九州大学大学院総合理工学府報告第 44 巻 第 1 号 22-29 頁 令和 4 年 9 月

Engineering Sciences Reports, Kyushu University
Vol. 44, No. 1, pp. 22-29, SEP, 2022

Low Temperature Pyrolysis of Woody Biomass underSteam for Selective Production of Coniferyl Aldehyde
Fu WEI*1 Shinji KUDO*2,*3,*4,† Xinyu WANG*1 Shusaku ASANO*2,*3
Jun-ichiro Hayashi*2,*3,*4
E-mail of corresponding author: shinji_kudo@cm.kyushu-u.ac.jp†(Received July 27, 2022, accepted August 4, 2022)
Multi-product strategy is a key to the establishment of economically feasible technologies for theutilization of biomass as feedstock for fuels and chemicals. Studies on this strategy generally consider
hemicellulose, cellulose, and lignin as sources of chemical compounds. This work focused on a minor
part of lignocellulosic biomass. We found pyrolysis of a woody biomass under steam at low
temperatures enabled selective production of coniferyl aldehyde that was rarely reported in literature
as a compound in pyrolysis products. Experiments under different pyrolysis conditions revealed thatthe release of coniferyl aldehyde from biomass needed steam and a temperature of around 220°C. A
comparative study with lignin as a reference feedstock suggested that it was derived from lignincarbohydrate complex. Furthermore, staged pyrolysis produced terpenes as well as coniferyl aldehyde
as separate products. The yield of coniferyl aldehyde was very low because it was derived from minor
structure in biomass. Meanwhile, the solid residue after pyrolysis largely retained original chemical
structure, enabling its further conversion into chemicals.
Key words: Lignocellulosic biomass, Pyrolysis, Steam, Multi-product, Extractives, Coniferyl aldehyde

1.

Introduction

The world is currently facing a challenge ofshifting from reliance on fossil fuels tosustainable resources. Biomass, especiallylignocellulosic biomass, is a unique, renewable,
and carbon-neutral resource that can be used
to produce green fuels and chemicals.1–3)
Lignocellulosic biomass consists mainly ofhemicellulose, cellulose, and lignin. Glucose isconsidered to be a key platform for various
chemical compounds in a future biomass-based
chemical industry.4,5) Glucose is available fromlignocellulosic biomass by the separation ofcellulose from other components, followed bysaccharification. Many technologies have beendeveloped for the components separation andsaccharification, but lignocellulose-derived
glucose is currently too expensive to becompetitive with petrochemicals and widely
prevalent as feedstock for fuels and chemicals.6)
The manufacturing process is generally*1 Department of Applied Science for Electronics andMaterials, Graduate student*2 Department of Applied Science for Electronics andMaterials*3 Institute for Materials Chemistry and Engineering*4 Transdisciplinary Research and Education Center forGreen Chemistry

designed so as to produce only glucose withother components being combusted forgenerating a low-grade heat. An effective way
for reducing the cost of glucose production is tovalorize other components (multi-productstrategy), which include not only hemicellulose
and lignin, but also minor components such as
terpenes.7)
Pyrolysis is a thermal conversion method fordecomposing biomass, which produces solid(char), liquid (biooil), and gaseous products.
During heating up, hemicellulose firstly starts
to decompose, followed by cellulose and thenlignin, although there is overlapping intemperature
ranges.8–10)
Focusingondifferences or heterogeneity of biomass
components in reactivity, we have recently
proposed staged pyrolytic conversion as amethod for multi-product production fromlignocellulosic biomass.11) When Japanese
cedar
was
pyrolyzedat250−350°C,
anhydrosugars
consisting
mainlyoflevoglucosan were selectively obtained. Glucose
is readily available from levoglucosan by its
hydrolysis under acid catalysis.12,13) Further
pyrolysis of the solid residue after pelletization
simultaneously
producedlignin-derived
phenolic compounds, a mechanically strong

九州大学大学院総合理工学報告 第 44 巻 第 1 号

2.

