S1

Appendix 1

Updated kinetic model of Biomass pyrolysis (POLIMI_BM_1402)

Activation energies and heats of reaction in [J/mol]; R in [J/(mol K)]; T in K.
The names of chemical compounds are explained by Ranzi et al.10.

Heat of
-1
Reaction Kinetic constant [s ] Reaction
[J/mol]
CELL
CELLA 4×1013exp(-188370/(RT)) 0
CELLA
0.45 HAA + 0.2 Glyoxal + 0.1 C2H4O
+ 0.25 HMFU + 0.3 C3H6O + 0.15 CH3OH + 0.4
CH2O + 0.31 CO + 0.41 CO2 + 0.05 H2 + 0.83 2×106exp(-80000/(RT)) 109500
H2O + 0.02 HCOOH + 0.2 G{CH4} + 0.05 G{H2}
+ 0.61 Char
CELLA
LVG 4×T×exp(-41860/(RT)) 100900
7
CELL
5 H2O + 6 Char 6.5×10 exp(-129766/(RT)) -268000
HCE
0.58 HCE1 + 0.42 HCE2 1×1010exp (-129766/(RT)) -10900
HCE1
0.025 H2O + 0.5 CO2 + 0.025 HCOOH
+ 0.5 CO + 0.8 CH2O + 0.125 C2H5OH + 0.1
CH3OH + 0.25 C2H4 + 0.125 G{H2} + 0.275 1.2×109exp (-125580/(RT)) -600
G{CO2} + 0.4 G{COH2} + 0.45 G{CH3OH} +
0.325 CH4 + 0.875 Char
HCE1
0.25 H2O + 0.8 CO2 + 0.05 HCOOH +
0.1 CO + 0.3 CH2O + 0.2 G{H2} + 0.15 G{CO} +
0.15×T×exp (-33500/(RT)) -181500
0.15 G{CO2} + 1.2 G{COH2} + 0.625 G{CH4} +
0.375 G{C2H4} + 0.875 Char
HCE1
XYLAN 3×T×exp (-46046/(RT)) 77600
HCE2
0.2 H2O + 0.175 CO + 0.275 CO2 + 0.5
CH2O + 0.1 C2H5OH + 0.2 HAA + 0.025 HCOOH
0.5×1010exp (-138138/(RT)) 50200
+ 0.25 G{CH4} + 0.3 G{CH3OH} + 0.275
G{C2H4} + 0.4 G{CO2} + 0.925 G{COH2} + Char
LIG-C
0.35 LIGCC + 0.1 COUMARYL + 0.08
PHENOL + 0.41 C2H4 + H2O + 0.3 CH2O + 0.32 1.33×1015exp(-203021/(RT)) -43000
CO + 0.7 G{COH2} + 0.495 G{CH4} + 5.735 Char
LIG-H
LIGOH + 0.5 C3H6O + 0.5 C2H4 + 0.25
0.67×1013exp(-156975/(RT)) 128300
HAA
LIG-O
LIGOH + CO2 0.33×109exp(-106743/(RT)) 108600
LIGCC
0.3 COUMARYL + 0.2 PHENOL + 0.35
HAA + 0.7 H2O + 0.4 CO + 0.65 G{CH4} + 0.6 1.67×106exp(-131859/(RT)) -130000
G{C2H4} + G{COH2} + 0.4 G{CO} + 6.75Char
LIGOH
LIG + 0.9 H2O + 0.1 CH4 + 0.6 CH3OH
+ 0.1 G{H2} + 0.3 G{CH3OH} + 0.05 CO2 + 0.55
1×108exp(-125580/(RT)) -109400
CO + 0.6 G{CO} + 0.05 HCOOH + 0.85 G{COH2}
+ 0.35 G{CH4} + 0.2 G{C2H4} + 4.15 Char
S2

LIG
FE2MACR 4×T×exp(-50200/(RT)) 142600

LIG
0.95 H2O + 0.2 CH2O + 0.2 C2H4O + 0.2
C3H6O + 0.4 CH3OH + CO + 0.2 CH4 + 0.05
0.4×109exp(-125580/(RT)) -92800
HCOOH + 0.4 G{CH4} + 0.65 G{C2H4} + 0.45
G{CO} + 0.5 G{COH2} + 5.5 Char
LIG
0.6 H2O + 0.4 CO + 0.2 CH4 + 0.4 CH2O
+ 0.2 G{CO} + 0.4 G{CH4} + 0.5 G{C2H4} + 0.4 0.083×T×exp(-33500/(RT)) -345900
G{CH3OH} + 2 G{COH2} + 6 Char
G{CO2}
CO2 1×106exp(-100464/(RT)) -121600
G{CO}
CO 0.5×1013exp(-209300/(RT)) -56200
G{COH2}
CO + H2 5×1011exp(-297200/(RT)) 203300
G{H2}
H2 5×1011exp(-313959/(RT)) 0
G{CH4}
CH4 0.5×1013exp(-300000/(RT)) 0
G{CH3OH}
CH3OH 0.2×1013exp(-209300/(RT)) 0
G{C2H4}
C2H4 0.5×1013exp(-300000/(RT)) 0
S3

