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Title

Properties of bio‑oil generated by a pyrolysis offorest cedar residuals with the movable Auger‑
type reactor

Author(s)Nishimura, Shun; Miyazato, Akio; Ebitani, Kohki

Citation

AIP Conference Proceedings, 1709: 020026‑1‑
020026‑8

Issue Date

2016‑02‑01

Type

Conference Paper

Text version

publisher

URL

http://hdl.handle.net/10119/13508

RightsCopyright 2016 American Institute of Physics.
This article may be downloaded for personal use
only. Any other use requires prior permission of
the author and the American Institute of Physics.
The following article appeared in Shun Nishimura,
Akio Miyazato, Kohki Ebitani, AIP Conference
Proceedings, 1709, 020026 (2016) and may be foundat http://dx.doi.org/10.1063/1.4941225

Description

Japan Advanced Institute of Science and Technology

Properties of bio-oil generated by a pyrolysis of forest cedar
residuals with the movable Auger-type reactor
Shun Nishimura1, Akio Miyazato2 and Kohki Ebitani1,*
1

School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa
923-1292, Japan.

2

Nanotechnology Center, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 9231292, Japan.
*

K. Ebitani: ebitani@jaist.ac.jp

Abstract. Our research project has developed the new movable reactor for bio-oil production in 2013 on the basis of Augertype system. This package would be a great impact due to the concept of local production for local consumption in the hilly
and mountainous area in not only Japan but also in the world. Herein, we would like to report the properties of the bio-oil
generated by the developing Auger-type movable reactor. The synthesized bio-oil possessed C: 46.2 wt%, H: 6.5 wt%, N:
0.5 wt%, S: <0.1 wt%, O: 46.8 wt% and H2O: 18.4 wt%, and served a good calorific value of 18.1 MJ/kg. The spectroscopic
and mass analyses such as FT-IR, GC-MS, 13C-NMR and FT-ICR MS supported that the bio-oil was composed by the finemixtures of methoxy phenols and variety of alcohol or carboxylic acid functional groups. Thus, it is suggested that the biooil generated by the new movable Auger-type reactor has a significant potential as well as the existing bio-oil reported
previously.
Keywords. Auger-type movable reactor, cedar pyrolysis, bio-oil, FT-ICR MS.

INTRODUCTION
Fast pyrolysis of biomass resources towards liquid (called as pyrolysis oil or bio-oil) has much attraction as aneffective tool for productions of liquid fuels and derived feedstocks for chemical materials. Since the product bio-oil
was yielded up to 80 wt% on dry feed via a fast pyrolysis, this liquefaction approach is highly anticipated by many
researchers. They have been developing the numerous system for fast pyrolysis affording to the bio-oil to meet thevariety of biomass resources such as straw, olive pits, nus shells, miscanthus, sorghum and so on, nearly 100 types ofbiomass have been tested [1-4]. Predominantly, most technologies for the pyrolysis of wood have been studied on a
static plant with a large scale in order to treat a large amount of biomass resources in a day, however, the plants cannot
be moved out from the factory. The development of movable pyrolysis reactor was rarely reported in the world.
In our research project, we focused on the development of a compact/movable reactor package for bio-oil
production. Especially, in the hilly and mountainous area in Japan, the unutilized resources of forest scraps and wood
waste were kept intact a lot in the area, because no human power or high costs (low benefits) was ensured to collectsuch worthless resources into the business place. If the movable pyrolysis reactor could be transported into andoperated in such field, ex. the timber basin area close to the mountain, the unutilized resources would be upgradedtowards the bio-oil, useful energy and chemical resources, with more effective manner. This futural approach will

The Irago Conference 2015
AIP Conf. Proc. 1709, 020026-1–020026-8; doi: 10.1063/1.4941225© 2016 AIP Publishing LLC 978-0-7354-1356-6/$30.00

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serve not only for encouragements in the utilization of unharnessed biomass resources but also for generation of newlife-style and energy cycles in accordance with the bio-refinery.
In a recent few years, our research project has been developing the movable Auger-type reactor for bio-oil
production in the mountain area. Herein, we would like to report and discuss the properties of the bio-oil generated
by the new movable Auger-type reactor.