Experimental

As-received Japanese cedar from Oita
prefecture, Japan, was ground and sieved tosizes of 2.0–4.0 mm for the use as feedstock.
Alkali lignin purchased from Sigma-Aldrich
was also used as feedstock. The samples weredried before use in pyrolysis experiments.
Steam pyrolysis experiments were performed
in a home-made reaction system shown in Fig.
1. The system consisted of a reaction tube,
steam and N2 mixing-supplying system, oven,and liquid product recovery system. The
reactor loaded with 8 g of sample was heated toa prescribed temperature (Tp = 130, 160, 190,
220, or 250°C) under 10 mL/min of N2. Afterreaching the temperature, water was supplied
to the system with a syringe pump for 2 h at aflow rate that made a mass ratio between total
suppliedwater
andloadedbiomass(water/biomass) be 0, 2, 5, 10, or 15. Steam andcompounds volatilized from biomass wererecovered as liquid products in the recovery
system at 0°C. After stopping the water supply,

the oven was left at Tp for 10 min to completely
remove the moisture inside reactor, and thencooled to a room temperature.
The pyrolysis experiments were carried out
in two modes. The one is a direct pyrolysis mode(DP) mentioned above. Another is a staged
pyrolysis mode (SP), where the steam
treatment was carried out in sequence at 130,
160, and 220°C. Briefly, after the pyrolysis
under steam at 130°C (1st step), the sample
was heated to 160°C without cooling, followedby the steam treatment for 2h (2nd step). The
treatment was further carried out at 220°C in
the same manner (3rd step).
Oven

N2
MFC
Water

Syringe pump
Thermocouple

Biomasscoke, and combustible gas. The staged pyrolysis,thus, enables valorization of a large portion of
lignocellulosic biomass.
In the present work, pyrolysis attemperatures lower than 250°C is investigatedas a part of staged pyrolysis. Steam is employed
as an agent to support the release of desired
compounds during pyrolysis. Heating of
biomass under steam, known as steam
distillation, is widely used in industry for
extracting essential oils consisting mainly of
terpenes. Steam also induces thermal
degradation and/or hydrolysis of some biomass
active components over a wide range oftemperatures and treatment times as achemical-freeandwater-only
media
treatment.14,15) Herein we report that coniferyl
aldehyde (CA) is selectively obtained withsteam pyrolysis under appropriate conditions.
This is a high-value added compound andrarely found in products of biomass pyrolysis.
To the best of our knowledge, there has been noreport on the pyrolytic synthesis of thiscompound, excepting organic- or bio-synthesis
approach using phenolic compounds as
substrates.16) The yields of CA reported in thiswork are low, well below 1 wt%, but its
production as a part of staged pyrolysis or otherbiomass conversion processes would have aconsiderable impact on economic performanceof the processes, considering the current pricein market.

23

Mixer/buffer

令和 4 年度

Liquidproduct

Fig. 1 Experimental apparatus for pyrolysis of biomass
under steam.

The pyrolysis experiments were hereafter
denoted by DP-Tp or SP-Tp, using the mode ofpyrolysis and temperature for steam treatment.
The recovered liquid products contained not
only the product from pyrolysis under steam,
but also volatiles generated in the course ofheating under N2. In SP, the liquid products
were recovered separately at the three steam
treatments: initial 130°C steam treatment (SP130), 160°C steam treatment including heatingfrom 130°C (SP-130-160), and 220°C steam
treatment including heating from 160°C (SP160-220).
The liquid product was mixed withdichloromethane (DCM) for extracting DCMsoluble compounds, and the extracts wererecovered by evaporating DCM with a rotary
evaporator operated at 30°C for 6 h. The yields
of DCM extracts and solid product on afeedstock sample basis were calculated fromtheir mass.
DCM
extracts
weredissolvedintetrahydrofuran and then subjected to acomposition analysis by gas chromatographymass spectrometry (GC-MS) on a PerkinElmer
Clarus SQ8. Details for the analytical method
arereportedelsewhere.11,17)
RelativeLow Temperature Pyrolysis of Woody Biomass under Steam for Selective Production of Coniferyl Aldehyde

percentages of identified compounds were
calculated from their peak area in the total ion
chromatogram for a semi-quantification ofcomposition of extracts. The concentration of
CA was determined using a gas chromatogramflame ionization detector (GC-FID: Shimadzu,
GC-2030). Chemical compositions of cedar andsolid residue (char) from pyrolysis wereanalyzed by two-step acid hydrolysis according
to a method reported by the US National
Renewable Energy Laboratory (NREL).18)

3.

