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a,*
Energy and Resources Research Institute, School of Process, Environmental and Materials Engineering (SPEME), University of Leeds, Leeds LS2 9JT, UK
b
Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT, UK
Received 9 July 2006; received in revised form 18 January 2007; accepted 23 January 2007
Available online 27 February 2007
Abstract
Short rotation willow coppice (SRC) and a synthetic biomass, a mixture of the basic biomass components (cellulose, hemicellulose
and lignin), have been investigated for the inuence of potassium on their pyrolysis behaviours. The willow sample was pre-treated
to remove salts and metals by hydrochloric acid, and this demineralised sample was impregnated with potassium. The same type of
pre-treatment was applied to components of the synthetic biomass. Characterisation was performed using thermogravimetric analysis
with measurement of products by means of Fourier transform infrared spectroscopy (TGAFTIR) and pyrolysisgas chromatographymass spectrometry (PYGCMS). A comparison of product distributions and kinetics are reported. While the general features
of decomposition of SRC are described well by an additive behaviour of the individual components, there are some dierences in the
magnitude of the inuence of potassium, and on the products produced. For both SRC and the synthetic biomass, TGA traces indicate
catalytic promotion of both of the two-stages of biomass decomposition, and potassium can lower the average apparent rst-order activation energy for pyrolysis by up to 50 kJ/mol. For both SRC and synthetic biomass the yields and distribution of pyrolysis products
have been inuenced by the presence of the catalyst. Potassium catalysed pyrolysis increases the char yields markedly and this is more
pronounced for synthetic biomass than SRC. Gas evolution proles during pyrolysis show the same general features for both SRC and
synthetic biomass. Relative methane yields increase during the char formation stage of pyrolysis of the potassium doped samples. The
evolution proles of acetic acid and formaldehyde change, and these products are seen in lower relative amounts for both the demineralised samples. A greater variation in pyrolysis products is observed from the treated SRC samples compared to the dierent synthetic
biomass samples. Furthermore, substituted phenols from lignin pyrolysis are more dominant in the pyrolysis proles of the synthetic
biomass than of the SRC, implying that the extracted lignins used in the synthetic biomass yield a greater fraction of monomeric type
species than the lignocellulosic cell wall material of SRC. For both types of samples, PYGSMS analyses show that potassium has a
signicant inuence on cellulose decomposition markers, not just on the formation of levoglucosan, but also other species from the noncatalysed mechanism, such as 3,4-dihydroxy-3-cyclobutene-1,2-dione.
2007 Elsevier Ltd. All rights reserved.
Keywords: Biomass; Pyrolysis; Catalysis; Potassium; Mechanism
1. Introduction
Biomass is well recognised as a potential renewable
source of energy and is considered to be the obvious candidate for contributing to carbon dioxide reduction in the
Corresponding author. Tel.: +44 113 343 27 44; fax: +44 113 244 0572.
E-mail address: j.m.jones@leeds.ac.uk (J.M. Jones).
0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.01.026
short-term, since it can be co-combusted with coal in existing facilities, and in longer term in dedicated systems. The
main alternatives for utilisation of biomass are pyrolysis,
gasication and combustion. Much of the energy consumed for electricity production, 97% in the case of the
UK [1], comes from non-renewable sources. The present
use of carbon-based non-renewable energy is unsustainable, among other things because of the eect of the resultant carbon dioxide (CO2) emissions on the global climate.
2390
wt.%
Volatile matter
Fixed carbon
Ash
Moisture
69.83
17.53
5.20
7.44
18.68
2391
Table 2
Metal analyses for willow samples; as received, after drying at 333 K
Sample
Moisture
(wt.%)
Al
(mg/kg)
Ca
(mg/kg)
Cd
(mg/kg)
Co
(mg/kg)
Cr
(mg/kg)
Cu
(mg/kg)
Fe
(mg/kg)
K
(mg/kg)
Mg
(mg/kg)
Mn
(mg/kg)
Willow raw
Willow HCl
treated
Willow
K-impregnated
5.89
3.75
50
42
11 020
119
6.35
<0.005
<0.009
<0.009
2.50
<0.007
38.1
<0.045
137
7.6
3770
<107
1350
5.3
181
<0.009
19
<0.005
<0.009
<0.007
0.9
17 000
6.5
<0.009
4.80
0.1
for 6 h. The sample was then ltered, then washed using deionised water until the ltrate was Cl free (checked by
0.1 M silver nitrate solution). Then sample was oven dried
at 333 K to constant weight. After demineralisation samples were analysed for minerals presence using energy dispersive X-ray (EDX) analysis. EDX results show that
demineralisation with HCl is very ecient, resulting in
complete removal of minerals [20].