EXPERIMENTAL
Production of the bio-oil by movable Auger-type reactor
The Japanese cedar chips excluding bark (2-3 mm, 8.21% H2O) was fed into with 45 kg/h rate and pyrolyzed at450-500 oC in the Auger-type reactor with iron shots (SINTOKOGIO Ltd.; SB-20, φ = 1.4-1.7 mm). The produced
bio-oil was collected by the condenser composed with a scrubber and mist collector attached with the reactor (Figure1) [5-6].
Japanese cedar(2-3 mm)Char

Pyrolysis oil
䠄Bio-oil)

Condenser

෭༷ሪ
Iron shot(1.4-1.7 mm)(a)

Pyrolyzer(450-500oC)

Gas

(b)

FIGURE 1. The developing movable Auger-type reactor; (a) overview on a truck bed and (b) schematic flow in the reactor.

Physical properties analysis
Elemental analysis for C, H, N and S was performed by the Vario EL3 elemental analyzer (Elementar). The
reduction tube, CO2 column, SO2 column, and H2O column was elevated to 850 oC, 100 oC, 210 oC and 150 oC,
respectively. 5 mg of bio-oil was sealed within the Tin capsule (0.05 mL vol.), and introduced into the furnace at 1150
oC. Sulfanilic acid (Merck Millipore) was used as the standard for C: 41.61wt%, H: 4.07wt%, N: 8.09wt%, and S:
18.50 wt%.
Water content was determined by the Karl Fischer (KF) moisture titration with a volumetric titration mode (MKA610, Kyoto Electronics Manufacturing Co., LTD.). HYDRANAL-KetoSolver (Fluka) and HYDRANAL-Composite
5K (Fluka) was used as solvent and titrant, respectively. 2.0 g of bio-oil was applied at a time for KF analysis.
NaOH titration was attempted to use for acidity test. 1.0 g of bio-oil was dispersed into 50 ml of pure water in a
conical beaker, and then neutralized by a 0.500 N of NaOH aqueous solution till the pH approaching to the range of
8.30-8.50.
Higher heating value (HMV) of the bio-oil was assigned by a calorific meter (IKA C200). 0.4 g of bio-oil wassealed in 0.118 g of gelatin capsule (18759 J/g) with the firework fuel of 0.0318 g of paraffin films (46619 J/g), andthen the ignition was occurred under the pressurized O2 gas (30 bar). For standard correction, 1.0 g of benzoic acidtablet (26460 J/g) was also measured.
A cone-plate type viscometer (TOKI SANGYO TVE-35H) attached with a 0.8o×R24 cone and a D-52 pH meter(HORIBA) was used for the measurement of viscosity and pH value, respectively.

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Spectroscopic and MS analysis
FT-IR (ATR) was obtained by a spectrum 100 meter (ParkinElmer) attached with the ATR accessary of a ZnSe
crystal plate. The 123 scans of IR spectra were performed in the range of 4000-400 cm-1 with 4 cm-1 resolution. The
characteristic peaks were identified by following literatures [7-8].
13
C-NMR spectrum was examined by an Avance III 400 spectrometer (400 MHz, Bruker BopSin Inc.) at room
temperature. Methanol-d4 (99.8 atm% D, Acros Organics) was used as solvent. The 5,000 numbers of scan wereoperated to brash up the S/N ratio.
For GC-MS analysis (Shimadzu QP-5000), the produced bio-oil was resolved in methanol to ca. 50 μl/ml, and a
0.1 μl of the sample was analyzed using a commercial NEUTRA ND-5 capillary column (GL Science, 0.25 mm ID ×30 m) under He gas flow (99.9999% purity, 20 ml/min). The injection temperature was 250 oC. The temperature of
GC column oven was conducted to the program: an initial 50 oC for 5 min, a ramp to 250 oC at a rate of 5.0 oC/min,and a constant 250 oC for 15 min. Ionization of the sample was treated by the electron ionization (EI) method. A fullMS spectrometry scan was acquired in the range of m/z = 35-700 at a rate of 0.5 s per scan. The GC chromatographic
peaks were characterized by the CLASS-5000 library (Shimadzu ver. 2.22).
FT-ICR MS (Bruker Daltonics Inc., SolariX) was obtained by using a 9.4 T superconducting magnet. The diluted
samples were prepared by mixing the bio-oil samples and methanol (1 μl/ml). Oleic acid (C18H33O2; 281.24860 Da(Monoisotopic) was used as an internal standard for adjustment of the m/z axis in MS spectrum. The electrosprayionization (ESI) method at 4.5 kV was applied for negatively-ionization of the sample. A 2 Mega-byte data set (3.84
M points) was acquired in the range of m/z = 100-1200. A number of 5 scans of FT-ICR data sets were added toenhance the S/N ratio. From the obtained negative-ion FT-ICR MS spectrum, the estimated composition formulas
determined by the actual m/z value below ±1.0 ppm error were listed up as the expected compounds (CDHEOFNG) in
the sample.