Results and discussion

CAformation
duringpyrolysisoflignocellulosic biomass under steam was
unexpectedly found during our experiments forinvestigating residual terpenes in hydrochars.
The
hydrochars
were
preparedbyhydrothermal treatment of cedar or rice straw
at 160°C for 1 h in an autoclave, and thenheated under steam at 220°C. Fig. 2 shows GCMS chromatograms for DCM extracts of liquid
products. CA was the major compound in theextracts from cedar. The extracts from ricestraw also contained CA and, in addition,
sinapyl aldehyde having a similar structure.
Aromatic compounds contained in biooil are
generally derived from lignin. Aromatic nuclei
in softwood lignin (cedar) and herbaceous
biomass (rice straw) are guaiacyl type andguaiacyl/syringyl/p-hydroxyphenyl
type,
respectively,19)whichroughly
explains
detection of sinapyl aldehyde only in theextracts of rice straw. Among aromaticcompounds in biooil, p-unsubstituted phenols
such as phenol, guaiacol, and syringol, are themost abundant, and phenols having propyl
chain at para-position like CA are scarcely
found.20) Because the chromatograms of Fig. 2
do not agree with this trend, it was anticipatedthat CA and sinapyl aldehyde were not derived
from lignin. The heating temperature of 220°C
was in fact too low to induce substantial
occurrence of lignin pyrolysis. Furthermore,
the formation of double bond between α and βcarbons in lignin was unlikely to occur during
the treatments (Fig. 3 (a) shows the typicallinkage between monolignol units). A potential
source of CA and sinapyl aldehyde was lignincarbohydrate complex (LCC). As shown in Fig.
3 (b), ferulic acid structure presents in LCC.21)
The hydrothermal treatment supposedly
removed hemicellulose, leaving ferulic acidbound to lignin, and the subsequent steam
treatment effectively cleaved the linkage torelease the ferulic acid portion as CA.

Because hemicellulose is removed during
pyrolysis at the lowest temperature among
three major components, it was believed thatthe selective formation of CA would occur evenfrom a raw cedar in the pyrolysis using steam
at low temperatures. Therefore, pyrolysis ofcedar using steam is investigated under
different conditions.
100
Relative abundance (%)

24

50

(a)
1
2

4

3

5

0
100 1 (b)
6

50

7
8

4

9

0
20

30

40
50
Retention time (min)6070Fig. 2 GC-MS chromatograms of DCM extracts frompyrolysis of (a) cedar and (b) rice straw hydrochars.
Major compounds: 1) furfural, 2) vanillin, 3) 4propyl-guaiacol, 4) CA, 5) a type of diterpene, 6)
coumaran,
7)
4-vinyl-guaiacol,
8)5hydroxymethylfurfural and 9) sinapyl aldehyde.

Fig. 3 (a) Typical linkage between monolignols (β-O-4linkage) and (b) a potential source of CA inlignocellulosic biomass: LCC.

Fig. 4 shows the yields of DCM extracts. DPof lignin under steam produced little extracts.
This was reasonable because employed alkali
lignin is produced under harsh conditions
during a type of kraft process, which removed
volatile small molecules. The yield of extracts
from cedar in DP increased with Tp andwater/biomass ratio. Compounds in theextracts could be derived largely from threedifferent pathways: (a) steam distillation ofwater-insoluble or slightly soluble compounds
such as terpenes, (b) pyrolysis of hemicellulose,
cellulose, and lignin, and (c) steam-induced
pyrolysis. Steam distillation occurs even at a
low temperature like 130°C,22) but the content
of terpenes in biomass is generally low asshown by the extracts yield of 0.1 wt% in DP.
The pathway (b) is affected significantly by Tp.
Although pyrolysis is not remarkable at therange of temperature examined in this study, asubstantial portion of extracts is considered to令和 4 年度