Impregnation. Three grams of sample, analysed before
impregnation for moisture content, was impregnated
by potassium (as potassium acetate) to yield a 1 wt.%
K-impregnated sample. After addition of potassium acetate
the sample was moistened by 1 cm3 of de-ionised water,
mixed and then oven dried at 333 K to constant weight.
6.8
-5
506
-10
-15
586
Willow raw
Willow HCl treated
Willow K-impregnated
647
-20
653
-25
500
700
800
900
Temperature, K
-5
533
DTG, %/min.
600
588
-10
595
-15
606
Mixture raw
Mixture HCl treated
Mixture K-impregnated
-20
647 662
-25
500
600
700
800
900
Temperature, K
Fig. 1. DTG proles for (a) willow SRC and (b) synthetic biomass
samples.
2392
Table 4
Activation energies for pyrolysis of willow and synthetic biomass samples
Sample
Willow
Willow
Willow
Willow
raw
HCl treated
K-impregnated [A]
K-impregnated [B]
Mixture
Mixture
Mixture
Mixture
Mixture
raw [A]
raw [B]
HCl treated
K-impregnated [A]
K-impregnated [B]
Ea (kJ/mol)
ln A (s 1)
k623 (s 1)
89.0
178.4
131.7
132.7
13.03
29.80
28.56
24.22
1.58 10
9.56 10
22.90
2.48 10
121.5
194.8
174.2
113.2
147.9
21.01
32.45
29.05
21.88
26.41
8.60 10
5.56 10
1.02 10
1.03
1.17 10
3
2
Volatiles
Char
Willow raw
Willow HCl treated
Willow K-impregnated
87.7
93.3
80.2
12.3
6.7
19.8
Mixture raw
Mixture HCl treated
Mixture K-impregnated
81.7
83.1
68.7
18.3
16.9
31.3
The main volatile components such as carbon monoxide, carbon dioxide, methane, acetic acid, formaldehyde
and acetone have been identied by FTIR. The typical
spectral output from the TGAFTIR analysis is shown in
Fig. 3 for the potassium impregnated sample and is known
as a waterfall spectrum. The gas evolution proles shown
-2
-3
-4
[A]
[B]
ln k
-5
-6
-7
-8
-9
0.0014
Willow raw
Willow HCl treated
Willow K-impregnated
0.0016
0.0018
0.0020
0.0022
-1
1/T [K ]
Mixture raw
Mixture HCl treated
Mixture K-impregnated
-2
-3
ln k
-4
-5
[A]
[B]
[A]
-6
[B]
-7
-8
0.0014
0.0016
0.0018
0.0020
-1
1/T [K ]
Fig. 2. Arrhenius plots for the pyrolysis of (a) willow SRC and
(b) synthetic biomass samples.
CH3COCH3
CO2
HCHO
CH3CHO
0.14
Absorbance
CO2
H2O
0.10
CH3OH
HCOOH
CH3COOH
CO
CH4
0.12
2393
CO
0.08
0.06
750
625
0.04
500
375
0.02
3500
3000
2500
2000
1500
1000
500
125
(C
ra
pe
250
0.00
e
ur
em
Wavenumbers (cm-1)
Fig. 3. Waterfall spectrum showing volatile components from the TGA-FTIR pyrolysis of potassium impregnated willow SRC sample.