Appendix 2

Key GASDS and COMSOL input parameters

T is in [K]
Unit of COMSOL value or
GASDS value or expression
measure expression*
Wood thermal
[W/(m K)] .1937 .1937
conductivity
Char thermal
[W/(m K)] .1405 .1405
conductivity
Wood specific heat [J/(kg K)] 1500 + T 1500 + T
Char specific heat [J/(kg K)] -69.77 + 3.46*T 420 + 2.09*T + 6.85E-4*T2
poplar: 506, maple: 630,
beech: 700 (apparent
Initial wood density [kg/m3] 850 (intrinsic density)
density; including pore
volume)
not specified; determined
char density [kg/m3] 850 (intrinsic density)
from mass loss
poplar: 0.40, maple: 0.26,
Initial porosity [-] 0.4
beech: 0.18
wood permeability [m2] 3.e-14 5E-16
Char permeability [m2] 3.e-14 1E-13
Defined for each species
Vapor viscosity [kg/(m s)] (e.g. for CO = 6.19E-6 + 3E-5
3.896E-8*T)
Wood pore diameter, for -- radiative heat transfer is
[m] 5E-5
radiative heat transfer not treated explicitly
Char pore diameter, for -- radiative heat transfer is
[m] 1E-4
radiative heat transfer not treated explicitly
-- radiative heat transfer is
Wood emissivity 0.7
not treated explicitly
-- radiative heat transfer is
Char emissivity 0.92
not treated explicitly
*All parameters in COMSOL model are the same as in Park et al.13 model, with the exception of the char
thermal conductivity; see discussion in text.
S4

Appendix 3

If biochemical composition of the biomass is not available, then a suitable combination of the reference
species can be derived from the atomic balances for C, H, and O (see Ranzi et al.12).
For this reason three mixtures of the reference components (cellulose, hemicellulose, and the three
lignin species) are defined, and the biomass feedstock is characterized as a linear combination of these
reference mixtures. The first is a molar mixture of 60 % cellulose and 40 % hemicellulose, while the
remaining ones are mixtures of the reference lignins (80 % LIGO + 20 % LIGC, and 80 % LIGH + 20 %
LIGC).

Initial compositions used in simulations are provided in the table below along with elemental analysis
(when available).

Initial mass fractions

Ultimate
Wood Biochemical analysis Figure
analysis % daf
type number
Lignin components
C H O Cellulose Hemicellulose Ash
LIGC LIGH LIGO
lignin15 - - - 0 0 0.540 0.230 0.230 0 3d
almond - - - 0.3724 0.2023 0.0552 0.2865 0.0837 0 5a
shell33
beech 52.9 5.9 41. 0.4537 0.2419 0.0363 0.1021 0.1385 0.0270 5b
wood34 2
lignin34 65.8 6.5 27. 0.0797 0.0349 0.3784 0.3784 0 0.1210 5b
7
poplar 50.2 6 43. 0.4806 0.2611 0.0214 0.0957 0.1325 0.0086 6a,7,13
wood 8
(Cornell)
softwood 53.2 6 40. 0.2959 0.1608 0.0707 0.3107 0.1619 0 6b
bark35 8
beech 49 6.3 44. 0.4699 0.2553 0.0347 0.1604 0.0718 0.0080 8, 16-18
wood 4 66
(CEA14)
maple - - - 0.3829 0.2080 0.0511 0.2553 0.0872 0.0155 9-12
wood
(Park13)
S5

Appendix 4
Gas-phase pyrolysis experiments and determination of contact time of released vapor in CEA
experimental device

Pyrolysis experiments with a nitrogen-diluted hydrocarbon feedstock have been performed in the
PYRATES experimental setup, in order to highlight the effect and temperature dependence of secondary
gas-phase reactions. An effective contact time for secondary gas-phase reactions in the PYRATES device
was determined by comparing measured exit compositions to the exit compositions calculated for
different residence times. The initial composition (mol%) was as follows, and the gas flowrate was the
same as in the wood pyrolysis experiments.

CO 3 C2H4 0.2
CO2 1 C2H6 0.05
H2O 2.3 C2H2 0.02
H2 2 C3H8 0.16
CH4 0.6 N2 90.67

Figure A4.1 compares experimental and predicted values of these species, at contact times of 100 and
200 ms. Predicted values were obtained from isothermal simulations by using the gas-phase kinetic
scheme BIO_131117. These data, especially the evolution of ethane and propane between 1000 and
1200 K, confirm the reasonableness of the assumed contact times for evaluating the effect of secondary
gas phase reactions. The importance of gas phase reactions is evident above 950 K, in accordance with
the evaluations presented above in Figure 16. The experimental observation of unconverted propane at
temperatures above 1300 K suggests some difficulty either in the proper simulation or in the
temperature control of the reactor under these extreme conditions. Furthermore, Figure A4.2 shows
that benzene is formed, confirming the observations reported by Norinaga16 and shown Figure 19.
S6

Figure A4.1 Evolution of hydrocarbons through gas-phase reactions in the PYRATES experimental set-up.
Experimental composition (filled diamonds) is compared to composition obtained in simulations that
assume residence time of 100 ms (dashed lines) and 200 ms (solid lines)

Figure A4.2 Secondary gas phase reactions in the PYRATES experimental set up. Comparison of
experimental (filled diamonds) and predicted values of benzene at 100 ms (dashed lines) and 200 ms
(solid lines).