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Detailed Kinetic Modeling of the Thermal Degradation of Lignins

T. Faravelli(1), A. Frassoldati(1) G. Migliavacca(2), E. Ranzi(1)


(1)
Dipartimento di Chimica, Materiali e Ingegneria Chimica, Politecnico di Milano - Italy
(2)
Stazione Sperimentale dei Combustibili – San Donato Milanese - Italy

Supplemental Material

In the kinetic mechanism the names of functional groups linked to the residue starts with P, while
the names of the radical species starts with R.
A detailed list of several species with names and formula is reported in Appendix A.

As a simple example, the reactions discussed in the paper are reported as:

LIGM2  RADIOM2+RphenoxM2 [R1]


LIGM2 + OH  RLIGM2A +H2O [R2]
RLIGM2A  FCHETOA + RFENOX [R3]
RADIO  COUMARYL + OH [R4]
RADIO  propen-1,3diol (C3H6O2) + Rphenol [R5]
ADIOM2 + RphenoxM2 Functional Groups + RC3H7O2 [R6]
LIGO  LIGM2 + CO2 [R7]
LIGC  LIG + CH2CO [R8]

The complete kinetic scheme is reported in Appendix B.


Appendix A - Molecules and Functional Groups
Name, Composition Name, Composition
Structure Structure
And MW and MW
OCH3
P OCH3
P
OH X= P PLIGH X=P PLIGO
C22H28O9 OH C20H22O10
O O
H3CO 436 422
OCH3 HO OCH3
OH C OH
H3C X=H LIGH O X=H LIGO
C22H29O9 C20H23O10
H3CO OCH3 437 H3CO OCH3 423
O-X
O-X

HO OCH3
P P
OH X=P PLIGC X=P PLIGM2
H3C C17H16O5 HO C19H22O8
O O
300 378
O OCH3

OH X=H LIGC X=H LIGM2


C17H17O5 CH3O OCH3 C19H23O8
O-X O-X
301 379
HO P HO
X=P PLIG X=P PADIOM2
HO C15H14O4 HO C11H15O5
O 258 227

X=H LIG X=H ADIOM2


C15H15O4 C11H16O5
CH3O OCH3
O-X
259 228
O-X

X=P PADIO
C9H11O 3
HO O-X 167
OH
X=H ADIO
C9 H12 O3
168
HO P PFET3 HO
OCH3
P PFET3M2
C9H9O3 C11H13O5
165 225
O O
O O OCH3
OCH3 Synapyl Coumaryl
C11H14O4 C9H10O2
HO OH 210 150
HO OH
OCH3

X=P PKETM2 X=P PKET


OCH3 C11H13O5 C9H9O3
225 HO OH 165
X-O OH
O O
OCH3 X=H KETM2 X=H KET
C11H14O5 C9H10O3
226 166
OCH3 KETDM2 KETD
C11H12O4 C9H8O2
OH OH
208 O 148
O
OCH3
OCH3 Phenol
MGUAI C6H6O
C8H10O3 OH 94
HO 154
OCH3
OCH3 OCH3
P OCH3 C10H2M4 P P C10H2M2
C14H14O4 C12H8O2
P 244 P P 182
CH3O
OCH3 OCH3
P P P
P P P P Char
C10H2
C10
C10H2
P P P P 120
122
P P P
PC2H2 PCH2P
P P C 2H 2 P P CH2
26 14
O PCOS O PCOH
CO CO
P P 28 P P 28
OH PCH2OH O PCHO
CH3O CHO
P 31 P 29
OH PCHOHP
CH2O
P P 30

Radical Species
Name, Name,
Structure Composition Structure Composition
And MW and MW
X=P
OCH3 PRLIGM2A, HO
X=P PRLIGA,
HO P R
PRLIGM2B PRLIGB
 C19H21O8 HO
 C15H13O4
HO
 

O 377   O 257
OCH3
X=H X=H
RLIGM2A, RLIGA, RLIGB
CH3O OCH3
RLIGM2B O-X
C15H14O4
O-X
C19H22O8 258
378
HO X=P PRADIOM2
 C11H14O5 X=P PRADIO
HO
226 C9H10O3