2394
1.4x10
Carbon monoxide
-3
Willow raw
Willow HCl treated
Willow K-impregnated
1.4x10
-3
Mixture raw
Mixture HCl treated
Mixture K-impregnated
-3
1.2x10
-3
Intensity/mg of sample
Intensity/mg of sample
1.2x10
Carbon monoxide
-3
1.0x10
-4
8.0x10
-4
6.0x10
-4
4.0x10
1.0x10
-4
8.0x10
-4
6.0x10
-4
4.0x10
-4
2.0x10
-4
2.0x10
0.0
0.0
-4
-2.0x10
400
500
600
700
800
900
1000
400
1100
500
600
700
800
900
1000
1100
Temperature, K
Temperature, K
-2
1.4x10
Carbon dioxide
-2
1.2x10
Willow raw
Willow HCl treated
Willow K-impregnated
-2
1.0x10
Carbon dioxide
Mixture raw
Mixture HCl treated
Mixture K-impregnated
-2
1.2x10
Intensity/mg of sample
Intensity/mg of sample
-2
1.0x10
-3
8.0x10
-3
6.0x10
-3
4.0x10
-3
2.0x10
-3
8.0x10
-3
6.0x10
-3
4.0x10
-3
2.0x10
0.0
0.0
-3
-3
-2.0x10
-2.0x10
400
500
600
700
800
900
1000
400
1100
500
600
700
800
900
1000
1100
900
1000
1100
Temperature, K
Temperature, K
-3
1.6x10
Methane
-3
1.4x10
Willow raw
Willow HCl treated
Willow K-impregnated
-3
Mixture raw
Mixture HCl treated
Mixture K-impregnated
-3
1.5x10
Intensity/mg of sample
Intensity/mg of sample
1.2x10
Methane
-3
1.8x10
-3
1.0x10
-4
8.0x10
-4
6.0x10
-4
4.0x10
-3
1.2x10
-4
9.0x10
-4
6.0x10
-4
-4
3.0x10
2.0x10
0.0
0.0
-4
-2.0x10
400
500
600
700
800
900
1000
1100
Temperature, K
400
500
600
700
800
Temperature, K
Fig. 4. Species evolution proles during the TGAFTIR pyrolysis of willow SRC and synthetic biomass sample (mixture).
2395
-4
7.0x10
Acetic acid
0.0016
Willow raw
Willow HCl treated
Willow K-impregnated
-4
6.0x10
-4
Mixture raw
Mixture HCl treated
Mixture K-impregnated
0.0012
Intensity/mg of sample
Intensity/mg of sample
5.0x10
Acetic acid
0.0014
-4
4.0x10
-4
3.0x10
-4
2.0x10
-4
0.0010
0.0008
0.0006
0.0004
1.0x10
0.0002
0.0
0.0000
-4
-0.0002
-1.0x10
400
500
600
700
800
900
1000
1100
400
500
600
Formaldehyde
-3
1.0x10
-4
900
1000
1100
-4
6.0x10
-4
4.0x10
Mixture raw
Mixture HCl treated
Mixture K-impregnated
-4
6.0x10
Intensity/mg of sample
Intensity/mg of sample
800
Formaldehyde
-4
7.0x10
Willow raw
Willow HCl treated
Willow K-impregnated
8.0x10
700
Temperature, K
Temperature, K
-4
5.0x10
-4
4.0x10
-4
3.0x10
-4
2.0x10
-4
2.0x10
-4
1.0x10
0.0
0.0
-4
-1.0x10
400
500
600
700
800
900
1000
1100
400
500
600
700
800
900
1000
1100
Temperature, K
Temperature, K
-3
1.0x10
Acetone
-4
Willow raw
Willow HCl treated
Willow K-impregnated
6.0x10
-4
-4
4.0x10
-4
3.0x10
-4
2.0x10
Mixture raw
Mixture HCl treated
Mixture K-impregnated
-4
8.0x10
Intensity/mg of sample
Intensity/mg of sample
5.0x10
Acetone
-4
6.0x10
-4
4.0x10
-4
2.0x10
-4
1.0x10
0.0
0.0
-4
-1.0x10
400
500
600
700
800
900
1000
400
1100
Temperature, K
500
600
700
800
900
1000
1100
Temperature, K
Fig. 4 (continued)
2396
3000000
Abundance
2500000
2000000
44
17
1500000
37
33
21-24
7-13
___
500000
20
18
15
16 19
42
28
26
__ 14
41
31
25
3 56
_______
1000000
36
__
27
29
30
39
32 34 38
40
35
45
47
48
46 49
50
43
43a
0
10
20
40
30
Time, min.