九州大学大学院総合理工学報告 第 44 巻 第 1 号

3

2

1.8

1.8

10

15

1.5
1.2

1.2

1

0
LigninYield of extracts (wt%)

3.2

DP

3

0.05 0.1

0.3

0.4

0.3

220 130 160 190 220 250 0
Tp (water/biomass = 2)2

5

Water/biomass (DP-220)

showed that steam had an important role in theformation of phenols and furans. These results
are supposed to be related to the permeabilityof steam, causing enhanced desorption,
distillation, and transport of the produced
volatiles. In addition, steam acts not only as acarrier, but also as a reactant to stabilize
radicals generated from thermal decompositionofbiomasscomponents
andinhibitpolycondensation to form less char.22) The
extracts from SP-160-220 had much smaller
terpenes content, compared to the extracts
from DP, because most of terpenes were
removed from cedar in previous steam
treatments (SP-130-160 and 130) as shown in
GC-MS chromatograms (Fig. 5). As a result, thechromatogram of extracts from SP-160-220
showed distinct peaks of CA and furans. Thus,
SP enables separate production of extracts richin terpenes and CA.

SP

100

4

SP-130

5

50
2

0
1

0.9

0.9

0.9

100

0.9

3
12
SP-130-160

5

50
0

4
12

Fig. 4 Yield of DCM extracts.

Figs. 5 and 6 show the composition of
extracts. Among GC-MS chromatograms of Fig.
5, CA was found only in SP-160-220 and DP250. The absence of CA in the extracts fromlignin supported our hypothesis that it was notderived from lignin. The result also indicatedthat steam and a temperature around 220°C
were necessary for cleaving the linkage holding
CA precursor. As shown in Fig. 6, extracts fromDP-130 and 160 consisted mainly of terpenes
because the temperature was too low for major
components in biomass to be pyrolyzed.
Pyrolysis of hemicellulose in biomass generally
becomes pronounced from around 180°C, where
pyrolysis of lignin also starts, although thereaction rate is much slower than that ofhemicellulose.9) Because the release of terpenes
was almost completed below 160°C, its portionin the extracts decreased with Tp, and, instead,the contribution of phenols and furansincreased. Furans were derived fromhemicellulose. Phenols included CA and ligninderived phenols. A large terpenes content in theextracts of DP-220 at water/biomass = 0

3

0

2
5
10
15
Water/biomass (SP-160-220)

100
Relative abundance (%)

Yield of extracts (wt%)

be derived from this pathway at high Tp. The
presence of pathway (c) is demonstrated by theincrease in yield with water/biomass ratio.
Different from DP, the yield of extracts in SP160-220 was hardly affected by water/biomass
ratio. In other words, a low water/biomass ratioof 2 sufficed for releasing compounds fromcedar treated by SP-130 and 130-160.

25

SP-160-220

6

2

50

4 5

1
0
100
50

4 5

DP-220(without steam)

12

7

0
2

100
50

DP-2501

7Lignin220

7

4

6

5

0
100
50

8

0
20

30

40
50
Retention time (min)6070Fig. 5 GC-MS chromatograms of DCM extracts obtained
from selected pyrolysis conditions. Water/biomass
ratio = 2. Major compounds: 1) furfural, 2) 2furanmethanol, 3) phyllocladene, 4) biformen, 5)
totarol, 6) CA, 7) guaiacol and 8) homovanillic acid.

Fig. 7 quantitatively shows the yield of CA in

26

Low Temperature Pyrolysis of Woody Biomass under Steam for Selective Production of Coniferyl Aldehyde

30

CA yield (wt%)

DP

80
60
40
20
0

220 130 160 190 220 250
Tp (water/biomass = 2)

100

0

5

10

15

80
60
40

0

2
5
10
15
Water/biomass (SP-160-220)

Fig. 6 Composition of DCM extracts (relative peak area ofcompounds identified in GC-MS analysis). See
Appendix for compounds contained in each category.