O-X
166
HO
X=H RADIOM2 X=H RADIO
OH
C11H15O5 C9H11O3
CH3O OCH3 227 167
O-X
X=P PRKETM2
OCH3
C11H12O5 RKET
 224  C9H9O3
X-O OH HO OH 165
O X=H RKETM2 O
OCH3
C11H13O5
225
OCH3 HO P
HO P
 PRFET3M2  PRFET3
C11H12O5 C9H8O3
O O
224 O
164
O OCH3
OCH3 Rguai Rphenol
C8H9O3 C6H5O
 OH 153  OH 91
OCH3
OCH3 RphenoxM2 Rphenox
P O C8H8O3 P O
C6H4O
152 90
OCH3
Appendix B
Kinetic scheme of thermal degradation of Lignin
(Kinetic constants are expressed as k(T)=A Tn exp (- E/RT). Units are l, mol, J, s)

Initiation Reactions A n E
PLIGH PRLIGH 1.00E+13 0 163254
LIGH C3H6+OH+RLIGM2A 1.00E+13 0 163254
LIGM2RPHENOXM2+RADIOM2 1.00E+13 0 163254
PLIGM2PRLIN 1.00E+13 0 163254
PLIGM2RPHENOXM2+PRADIOM2 1.00E+13 0 163254
LIGRFHENOX+RADIO 1.00E+13 0 184184
PLIGPRLINES 1.00E+13 0 184184
PLIGRPHENOX+PRADIO 1.00E+13 0 188370
PADIOM2PRADIOM2 1.00E+13 0 171626
PADIOPRADIO 1.00E+13 0 179998
PKETM2PRKETM2 1.00E+13 0 167440

Decomposition Reactions
PRKETM2KETDM2+OH 1.00E+13 0 121394
RPHENOXM2CO+.5C10H2M4+.5H2 4.00E+10 0 209300
RPHENOXCO+.5C10H2+1.5H2 4.00E+10 0 209300
RLIGH RLIGM2A+ALD3 1.00E+13 0 133952
PRLIGH 2PRLIGM2A+ALD3 1.00E+13 0 133952
RADIOM2RMGUAI+C3H6O2 1.00E+13 0 133952
RLIGM2AKETM2+RPHENOXM2 5.00E+12 0 133952
PRLIGM2APKETM2+RPHENOXM2 5.00E+12 0 133952
RLIGM2BRMGUAI+PFET3M2 1.00E+13 0 163254
PRFET3M2RPHENOXM2+C3H4O2 1.00E+13 0 133952
RADIORPHENOL+C3H6O2 1.00E+13 0 163254
RLIGAKET+RPHENOX 1.00E+13 0 138138
RLIGBRPHENOL+PFET3 1.00E+13 0 163254
PRFET3RPHENOX+C3H4O2 1.00E+13 0 138138
RADIOM2OH+SYNAPYL 3.00E+11 0 104650
RKETM2OH+KETDM2 3.00E+11 0 104650
RADIOOH+COUMARYL 3.00E+11 0 104650
RKETOH+KETD 3.00E+11 0 113022
RC3H7O2RCH3O+CH3CHO 1.00E+13 0 129766
C10H2M4RCH3O+0.5C10H2M4+RPHENOX 1.00E+13 0 196742
C10H2M2RCH3O+0.5C10H2+RPHENOX 1.00E+13 0 196742

Molecular reactions
PLIGCPLIG+CH2CO 1.00E+08 0 121394
PLIGOPLIGM2+CO2 1.00E+09 0 108836