50
60
Fig. 5. PyrolysisGCMS chromatogram for raw willow sample. The main peaks are assigned from mass spectral detection as follows: (1) acetic acid; (2)
2-methyl-1-propanol; (3) 1-hydroxy-2-propanone; (4) 3-butenoic acid, ethyl ester; (5) propanal; (6) furfural; (7) 5-methyl-2(3H)-furanone; (8) 2,5-dihydro3,4-dimethyl furan; (9) acetic acid, ethyl ester; (10) 2-ethyl-butanal; (11) methyl-cyclohexane; (12) 2H-pyran-2-one; (13) 2-cyclohexen-1-one; (14)
2-hydroxy-2-cyclopenten-1-one; (15) 5-methyl-2-furancarboxaldehyde; (16) 2H-furanone; (17) 3,4-dihydroxy-3-cyclobutene-1,2-one; (18) cycloheptanone;
(19) phenol; (20) 2-methoxy-phenol; (21) 4-methyl-phenol; (22) 4-ethyl-2-hydroxycyclopenten-2-en-1-one; (23) carbonic acid, ethyl 2-propenyl ester; (24)
2- or/and 3-methylphenol; (25) 2-methoxy-4-methylphenol; (26) cyclopropyl carbinol; (27) 4-ethyl-2-methoxyphenol; (28) 2-octenoic acid; (29) (Z)-2butene-1,4-dione; (30) 2-methyl-4-pentenoic acid; (31) 2-methoxy-4-vinylphenol; (32) 2-methoxy-4-(1-propenyl)-phenol; (33) 2,6-dimethoxy-phenol; (34)
(E)-3-methoxy-5-(1-propenyl)-phenol; (35) 3,6-dimethoxy-phenol; (36) 2-methoxy-4-(1-propenyl)-phenol; (37) 4-methoxy-3-(methoxymethyl)-phenol; (38)
vanillin; (39) 1-(2,6-dihydroxy-4-methoxyphenyl)-ethanone; (40) 1-(4-hydroxy-3-methoxyphenyl)-ethanone; (41) 4-formylphenoxy acetic acid; (42)
4-hydroxy-3-methoxy-benzoacetic acid; (43, 43a) 2,6-dimethoxy-4-(2-propenyl)-phenol; (44) levoglucosan; (45) 4-hydroxy-3,5-dimethoxy benzaldehyde;
(46) 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone; (47) 1-(2,4,6-trihydroxy-3-methylphenyl)-1-butanone; (48) desaspidinol; (49) aspidinol; (50) 1-(2,6dihydroxy-4-methoxyphenyl)-ethanone.
45
1800000
1600000
35,36
24
1000000
38
32
26-31
800000
20
7-13
400000
200000
25
18
19
15
14
_______
600000
__
16
_______
Abundance
34
17
1200000
____________________
1400000
39
___ 33
22 23
21
43 44
48
41
46
37
49
44 a
40
42
47
50
0
10
20
30
Time, min.
40
50
60
Fig. 6. PyrolysisGCMS chromatogram for HCl treated willow sample. The main peaks are assigned from mass spectral detection as follows: (1)
methoxyethanone; (2) propanonic acid; (3) carbonic acid, diethyl ester; (4) 2,3-dihydro-4-methyl-furan; (5) propanal; (6) furfural; (7) 5-methyl-2(3H)furanone (8) 2-furanmethanol; (9) acetic acid, ethyl ester; (10) pentane; (11) 1-(2-furanyl)-ethanone; (12) furan; (13) 2H-pyran-2-one; (14) 2-hydroxy-2cyclopenten-1-one; (15) hydroquinone; (16) 2(5H)-furanone; (17) 3,4-dihydroxy-3-cyclobutene-1,2-dione; (18) cycloheptanone; (19) phenol; (20)
2-methoxy-phenol; (21) 4-methyl-phenol; (22) 2-methyl-1,3-cyclohexanedione; (23) 2- or/and 3-methylphenol; (24) 2-methoxy-4-methyl-phenol; (25)
3,5-dihydroxy-2-methyl-4H-pyran and/or 5-hydroxy-2-(hydroxymethyl)-4H-pyran-4-one; (26) 4-ethyl-2-methoxyphenol; (27) 2-hydroxy-5-methoxybenzaldehyde; (28) 1,4-dimethoxy-2-methyl-benzene; (29) 2,5-dihydrofuran; (30) 1-hydroxy-2-butanone; (31) 4-methyl-2-hexene (cis and trans); (32)