The yield and chemical composition ofresidual char are presented in Fig. 8. Glucan isderived mainly from cellulose. Xylan, galactan,

20

10

220 130 160 190 220 250
Tp (water/biomass = 2)

0

2

0.3

SP

Yield
Content

20

0.2
10

0.1

0.0

5

10

15

0

Water/biomass (DP-220)

30

OthersTerpenes
Phenols
FuransKetones

20

Yield
Content

0.1

LigninWater/biomass(DP-220)

SP

DP

0.2

0.0

LigninRelative peak area (%)

0.3

CA yield (wt%)

Relative peak area (%)

100

CA content in extracts (wt%)

arabinan, and mannan are derived fromhemicellulose.
Becauseacharacteristic
structure of hemicellulose in softwood is Oacetylgalactoglucomannan,21) a part of glucan
should be derived from hemicellulose. Others
include ash, extractives, and acetyl groups. The
yield decreased with Tp. It was little influenced
by water/biomass ratio because the proportionof structure, which was decomposed only bysupply of steam, in cedar was negligibly small
as shown in the yield of extracts (Fig. 4). It was
noteworthy that the majority of hemicelluloserelated sugars survived the pyrolysis understeam in any conditions even at 250°C. Thiswas contrary to our expectation that CA wasgenerated from LCC after the removal ofhemicellulose. The result rather showed apossibility that steam had an ability to cleave
the linkages of ferulic acid structure in LCC
with both hemicellulose and lignin, leaving thethree main components in cedar with little
alteration of their chemical structure. Such atrend is favorable for the multi-productstrategy, where terpenes and CA production
with SP under steam adds value to processes
valorizing the main components.

2
5
10
15
Water/biomass (SP-160-220)

0

CA content in extracts (wt%)

each pyrolysis. The trend generally agreed withthat observed in the yield of overall extracts(Fig. 4), showing the importance of Tp andsteam. An exception was that the yield of CA
increased with water/biomass ratio whereas
the yield of overall extracts was unchanged. As
a result, the content of CA, i.e., selectivity to CA,
increased with water/biomass ratio up to 26.5
wt%. The result indicated higher steam
concentration was effective for suppressing
secondary reactions of CA to be degraded into
other products. According to Table A1,
guaiacylacetone could be one of the derivatives
from CA since its proportion in extracts
decreased with water/biomass ratio, although
the trend was not remarkable. The highest CA
yield was 0.28 wt%, achieved by DP-250.
However, due to the inclusion of terpenes andenhanced pyrolysis by the high temperature of
250°C, CA content in extracts was only 8.8 wt%.
In this regard, SP-160-220 at water/biomass ≥10 was considered to be a better condition for
selectively producing CA. Overall, the result
confirmed that the formation of CA during
pyrolysis needed steam and a temperature ofaround 220°C, and that lignin was not thesource of CA.

Fig. 7 Yield of CA and its content in DCM extracts.

4.

Summary and Conclusion

This study showed a value-added aromaticcompound, CA, was selectively available from
low temperature pyrolysis of cedar under steam.
Different from a common source of aromatic

令和 4 年度

九州大学大学院総合理工学報告 第 44 巻 第 1 号

compounds generated during pyrolysis, CA wasconsidered to be derived from ferulic acidstructure in LCC. SP under steam produced
terpenes as a main product below 160°C and
CA at 160–220°C as a main compound in
extractives. The yield and content of CA were
up to 0.23 wt% and 26.5 wt%, respectively, in
SP. The treatment hardly altered the chemical
structure of a main portion of cedar. Therefore,
pyrolysis under steam is expected to be used asa pretreatment step for extracting terpenes and
CA to add value to the process of main
conversion of lignocellulose.

Yield and composition ofsolid residue (wt%)

100
DP

80
60
40
20
0

Raw 130 160 190 220 250
Tp (water/biomass = 2)

Yield and composition ofsolid residue (wt%)

100
80

5

10

15

Water/biomass(DP-220)

SP

OthersLigninMannanArabinan
Galactan
Xylan
Glucan

60
40
20
0

0

2
5
10
15
Water/biomass (SP-160-220)

Fig. 8 Yield and composition of solid residue.