Substitutive addition Reactions


ADIOM2+RPHENOXM2C10H2M4+.5H2+PH2+2PCOH+RC3H7O2 1.00E+09 0 121394
KETM2+RPHENOXM2C10H2M4+.5H2+PH2+2PCOH+RC3H5O2 1.00E+09 0 121394
KETDM2+RPHENOXM2C10H2M4+.5H2+PH2+2PCOH+RC3H3O 1.00E+09 0 121394
SYNAPYL+RPHENOXM2C10H2M4+H2+1.5PH2+2PCOH+RC3H3O 1.00E+09 0 121394
ADIOM2+RPHENOX0.5C10H2M4+0.5C10H2+1.5H2+PH2+PCOS+PCOH+RC3H7O2 1.00E+09 0 121394
KETM2+RPHENOX.5C10H2M4+0.5C10H2+.5H2+ 2PH2+2PCOS+RC3H5O2 1.00E+09 0 121394
KETDM2+RPHENOX.5C10H2M4+0.5C10H2+.5H2+2PH2+PCOS+PCOH+RC3H3O 1.00E+09 0 121394
SYNAPYL+RPHENOX0.5C10H2+0.5C10H2M4+1.5H2+2PH2+PCOH+PCOS+RC3H3O 1.00E+09 0 121394
ADIO+RPHENOXC10H2+1.5H2+2PH2+2PCOS+RC3H7O2 1.00E+09 0 121394
KET+RPHENOXC10H2+1.5H2+2PCOS+RC3H5O2+2.0PH2 1.00E+09 0 121394
KETD+RPHENOXC10H2+1.5H2+2PCOS+RC3H3O+2.0PH2 1.00E+09 0 121394
COUMARYL+RPHENOXC10H2+2.5H2+2PCOS+RC3H3O+2.0PH2 1.00E+09 0 121394
ADIO+RPHENOXM2.5C10H2+.5C10H2M4+1.5H2+PH2+PCOS+PCOH+RC3H7O2 1.00E+09 0 121394
KET+RPHENOXM2.5C10H2+.5C10H2M4+1.5H2+PH2+PCOS+PCOH+RC3H5O2 1.00E+09 0 121394
KETD+RPHENOXM2.5C10H2+.5C10H2M4+1.5H2+PH2+PCOS+PCOH+RC3H3O 1.00E+09 0 121394
COUMARYL+RPHENOXM2.5C10H2+.5C10H2M4+1.5H2+2PH2+ PCOS+PCOH+ RC3H3O 1.00E+09 0 121394
C10H2M4+RPHENOXM2.5C10H2M2+C10H2M4+RCH3O+.5H2+PCOH 1.00E+09 0 115115
C10H2M2+RPHENOXM2.5C10H2M2+.5C10H2+RCH3O+.5C10H2M4+.5H2+PCOH 1.00E+09 0 115115
C10H2M4+RPHENOX.5C10H2M2+.5C10H2M4+RCH3O+.5C10H2+1.5H2+PCOS 1.00E+09 0 117208
C10H2M2+RPHENOX.5C10H2M2+RCH3O+C10H2+1.5H2+PCOS 1.00E+09 0 117208

Recombination reactions
RCH3O+RPHENOXRCH3+CO2+0.5C10H2+1.5H2 1.00E+08 0 54418
RCH3O+RPHENOXM2RCH3+CO2+0.5C10H2M4+0.5H2 1.00E+08 0 54418
RPHENOXM2+RCH3PCOH+0.5C10H2M4+.5PH2+PCH3 1.00E+08 0 48139
RPHENOX+RCH3PCOH+0.5C10H2+1.5PH2+PCH3 1.00E+08 0 48139
RCH3O+RCH3ETOH 1.00E+08 0 12558
RCH3O+RCH3OCH3CHO+H2O 1.00E+08 0 12558
RCH3O+PRADIOM2PCH2OH+PADIOM2 1.00E+08 0 52325
RCH3O+PRKETM2PCH2OH+PKETM2 1.00E+08 0 52325
RADIOM2+RADIOM22PCH2OH+2PCHP2+2PCHOHP+2PH2+C10H2M4+2PCOH 3.16E+07 0 83720
RLIGM2B+RLIGM2B.2CHAR+2PCH2OH+2PCHOHP+3PH2+2C10H2M4+4PCOH 3.16E+07 0 83720
RLIGM2A+RLIGM2A2PCOHP2+2H2O+2PC2H2+4PCOH+3PH2+2C10H2M4 3.16E+07 0 83720
RMGUAI+RMGUAI2PH2+C10H2M4+2PCOH 3.16E+07 0 83720
RKETM2+RKETM22PCHP2+2PCH2OH+2PH2+C10H2M4+4PCOH 3.16E+07 0 83720
RFET3M2+PRFET3M22PCOH+C10H2M4+2PCHP2+2PCHO+2PCHOHP+PH2 3.16E+07 0 83720
RC3H7O2+RC3H7O22H2O+2PC2H2+2PCHOHP+PH2 1.00E+08 0 12558
RC3H5O2+RC3H5O22H2O+2PC2H2+PH2+2PCOH 1.00E+08 0 12558
RC3H3O+RC3H3O2PC2H2+PH2+2PCOH 1.00E+08 0 12558
OH+RCH3CH3OH 1.00E+08 0 12558
RCH3+RCH3C2H6 1.00E+08 0 12558
RCH3+PRADIOM2PCH3+PADIOM2 1.00E+08 0 48139
RCH3+PRKETM2PCH3+PKETM2 1.00E+08 0 48139
RPHENOX+RLIGB3PCOS+PCOHP2+H2O+PC2H2+1.5C10H2+3PH2+2H2 3.16E+07 0 83720
RADIO+RADIO2PCH2OH+2PCHP2+2PCHOHP+PCOS+PCOH +C10H2+H2+3PH2 3.16E+07 0 92092
LIGB+RLIGBPCOS+.2CHAR+2PCH2OH+2PCHOHP+2.C10H2+3PCOS+5PH2+2H2 3.16E+07 0 83720
RLIGA+RLIGA2PCOHP2+2H2O+2PC2H2+2C10H2+4PCOS+5PH2+2.H2 3.16E+07 0 83720
RKET+RKET3PCOH+2PCHP2+2PCH2OH+PCOS+C10H2+2H2+2PH2 3.16E+07 0 83720
RFET3+PRFET32PCHP2+2PCHO+2PCHOHP+2PCOS+C10H2+H2+2.PH2 3.16E+07 0 83720
RLIGH+RLINH2PCOHP2+4H2O+2PC2H2+4PCOH+2C10H2M4+H2+2PCH3+2PCHP2+2PCH2P 3.16E+07 0 83720
RPHENOX+RPHENOL2PCOS+C10H2+1.5H2+2PH2 5.00E+07 0 83720
RPHENOX+RC3H3OPCOS+.5C10H2+H2+PH2+PC2H2+PCOH 1.00E+08 0 48139
RPHENOX+CHARPCOS+0.5C10H2+1.5H2+CHAR 3.00E+07 0 104650
RPHENOXM2+CHARPCOS+0.5C10H2M4+.5H2+CHAR 3.00E+07 0 104650