2-methoxy-4-vinylphenol; (33) 2-methoxy-3-(2-propenyl)-phenol; (34) 2,6-dimethoxy-phenol; (35) 1,2-epoxy-3-propyl acetate; (36) 3,6-dimethoxy-phenol;
(37) (E)-2-methoxy-5-(1propenyl)-phenol; (38) 2-methoxy-4-(1-propenyl)-phenol; (39) 4-methoxy-3-(methoxyphenyl)-phenol; (40) vanillin; (41) 1-(2,6dihydroxy-4-methoxy-phenyl)-ethanone; (42) 1-(4-hydroxy-3-methoxyphenyl)-ethanone; (43) 4-hydroxy-3-methoxy-benzoacetic acid; (44, 44a)
2,6-dimethoxy-4-(2-propenyl)-phenol; (45) levoglucosan; (46) 4-hydroxy-3,5-dimethoxy-benzaldehyde; (47) 1-(2,6-dihydroxy-4-methoxyphenyl)-ethanone;
(48) 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone; (49) desaspidinol; (50) aspidinol.
2397
6000000
1
5500000
5000000
4500000
Abundance
4000000
3500000
3000000
31
2500000
18-22
17
13-15
2
______
1500000
23-25
16
1000000
500000
12
6 8
7
11
5
9 10
4
3
______
_________
2000000
35
38
29
34
32 33
__ _
27
26 28 30
36
37
40
39
0
10
20
40
30
Time, min.
50
60
Fig. 7. PyrolysisGCMS chromatogram for potassium impregnated willow sample. The main peaks are assigned from mass spectral detection as follows:
(1) acetic acid; (2) 2-methyl-1-propanol; (3) 2-hydroxy-propanonic acid; (4) propanonic acid, anhydride or/and carbonic acid, diethyl ester; (5) propanal;
(6) furfural; (7) 2-furanmethanol; (8) acetic acid, ethyl ester; (9) 1-hydroxy-2-propanone; (10) 2-hydroxy-2-cyclopenten-1-one; (11) 3-methyl-2cyclopenten-1-one; (12) butyrolacetone; (13) 2,3-dimethyl-2-cyclopenten; (14) 32-hydroxy-3-methyl-2-cyclopenten-1-one; (15) 2-hydroxy-3,5-didimethylcyclopenten-2-en-1-one; (16) phenol; (17) mequinol or/and 2-methoxy-phenol; (18) 3-methyl-phenol; (19) 3-methyl-2-butenal; (20) 2,6-dimethyl-phenol;
(21) acetic acid, phenyl ester; (22) 2- or/and 3- or/and 4-methyl-phenol; (23) 2-methoxy-4-methyl-phenol; (24) cyclopropyl carbinol; (25) 2,3- or/and 3,5or/and 2,4- or/and 2,5-domethyl-phenol; (26) 2,3,5- or/and 2,4,6-trimethyl-phenol; (27) 4-ethyl-2-methoxy-phenol; (28) 2-ethyl-4-methyl-phenol; (29)
2-methoxy-4-vinylphenol; (30) eugenol or/and 2-methoxy-3-(2-propenyl)-phenol; (31) 2,6-dimethoxy-phenol; (32) 2-methoxy-4-(1-propenyl)-phenol or/
and 3-allyl-6-methoxy-phenol; (33) 4-methoxy-3-(methoxymethyl)-phenol; (34) 1-2,6-dihydroxy-4-methoxyphenyl-ethanone; (35) 1-(2,5-dimethoxyphenyl)-ethanone; (36) 4-hydroxy-3-methoxy-benzeneacetic acid; (37, 37a) 2,6-dimethoxy-4-(2-propenyl)-phenol; (38) levoglucosan; (39) 4-hydroxy-3,5dimethoxy-benzaldehyde; (40) desaspidinol.
3500000
3000000
Abundance
2500000
2000000
15
24,25
______
22
500000
13
5
7
11 14
6 8 9 12
10
26
21
__
23
38,39
__________
_______
___
27
16-20
1000000
__________
1500000
33-36
28-32
__
37
__
41
42
40
44
43
0
10
20
30
Time, min.