Acknowledgments
This work was financially supported by
MEXT/JSPS
KAKENHI
Grant
No.
JP21H04632/JP20K05210 and the CrossMinisterial Strategic Innovation Promotion
Program (SIP) “Technologies for smart
bioindustry and agriculture” administered bythe
Bio-oriented
Technology
Research
Advancement Institution, National Agriculture
and Food Research Organization (NARO). The

27

authors
gratefully
acknowledge
theCooperative Research Program of “Network
Joint Research Center for Materials andDevices”. F.W. thanks the China ScholarshipCouncil (Grant number 201806420016) for
financial support.
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Appendix
Table A1 Relative peak area (%) of compounds identified in extracts by GC-MS.
Compounds
Ketones
2,3-butanedione

LigninTp (°C)
220
5.9
3.7

DP, water/biomass = 2
Tp (°C)
130 160 190 220 250
0.1
5.7
6.0
5.1
7.9
0.1
5.7
4.2
1.2
1.5

DP, Tp = 220°C
Water/biomass
0
5
10
15
0.0
3.5
2.7
2.5
1.9
1.4
1.3

SP, 220°C
Water/biomass
2
5
10
15
7.4
5.9
4.1
3.9
1.0
0.9
1.5
1.4

28

Low Temperature Pyrolysis of Woody Biomass under Steam for Selective Production of Coniferyl Aldehyde

Table A1 Continued.
Compounds
2,3-pentanedioneacetolacetoin2-oxobutanolacetol acetate
2-cyclopentene-1,4-dione
2-hydroxy-2-cyclopentenone
3,4-dimethylcyclopent-2-enone
Furansfurfural2-furanmethanol
acetylfuran
5-methylfurfuralbutyrolactone2(5H)-furanone
methyl 3-furoate
4-methyl-2(5H)-furanone(5S)-5-(hydroxymethyl)oxolan-2-one
5-acetyloxolan-2-onehydroxymethylfurfuralPhenols
phenolguaiacolp-creosol
4-ethylguaiacol
4-vinylguaiacol
2-methoxy-3-allylphenol
syringolisoeugenol
vanillincerulignol
4-t-butylcatechol
guaiacylacetone
coniferolhomovanillyl alcohol
vanillacetic acidconiferyl aldehyde
Terpenoids
maltol(-)-bete-elemene
cedr-8-ene
2-isopropenyl-4a,8-dimethyl-1,2,3,4,4a,5,6,7
octahydronaphthalene
α-muurolene
δ-cadinene
isoledene
1,2,3,4,4a,7-hexahydro-1,6-dimethyl-4-(1methylethyl)-naphthalene
valencencalamenene
isolongifolene, 4,5,9,10-dehydroα-calacorene
3,4-dehydroionene
elemolγ-elemene
2,5,8-trimethyltetralin
naphthalene, 1,2,3,4,6,8a-hexahydro-1isopropyl-4,7-dimethylγ-eudesmol
T-muurolol
torreyolα-cadinol
juniper camphor
apo-12-lycopenal
isophyllocladen
1-oxaspiro[2.5]octane, 5,5-dimethyl-4-(3methyl-1,3-butadienyl)atiserene
1,5-cyclooctadiene, 3,4,7,8-tetrakis(1methylethylidene)cembrene
ethyl cholate
o-methylpodocarpinol
androstan-17-one, 3-ethyl-3-hydroxy-, (5α)phyllocladene

LigninTp (°C)
220
0.9
0.4
0.1
0.8
3.2
0.4
0.1
1.6
1.1
89.4
4.0
60.7
0.6
1.9
0.8
0.2
0.2
0.3
3.7
0.1
3.3
1.2
0.7
11.5
0.0
-

