catalyst

Si, P and Al known to deactivate catalytic activity
Difficult to observe actual catalytic activity due to its
own transformation (vaporization, reaction,
sintering)
In-situ experiments are necessary for the
observation of catalytic activity
Previous models describing catalytic activity
Ref. Model

Zhang et al. Fuel

(2008)

rint k (1 X ) 1 ln(1 X ) 1 cX
p

Zhant et al. Fuel
(2010)

rint k (1 X ) 1 ln(1 X ) 1 p
Struis et al. Chem Eng
Sci (2002)
rint k (1 X ) 1 ln(1 X ) 1 p 1bt
p

Dupont et al. Bioresour
rint k amk mSi b 1 X
2/3
Technol (2011)
Kitsuka et al. Energy
Fuel (2007)
rint k1 exp k 2 t k 2 (1 X )
Kajita et al. Energy
rint k1 k 2 (1 X )
Fuel (2010)
Lwenthal, PhD thesis
(1993)
2

rint k1 1 k 2 t k3 (1 X ) 1 ln(1 X )
Isothermal TGA

Schematic diagram of isothermal TGA will be shown.here.

Mimic reaction conditions of commercial

gasifiers
Rapid heating rate and in-situ
gasification (no cooling and reheating)
Reaction conditions of FBG and cyclone
gasifiers (973-1123 K; CO2-CO-H2O-H2;
0.1-3.0 MPa)

[A. Moilanen, Doctoral thesis, VTT publication 607, 2006]

Conversion rate analysis by integral method
If conversion rate is first-order: / = 1
By integration:1 = ()
ln(1-X) should be linear function of t

1st/2nd regimes: linear functions

Which is first-order reaction
with respect to char conversion?

Three regimes were observed.

Typical experimental data

 Instantaneous reaction rate

2nd regime is first-order reaction!

If / = 1
1
= .
1

Typical experimental data

Initial stage of char gasification: K, Na evaporation

1st regime Loss of catalytic activity?
 Observed reaction mechanism

1. Catalytic char gasification w/ fast catalyst loss

2. Non-catalytic char gasification
3. Catalytic char gasification w/o catalyst loss
 Three-parallel reactions model

=

= ,1 + + ,2
1st regime: Catalytic gasification with deactivation
,1 = ,1 2

2nd regime: Non-catalytic gasification

= 1

3rd regime: Catalytic gasification without deactivation

,2 = ,2
 Effect of biomass species

Biomasses with low Si in ash Biomasses with high Si in ash

Poor predictability. Good model predictability!!
Negative rate coefficient

Governing deactivation mechanism

Reaction with Si?
 Effect of reaction atmosphere

H2O-H2 system CO2-CO system

Poor predictability. Good model predictability!!

Catalytic activity maintained under H2O-H2 system?

 Intra-particle mass diffusion
K. Umeki, S. Roh, T. Min, T. Namioka, K. Yoshikawa, A simple expression for the
apparent reaction rate of large wood char gasification with steam,
Bioresource Technology 101 (2010), 4187-4192
 Models describing pore diffusional effect
: very good Pseudo- Effective Simplified Direct
: good activation factor numerical numerical
: not so good energy simulation simulation
Effect of
initial
diameter
Diameter

change
Comp. time
General
versatility
Calc. method Arrhenius Theoritical Quantum Numerical
plot value method solution of
PDEs
Modify!
(Effective factor) = rapp/rint
 Macro-TG experiments
Precision scale
Gas
cylinder

Temp.: 1123, 1173, 1223 K

MFC
Steam: 0.02, 0.04, 0.06 Mpa
Gas velocity: 5 L/min
Pump
Syringe pump
(water)

Thermocouple
 Effect of particle diameter

(1173 K, PH2O =0.04 MPa)

 Simplified reaction model
0 < X < X1 X1 < X < X2
X2 < X <1

X X
1

X1

r r r r

Change of local char conversion and particle size

0 < X < X1 Uniform reaction

X1 < X < X2 Shrinking reaction
X2 < X < 1 Uniform reaction
 Modification of effective factor
Original Modified expression
Thiele module

Thiele module
n 1
V n 1 c k cg C AS

S 2 DeA
Effective factor
1 1 1 Effect of particle size change
Effective factor
tanh(3 ) 3
[Bischoff 1965]

= rapp/rint Effect of local intrinsic rate

 Predictability with theoretical parameters

(1173 K, H2O: 0.04 MPa)

Experimental data: solid lines
Calculated data: dashed lines
External mass diffusion
 Overall conversion rate with external diffusion
C+a Agases (CO, H2 and CO2)
(Amount of agent consumed in particle) =
(Amount of agent diffusing to char surface)
S p kC As S p D Ab As D
As
kC D
Ab
Mass loss rate of carbon from stoichiometry
dmc dm A
a
dt dt
M k
a C c D S p Ab
M A kc D
dmc M
a C S p ke Ab
dt MA
Effective rate constant:
k c D DAB
ke D Sh
kc D dp
 Summary

Intrinsic rate can be usually expressed as k(p,T)f(X),

but parallel reaction model may be appropriate for
describing catalytic activity
Effect of intra-particle diffusion can be included by
applying effectiveness factor
Effect of external diffusion can be included by
effective rate constant
Future works
More understanding of ash transformation and
modification of models of catalytic activity
Consideration of fragmentation in particle scale
models
Generalization of models to various shape
 Acknowledgment
Co-workers
Catalyst model: Dr. A. Moilanen (VTT); Prof. A. Gmez-Barea (U.
Sevilla); Prof. J. Konttinen (U. Jyvskyl)
Intra-particle diffusion model: Dr. S. Roh and Dr. M. Taijin (Korean
Inst. Machinery and Materials); Prof. T. Namioka and Prof. K.
Yoshikawa (Tokyo Inst. Tech.)

Finance
Catalyst model: Bio4Energy, Nordic Energy Top-Level Initiative
Pore diffusion model: Japan Society for the promotion of Science
and Korea Science and Engineering Foundation