40
50
60
Fig. 8. PyrolysisGCMS chromatogram for raw synthetic biomass sample. The main peaks are assigned from mass spectral detection as follows: (1)
acetic acid; (2) acetic acid, 2-propenyl ester; (3) 1-hydroxy-2-propanone; (4) propanal; (5) 3(2H)-pyridazinone; (6) cycloheptane; (7) 1-methylenencyclopropenyl)-ethanone; (8) 2-butanone; (9) 3-furanmethanol; (10) 2H-pyran-2-one; (11) butyrolacetone; (12) 2(5H)-furanone; (13) 2-hydroxy-3-methyl-2cyclopenten-1-one; (14) phenol; (15) 2-methoxy phenol; (16) 2-methyl phenol; (17) 2-hexyn-1-ol; (18) 2,3-dimethyl phenol; (19) propanal; (20) 2-methyl
phenol; (21) 2-methoxy-4-methyl; (22) 2,4-dimethyl phenol; (23) 4-ethyl-2-methoxy phenol; (24) (Z)-2-butene-4-diol; (25) 3,3-dimethyl-1-pentene; (26)
2-methoxy-4-vinyl-phenol; (27) 2,6-dimethoxy-phenol; (28) 2-methoxy-4-(1-propenyl)-phenol; (29) 4-hydroxy-3-methoxy benzoic acid; (30) vanillin; (31)
hydroquinone; (32) 4-hydroxy benzaldehyde; (33) 3-methoxy-phenol; (34) 1-(2,6-dihydroxy-4-methoxyphenyl)-ethanone; (35) 2-methoxy-1,4-benzenediol;
(36) 1-(4-hydroxy-3-methoxyphenyl)-ethanone; (37) 1-(3,4-domethoxyphenyl)-ethanone; (38) 4-hydroxy-3-methoxy-benzeneacetic acid; (39) 1-(4-methylphenyl)-ethanone; (40) levoglucosan; (41) 2,6-dimethoxy-4-(2-propenyl)-phenol; (42) 4-hydroxy-3,5-dimethoxy-benzaldehyde; (43) 1-(4-hydroxy-4,5dimethoxyphenyl)-ethanone; (44) 1-(2,4,6-trihydoxy-3-methylphenyl)-1-butanone.
2398
4000000
3500000
27,28
3000000
18-22
2000000
1 2
17
9-14
_____
1500000
16
15
1000000
3
500000
67 8
_________
2500000
__
___
26
23
_____________
_______
Abundance
4500000
32
30
24
25 29
31
34
33
35 38
36
37 39
40
41
42
43
0
10
20
40
30
Time, min.
50
60
Fig. 9. PyrolysisGCMS chromatogram for HCl treated biomass mixture sample. The main peaks are assigned from mass spectral detection as follows:
(1) acetic acid; (2) acetic acid, 2-propenyl ester; (3) formic acid, ethyl ester; (4) pentenyl, hydroperoxide; (5) 2H-pyran-2-one; (6) isobutane; (7) 2-butanone;
(8) 3-furanmethanol; (9) 5-methyl-2-furancarboxaldehyde; (10) (Z)-2-butene-1,4-diol; (11) 1-ethyl-cyclopentene; (12) butyrolacetone; (13) cyclopentanone;
(14) 3,4-dimethyl-3-cyclobutene-1,2-dione; (15) 2-hydroxy-3-methyl-2-cyclopenten-1-one; (16) phenol; (17) 2-methoxy-phenol; (18) 3-methyl-phenol; (19)
2-hexyn1-ol; (20) 2-methyl-1,3-cyclohexanedione; (21) propanal; (22) 2-methyl-phenol; (23) 2-methoxy-4-methyl-phenol; (24) 2,4-dimethyl-phenol; (25)
4-ethyl-2-methoxy-phenol; (26) 2,5-dihydro-furan; (27) (Z)-2-butene-1,4-diol; (28) 3-methoxy-1-propanone; (29) 4-methyl-2-hexene (cis and trans); (30)
2-methoxy-4-vinylphenol; (31) 2-methoxy-4-(1-propenyl)-phenol; (32) 2,6-dimethoxy-phenol; (33) 2-methoxy-4-(1-propenyl)-phenol/strong/; (34)
4-hydroxy-3-methoxy-benzoic acid; (35) vanillin; (36) 4-hydroxy-3-methoxy-benzoacetic acid; (37) 1-(4-hydroxy-3-methoxyphenyl)-ethanone; (38)
1-(3,4-dimethoxyphenyl)-ethanone; (39) 1-(4-hydroxy-3-methoxyphenyl)-2-propanone; (40) levoglucosan; (41) 4-hydroxy-3,5-dimethoxy-benzaldehyde;
(42) 1-(4-hydroxy-4,5-dimethoxyphenyl)-ethanone; (43) 1-(2,4,6-trihydoxy-3-methylphenyl)-1-butanone.