DP, water/biomass = 2
Tp (°C)
130 160 190 220 250
0.6 <0.1 0.2
1.4
1.9
0.6
0.3
0.2
0.2
0.5
0.6
0.1
0.2
0.2
0.1
0.2
0.3
1.4
2.7
0.5
1.1
2.5 10.1 13.2 13.2
0.7
1.0
3.8
3.0
2.4
0.2
0.9
4.4
6.7
7.0
0.1
0.1
0.1
0.1
0.2
0.9
0.5
0.6
0.1
0.2
0.2
0.3
0.5
0.1
0.2
0.6
1.0
1.4
0.2
0.2
<0.1 0.1
0.3
0.1
0.1
0.1
0.2
1.1
0.8
3.0
2.4
9.6 27.5 33.9
0.5
0.4
0.8
0.1
0.3
0.4
1.1
2.6
0.2
0.7
0.1
0.1
0.1
0.1
3.0
0.7
<0.1 0.4
0.8
3.2
0.2
0.4
0.8
1.7
1.9
0.2
0.6
0.9
0.6
2.6
1.2
3.5
5.6
4.7
0.3
0.9
1.2
1.6
2.9
2.8 15.2 10.8
93.7 88.4 72.1 51.2 39.1
0.3
0.6
0.1
0.7
0.2
0.2

DP, Tp = 220°C
Water/biomass
0
5
10
15
0.3
0.1
0.1
0.3
0.2
0.2
0.1
0.1
0.1
0.2
0.1
0.1
0.1
0.1
0.1
0.2
0.1
0.1
0.4
0.5
0.5
4.9
9.6
8.6
7.9
<0.1 3.4
2.2
2.0
3.5
4.2
4.3
4.0
<0.1 <0.1 <0.1
0.7
0.5
0.3
0.3
0.4
0.2
0.2
0.2
0.2
0.7
0.7
0.6
0.1
0.2
0.1
<0.1 <0.1 <0.1
0.1
0.1
0.1
<0.1 <0.1 <0.1
0.1
0.3
0.5
0.5
9.6 31.0 34.6 39.8
0.3
0.3
0.2
0.2
0.5
0.8
0.7
0.6
0.2
0.1
0.1
1.3
0.3
0.7
0.7
0.6
0.3
1.5
1.7
1.5
<0.1 0.7
0.6
0.5
4.3
6.3
5.9
5.4
0.1
0.2
0.6
0.5
1.2
1.6
1.4
2.5 19.2 22.6 28.7
84.7 53.0 51.7 47.6
0.1
0.1
0.1
0.7
0.1
0.1
0.1
0.2
0.2
0.2
0.2

SP, 220°C
Water/biomass
2
5
10
15
0.1
0.6
0.1
0.1
2.8
1.4
0.8
0.8
0.4
0.3
0.2
0.2
0.7
0.5
0.3
0.3
0.2
0.2
0.2
0.1
0.2
0.2
0.2
0.1
2.0
1.7
0.9
0.9
20.1 16.4 15.1 14.1
4.4
4.0
3.9
3.7
11.0 8.4
8.1
7.6
0.1
0.1 <0.1 <0.1
0.6
0.5
0.5
0.5
0.4
0.3
0.3
0.3
1.4
1.3
1.1
0.9
0.3
0.2
0.1
0.1
0.1
0.1
0.1
0.4
0.3
0.1
0.1
0.1
0.1
0.1
0.1
1.6
1.2
0.8
0.7
32.5 35.7 38.8 42.4
0.5
0.4
0.4
0.4
1.2
1.0
1.1
1.1
0.3
0.2
0.2
0.2
0.9
0.7
0.8
0.8
1.5
1.4
1.8
1.7
0.6
0.7
0.7
0.7
0.3
0.3
5.8
5.8
4.4
4.2
0.2
0.2
0.3
0.3
1.2
1.6
2.1
2.0
20.3 23.6 26.6 30.9
35.9 38.0 36.6 34.4
1.4
0.2
0.3
0.3
0.1
0.1
0.1
0.1
0.7
0.2
0.1
0.1