Volatilization Reactions
ADIOM2VADIOM2 1 1 62790
KETM2VKETM2 1 1 62790
KETDM2VKETDM2 1 1 58604
SYNAPYLVSYNAPYL 1 1 62790
MGUAIVMGUAI 1 1 66976
COUMARYLVCOUMARYL 1 1 83720
ADIOVADIO 1 1 66976
KETVKET 1 1 66976
KETDVKETD 1 1 83720
PHENOLVPHENOL 1 1 58604

Char Devolatilization Reactions


PCOSCO 2.00E+08 0 209300
PCOHCO 1.00E+07 0 138138
PH2H2 1.00E+10 0 209300
PC2H2H2+.2CHAR 5.00E+08 0 205114
PCH2OHOH+PCH2P 5.00E+08 0 0
PCHOHPOH+.5PC2H2 5.00E+08 0 0
PCOHP2OH+.1CHAR 5.00E+08 0 0
PCH3RCH3 1.00E+13 0 125580
PCH2PPCHP2+.5H2 5.00E+08 0 209300
PCHP2.1CHAR+.5H2 5.00E+08 0 209300
H-abstraction reactions H type
R+LIGH RH+RLIGH 2exp (4186./RT)
R+PLIGH RH+PRLIGH 2 2exp (4186./RT)
R+PLIGM2RH+PRLIGM2A 2exp (4186./RT)
R+LIGM2RH+RLIGM2A exp (4186./RT)
R+LIGM2RH+RLIGM2B exp (4186./RT)
R+PFET3M2RH+PRFET3M2 2exp (4186./RT)
R+ADIOM2RH+RADIOM2 exp (4186./RT)
R+KETM2RH+RKETM2 exp (4186./RT)
R+C10H2RH+.5C10H2+.5CHAR exp (-20930./RT)
R+LIGRH+RLIGA exp (4186./RT)
R+LIGRH+RLIGB exp (4186./RT)
R+PFET3RH+PRFET3 2exp (4186./RT)
R+ADIORH+RADIO exp (4186./RT)
R+KETRH+RKET exp (4186./RT)

Reference kinetic parameters of H-abstracting radicals


OH 109.5 exp (-14651./RT)
RCH3 108.5 exp (-48139./RT)
RCH3O 108.5 exp (-33069./RT)
RKET, RPHENOL 108.5 exp (-54418./RT)
RLIGA, RLIGB 108. exp (-56511./RT)
RC3H7O2 108. exp (-62790./RT)
RC3H5O2 108. exp (-71162./RT)
RC3H3O 108. exp (-83720./RT)
PRADIO 108. exp (-46046./RT)
PRLIGH, PRLIN, PRLINES, PRADIOM2, RADIOM2, RADIO 108.5 exp (-41860./RT)
RADIOM2, RADIO , RMGUAI, RLIGM2A, RLIGM2B, PRFET3M2, PRKETM2, PRFET3 108. exp (-54418./RT)