HELSINKI UNIVERSITY OF TECHNOLOGY

Current Status of Black Liquor Droplet

Combustion Modelling and CFD Sub-
Model Development

Mika Jrvinen
Helsinki University of Technology

Christian Mueller and Mikko Hupa

bo Akademi University
Contents
1. Introduction
2. Black liquor combustion modeling since 1980s
3. Detailed droplet model, Jrvinen et al. (2002)
4. Important observations from latest droplet models and
their implications
5. Description of the new simplified comprehensive droplet
model
6. Towards a sub-model for CFD applications
7. First application of the sub-model
8. Summary
Introduction
Many single droplet combustion models have been developed
for black liquor since 1980s
Some models have been used to study combustion behavior
under constant reactor conditions, allowing a very detailed
description of the processes
Models that are used in connection to CFD software should be
relatively simple but effective, development work very
challenging
This presentation will concentrate on the current status of
black liquor combustion modeling mainly in Finland, but also
gives a short history review of single droplet model
development
Black liquor combustion modeling
since 1980s
Modeling of black liquor combustion was initiated by Merriam (1980)
introducing a 1D equilibrium furnace model
Droplet model was generally based on coal work, no BL
specific data available
Modeling approved to be very useful tool for RB analysis
1989 Walsh and Grace presented a first FLUENT based recovery
boiler CFD model
Droplet combustion and spray properties were based on
experiments
Isothermal droplet, sequential stages
Included drying, devolatilization, char oxidation and smelt
oxidation
 Frederick (1990) presented a single droplet model based on large set
of experimental data and conservation laws for mass and energy
Experimental determination of droplet swelling during drying
and devolatilization and size reduction during char burnout
Non-isothermal droplet during drying and devolatilization,
isothermal assumption gave too high drying rates
Char conversion by external mass transfer of O2, CO2 and
H2O, intra-particle mass transfer and reaction included later
by Frederick et al. (1993)
This model has been widely used later by other researches
Wg et al. (1995) presented a detailed isothermal char conversion
model
Char could react with O2, CO2 and H2O, and also with sulfates
and carbonates
Model considered boundary layer gas mass transfer with pore
diffusion and heterogeneous reactions in pores
Good correlation with experimental data
 Models of Verrill and Wessel (1996) and Saastamoinen (1996)
numerically solved intra-particle temperature distribution during
drying and devolatilization
Particles found to be highly non-isothermal
Simultaneous drying and devolatilization
Role of intra-particle thermal radiation found important, Verrill
and Wessel
Jrvinen et al. extended (2002) the work of Verrill and Wessel and
Saastamoinen by developing a general heat and mass transfer
model for porous particles
Solving numerically the boundary layer and intra-particle
heat- and mass transfer and reactions during the gas phase
Overlapping of all combustion stages, important role of char
conversion during drying and devolatilization
Detailed droplet model
Published by Jrvinen
et al. 2002 (Doctoral
thesis)
Tekes/CODE
programme 1999 -
2002
Academy of Finland
2003-2005
Tekes ChemCom
2005-2007
 Detailed droplet model - Internal profiles
300 1500 60
Ri
240
Dry Pyro
1200 Temperature and 50

Temperature (C)
reaction profiles 40

R i, mol/m s
R i (mol/m s)

3
3

180 900 H2O + C

120 600 during pyrolysis

30

20
O2 + C
CO2 + C
r
60 300 10

0
0 0
0 0.2 0.4 0.6 0.8 1
0 0.2 0.4 0.6 0.8 1
Radial coordinate, r/rs
Radial coordinate (r/rs)

200 1250 50
Temperature and
150 1000 40
reaction profiles
Temperature (C)

H2 O + C O2 + Na2S

R i (mol/m s)
R i (mol/m s)