-

-

-

0.4

0.8

0.5

0.9

0.8

0.7

0.7

1.1

0.9

0.6

0.5

-

0.3
0.8
-

0.3
0.4
-

1.0
0.8
0.1

1.8
0.8
0.2

1.8
0.6
0.3

2.1
0.2

1.9
0.9
0.2

1.7
0.8
0.2

1.6
0.8
0.2

2.5
1.1
0.3

2.3
1.0
0.2

1.9
0.8
0.2

1.8
0.8
0.2

-

0.2

0.2

0.6

0.5

0.4

0.8

0.6

0.6

0.5

0.7

0.6

0.6

0.6

-

1.2
0.8
2.1
0.5
1.1
0.4
-

0.9
0.9
0.8
0.2
0.4
0.2
-

1.5
0.6
1.4
0.6
0.3
0.1

0.1
1.8
0.5
1.0
0.6
0.3
-

1.4
0.3
0.6
0.6
0.3
-

0.1
2.3
0.7
1.6
0.9
0.3
0.1

0.1
1.9
0.4
1.1
0.6
0.3
-

0.1
1.9
0.5
1.0
0.6
0.3
0.1

0.1
1.7
0.3
0.9
0.5
0.4
0.1

0.1
2.4
0.5
1.4
0.5
0.3
0.2

0.1
2.1
0.5
1.0
0.5
0.3
0.1

0.1
2.2
0.5
0.9
0.4
0.3
0.1

0.1
2.0
0.3
0.8
0.4
0.4
0.1

-

4.0

1.7

-

2.8

1.8

2.9

2.4

2.4

2.2

2.1

1.9

1.6

1.5

-

0.7
0.8
1.3
0.4
1.5
3.4
3.5

0.3
0.2
0.4
0.1
0.5
0.9
2.0

0.6
1.2
0.3
0.7
2.2
2.2

0.7
1.2
0.3
1.9
2.4

0.7
0.4
0.7
0.2
0.5
1.1
2.1

0.9
0.9
0.4
0.5
2.5
4.0

0.8
0.9
2.2
2.6

0.7
0.9
0.3
1.9
3.0

0.7
0.9
0.3
1.8
2.8

0.8
1.2
0.2
1.9
1.8

0.8
0.9
0.3
2.0
2.3

0.8
0.9
0.2
2.1
2.9

0.7
0.9
0.2
2.0
2.7

-

2.1

0.7

1.6

2.0

-

2.5

2.2

2.2

2.0

2.0

2.0

2.4

2.3

-

0.8

0.4

-

-

0.7

-

-

-

-

-

-

-

-

-

3.3

3.1

3.5

2.0

1.2

4.5

1.8

1.7

1.6

1.3

1.4

1.2

0.9

-

0.9
1.4
1.9
9.5

0.4
1.2
3.9

0.3
0.7
2.2
-

0.2
0.4
1.1
-

0.2
1.1
0.6
0.5

0.3
0.4
1.0
-

0.3
0.4
1.2
-

0.3
0.4
1.1
-

0.3
0.4
1.0
-

0.2
0.2
0.8
-

0.3
0.3
0.9
-

0.2
0.3
0.8
-

0.2
0.5
0.7
-

令和 4 年度

九州大学大学院総合理工学報告 第 44 巻 第 1 号

29

Table A1 Continued.
Compounds
17-oxoandrosta-5,7-dien-3-yl acetate
biformenandrosta-5,7-diene, 4,4-dimethyltotarol
14-isopropylpodocarpa-8,11,13-triene-7,13diol
OthersLigninTp (°C)
220-

DP, water/biomass = 2
Tp (°C)
130 160 190 220 250
1.8
1.3
23.5 27.4 21.3 12.2 8.4
4.4
3.2
1.5
18.7 29.8 23.4 11.7 6.3

DP, Tp = 220°C
Water/biomass
0
5
10
15
26.6 14.6 14.3 13.2
21.7 11.1 10.7 9.8

SP, 220°C
Water/biomass
2
5
10
15
4.3
8.1
7.1
6.7
4.1
4.7
4.9
4.6

-

2.2

6.6

4.6

3.1

2.7

4.5

3.3

3.0

2.7

1.6

2.0

2.0

1.9

1.5

2.1

0.9

2.1

3.1

5.9

0.7

2.9

2.3

2.2

4.1

4.0

5.4

5.2