5500000
5000000
4500000
3500000
18-22
3000000
2500000
13-16
2
12
1000000
500000
23-25
17
2000000
1500000
_________
______________
_________
Abundance
4000000
__
7
9
6 8
3
11
__ _26 28
31
30
27 29
10
32 33
34
35
36
39
40
37
38
41
0
10
20
30
Time, min.
40
50
60
Fig. 10. PyrolysisGCMS chromatogram for potassium impregnated synthetic biomass sample. The main peaks are assigned from mass spectral
detection as follows: (1) acetic acid; (2) acetic acid, 2-propenyl ester or/and 1-hydroxy-2-propanone; (3) 1-methoxy-2-propanone; (4) 2-propen-1-ol; (5)
2-octenoic acid; (6) 2-methyl-butanal; (7) 2-cyclopenten-1-one; (8) 2-furanmethanol; (9) 2-methyl-2-cyclopenten-1-one; (10) 3-furanmethanol; (11)
3-methyl-2-cyclopenten-1-one; (12) butyrolacetone; (13) 2,3-dimethyl-2-cyclopenten-1-one; (14) 2-hydroxy-3-methyl-2-cyclopenten-1-one; (15) 2-hydroxy3,5-dimethylcyclopenten-2-en-1-one; (16) phenol; (17) 2-methoxy-phenol; (18) 2-methyl-phenol; (19) 3-methyl-2-hydroxy-2-cyclopenten-1-one; (20)
4,6-dimethyl-2H-pyran-2-one; (21) 2-ethyl-2-methyl-1,3-cyclopentanedione; (22) 4-methyl-phenol; (23) 2-methoxy-4-methyl-phenol; (24) cyclopropyl
carbinol; (25) 2,4-dimethyl-phenol; (26) 3,4,5-trimethyl-phenol; (27) 2,5-dimethyl-phenol; (28) 4-ethyl-2-methyl-phenol; (29) 2,4,6- or/and 2,3,5-trimethylphenol; (30) 2-methoxy-4-vinylphenol; (31) 3,4-dimethoxy-phenol; (32) 2-methoxy-4-(1-propenyl)-phenol; (33) 4-methoxy-3-(methoxymethyl)-phenol; (34)
vanillin; (35) 1-(2,6-dihydroxy-4-methoxyphenyl)-ethanone; (36) 4-methyl-2,5-diethoxybenzaldehyde; (37) 1-(4-hydroxy-3-methoxyphenyl)-2-propanone;
(38) 2,5-dimethoxy-4-ethylbenzaldehyde; (39) levoglucosan; (40) 4-hydroxy-3,5-dimethoxy-benzaldehyde; (41) 1-(2,4,6-trihydoxy-3-methylphenyl)-1butanone.
2399
and potassium impregnated willow samples and for synthetic mixture in Figs. 810, respectively. The main peaks
were assigned from mass spectral detection and from the
literature [2426] and are given under the each gure.
One product, namely squaric acid, 3,4-dihydroxy-3-cyclobutene-1,2-dione, has not been identied previously in the
literature.