M2CO3 + 2 C

3
CO2 + C 30
3

100 750
O2 + C
CO + H2O
during char 20
M2SO4 + 2 C

50 500

0 250
combustion 10

-50 0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Radial coordinate (r/rs) Radial coordinate (r/rs)
Important observations and their
implications
Overlapping drying and devolatilization stages in thin cores with
characteristic temperatures: Tb ~ 150C, Tp ~ 250-300C
Shrinking core approach applicable
Intraparticle thermal radiation is important aR ~ 850 1/m
should be considered
During drying and devolatilization, temperature profile
approaches quasi-steady state profile
analytical solution for T(r) possible, sensible heat term dT/dt
negligible (however, used to obtain a stable solution)
 Char conversion occurs simultaneously with drying and
devolatilization at the particle surface
Overlapping effects to be considered
During pure char combustion stage particle is almost
isothermal
Possible to model chemical reactions at T(t), not T(r,t)
No single dominating char reaction
All reactions to be included
The simplified comprehensive droplet
model
Tg
- only one temperature
Ts(t) + 8 tracked species
Ts(t) mi(t) to be solved
- const. Tb, Tp
Tp= const - Na + K => M
Tb= const

H2O(l)
C(s)
+ DS N(s)
DS MCl(s)
M2S(s)
M2SO4(s)
M2CO3(s)
Reactions in the simplified model
H2O(l) H2O

DS (dry solids) volatiles, C(s), N(s), M2S(s), M2SO4(s),

M2CO3(s), MCl

Pyrolysis and drying modeled as a heat transfer

limited processes, taking place at a single
temperature determined by the detailed model,
resulting a shrinking core approximation
Volatile combustion around droplet / in far field ?
Parallel oxidation reactions

C(s) + 0.5O2 CO Smith 1982

M2S(s) + 2 O2 M2SO4(s) --

Heterogeneous oxidation reactions are calculated

from analytical expressions, including mass transfer
and continuous reaction in porous isothermal char
layer.
Char gasification

C(s) + H2O CO + H2 Li et al. 1991

C(s) + CO2 2 CO Li et al. 1990

Heterogeneous reactions of char are calculated from

analytical expressions, including mass transfer and
continuous reaction in porous isothermal char layer.
Inorganic reactions

M2CO3(s) + 2 C(s) 2 M + 3 CO Li et al. 1991

M2SO4(s) + 2 C(s) Ma2S(s) + 2 CO2 Wg et al., 1995

Inorganic reactions of char are calculated from kinetic

expressions, no mass transfer effects, isothermal char
layer
Towards a sub-model for CFD
Developed C-source code of the stand-alone droplet model
delivered to A by HUT

Conversion of source code to Fluent UDF and implementation

into Fluent at A

Fluent UDF in use at A and HUT, common test case

Sensitivity analysis, comparison and application of all single

droplet/particle models developed at HUT and A at well defined
conditions
Detailed and comprehensive black liquor droplet model
Current droplet/particle models in the A Furnace Model
First application of the sub model
Comprehensive single droplet model programmed in form of
one DPM law
Iterative determination of droplet conditions per timestep x on the
droplet trajectory

x x x
x
x
x Computationally demanding
x
x

Common procedure: 10 fluid flow iterations per DPM iteration

First application of the sub model
Testcase 625 tDS/day boiler

28.5 m
A3, 11m (22%)
Domsj
BL, 7 m - 2450 t/day air
- 625 tDS/day black liquor
A2, 3m (45%)
A1, 1m (33%) - rotational firing mode of
6.2 m tertiary air
6.7 m
First application of the sub model
Droplet Diameter [m]

A Furnace Model Comprehensive SDM

First application of the sub model
Droplet Temperature [K]

A Furnace Model Comprehensive SDM

First application of the sub model
Droplet Drying [kg H2O/s]

A Furnace Model Comprehensive SDM

First application of the sub model
Droplet Diameter [m] 500 Droplet Trajectories

A Furnace Model Comprehensive SDM

First application of the sub model
Computational Demand, CPU-time [s]

10 droplets from one liquor gun, 50 stochastic tries

500 droplet trajectories

A Furnace Model: 9 s

Comprehensive SDM: 109 s

Increase in computational time per DPM iteration: ~ factor 12

Summary
A new comprehensive single black liquor droplet combustion
sub-model has been implemented into FLUENT software and
is currently in use at HUT and A
Simplified model is based on the experimentally validated
detailed model, using the most essential physical and
chemical mechanisms observed by simulations and
experiments
Close co-operation between Helsinki University of
Technology and bo Akademi University has been essential
for effectively combining the knowledge on detailed model
development, combustion experiments and CFD model
implementation
The project has been definitely a Win- Win deal for both
parties