Table 5
Key markers assignment for PYGCMS of willow and synthetic biomass samples
Name of compound, chemical formula
Structure, chemical
formula
Phenol, C6H6O
Furfural, C5H4O2
Molecular
weight
m/z
Cellulose and
lignin
94.11
Cellulose
96.08
Cellulose
98.10
Cellulose
98.10
OH
Cellulose
114.06
Guaiacol lignin
124.14
Guaiacol lignin
150.17
Guaiacol lignin
152.10
Syringol lignin
154.16
Cellulose
162.05
Guaiacol lignin
164.20
Guaiacol lignin
168.19
Lignin
182.17
Syringol lignin
182.17
Syringol lignin
194.23
Lignin
210.23
OH
Type of key
marker
O
HO
2-Hydroxy-2-cyclopenten-1-one, C5H6O2
3-Furanmethanol, C5H6O2
HO
3,4-Dihydroxy-3-cyclobutene-1,2-dione,
C4H2O4
O
OH
OH
2-Methoxy-phenol, C7H8O2
O
OH
2-Methoxy-4-vinylphenol, C9H10O2
O
HO
Vanillin, C8H8O3
2,6-Dimethoxyphenol, C8H10O3
O
OH
HO
O
O
1,6-Anhydro-b-D-glucopyranose
(levoglucosan), C6H10O5
HO
OH
OH
2-Methoxy-4-(1-propenyl)-phenol, C10H12O2
O
O
4-Methoxy-3-(methoxymethyl)-phenol,
C9H12O3
OH
OH
O
HO
O
4-Hydroxy-3,5-dimethoxy benzaldehyde,
C9H10O4
O
OH
O
O
O
2,6-Dimethoxy-4-(2-propenyl)-phenol,
C11H14O3
HO
O
HO
1-(2,4,6-Trihydroxy-3-methylphenyl)-butan-1one, C11H14O4
OH
OH
2400
Furfural
Willow raw
Willow HCl treated
Willow K-impregnated
2-hydroxy-2-cyclopenten-1-one
3,4-dihydroxy-3-cyclobutene-1,2-dione
Phenol
2-methoxyphenol
2-methoxy-4-vinylphenol
2,6-dimethoxyphenol
2-methoxy-4-(1-propenyl)-phenol
4-methoxy-3-(methoxymethyl)-phenol
4-hydroxy-3-methoxy-benzoacetic acid
2,6-dimethoxy-4-(2-propenyl)-phenol
Levoglucosan
0
Area, %
Fig. 11. Peak areas for key markers from PYGCMS analysis for willow samples (raw, HCl treated and potassium impregnated). (Peak areas have been
normalised per mg of volatile products.)
2401
3-furanmethanol
Phenol
2-methoxyphenol
2-methoxy-4-vinylphenol
2,6-dimethoxyphenol
2-methoxy-4-(1-propenyl)-phenol
Vanillin
Levoglucosan
Mixture raw
4-hydroxy-3,5-dimethoxy benzaldehyde
1-(2,4,6-trihydroxy-methylphenyl)-1butanone
0.0
1.0
2.0
3.0
4.0
5.0
Area, %
Fig. 12. Peak areas for key markers from PYGCMS analysis for synthetic biomass, a mixture of the basic biomass components (raw, HCl treated and
potassium impregnated). (Peak areas have been normalised per mg of volatile products.)
4. Conclusions
A willow SRC biomass sample and a synthetic biomass,
a mixture of the basic biomass components were subjected
to two types of pretreatment: HCl demineralisation and
impregnation of the demineralised sample by potassium
(as potassium acetate).
Pyrolysis tests revealed additive properties of the mixture of the basic biomass constituents, in that the features
of the DTG pyrolysis proles were directly comparable
to those of the willow samples. The yields of pyrolysis
products were inuenced by the presence of the catalyst.
Potassium catalysed pyrolysis resulted in increased char
yields (from 6.7% for HCl treated willow sample to
19.8% for K-impregnated willow sample and from 16.9%
to 31.3% for synthetic biomass sample). Furthermore,
potassium lowered the average apparent rst-order activation energy for pyrolysis by up to 50 kJ/mol, and the catalysis was greater in SRC than in the synthetic biomass.
DTG analysis of the potassium impregnated sample
revealed that its thermal degradation occurs in two steps,
and the main pyrolysis DTG peak temperature shifted
67 K for the willow sample and 41 K for the synthetic biomass. A similar shift to lower temperature was observed in
gas evolution proles for all species, except methane. Relative methane yields increased during the char formation
stage of pyrolysis of the potassium doped samples. The
2402