RESULTS AND DISCUSSIONS
Physical properties
The physical properties of the produced bio-oil are listed in Table 1. The elemental analysis indicated that asproduced bio-oil contained C: 46.2 wt%, H: 6.5 wt%, N: 0.5 wt%, S: <0.1 wt% (below limit), and O: 46.8 wt%. The
pH value was 2.60. The NaOH titration led to the acidity of 4.66 (NaOH g/ 100 g oil) corresponding to the 7.0 wt%
of acetic acid (if these were derived from acetic acid all). As is usual in bio-oil properties, high oxygen content, nosulfur production, and acidic pH were also detected in our product.

TABLE 1. Physical properties of the as-prepared bio-oil.
Indexes

C
H
N
S
O
pH
H 2O
Acidity (NaOH g/ 100 g oil)
Viscosity
Kinetic viscosity
Calorific value

ValuesNote

46.2 wt%
6.5 wt%
0.5 wt%<0.1 wt%
46.8 wt%
2.60
18.4 wt%
4.66
0.467 Pa•s (at 25 oC)
0.019 Pa•s (at 50 oC)
17 cSt (at 50 oC)
18.1 MJ/kg (Higher)
16.8 MJ/kg (Lower)

Limit value: 0.1 wt%
Limit value: 0.1 wt%
Limit value: 0.1 wt%
Limit value: 0.1 wt%
Difference of CHNS values

Limit value: 3.33 mPa•s

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The viscosity was 0.467 Pa•s measured at 25 oC and 0.019 Pa•s at 50 oC. When the specific gravity of the bio-oil
was set as 1.1 g/cm3 tentatively, the kinetic viscosity was estimated to 17 cSt at 50 oC. This value was superior thanthat of the heavy fuel oil A grade based on the Japan standard (JIS K 2205-1991) (< 20 cSt). The high calorific value
was 18.1 MJ/kg which was approximately half value of the conventional fuel oils such as gasoline, light diesel oil andheavy fuel oil (42-45 MJ/kg). Since the latent heat of the contained/produced water produced ca. 1.33 kJ/g heat, thelower calorific value was calculated to be 16.8 MJ/kg.

Solubility test
To select the solvent having nice affinity for bio-oil, several solvents (4 ml) were mixed with the bio-oil (1 ml),and the solubility was tested. The Figure 2 shows the photograph for the mixed solvent after shaking. The water madeclouded brownish yellow suspension with non-soluble bio-oil precipitation (ii) whereas the hexane (iv) and petroleum
ester (viii) were hardly mixed with the bio-oil at all. From the observation in the case of benzene (vii), the bio-oil
supposedly included two phase of soluble (light brownish yellow color) and insoluble (dark brown) in benzene. The
cases of AN (v) and THF (vi) were visualized that almost all bio-oil was miscible, however a few precipitants and/or
extractions were observed at the bottom of the glass tube. The MeOH was only the solvent nicely mixable with biooil, homogeneously (iii).

(i)

(ii)

(iii)

(iv)

(v)

(vi)

(vii)

(viii)FIGURE 2. Solubility tests of the bio-oil in (i) None (itself), (ii) Water, (iii) Methanol, (iv) Hexane,(v) Acetonitrile, (vi) Tetrahydrofuran, (vii) Benzene, and (viii) Petroleum ester.

FT-IR spectroscopy
Figure 3 shows the FT-IR spectrum of the bio-oil. There is a large/broad peak around at 3000-3800 cm-1 which
attributed to the O-H stretching vibration in alcohol, phenol or water. Because the large quantity of water was detectedin the bio-oil (18.4 wt%), it will be mainly originated from co-existence water molecule. The peak at 1713 cm-1 was
assigned to the stretching vibration of carboxylic acid (COOH) or ketone (C=O). The C-H bending vibration in alkane
and O-H bending/C-O stretching vibrations in alcohols or phenol were detected at 1363-1452 cm-1. The latter would
be also assigned at 1033-1073 cm-1. The peaks appeared at 1270-1235 cm-1 would be derived from ester in arylalkyl
group (aryl-O-C). The multiple connected C-C stretching mode in aromatic compounds and C-H bending vibration in
substituted benzenes were at around 1600-1650 cm-1 and 860 cm-1, respectively. Though it is a large quantity at 1514
cm-1, it seems to be difficult to estimate its derivations: i.e. a lot of candidates were proposed. Possibility of surfer
compounds such as sulfuric acid (R-SO3H at 1210-1150 cm-1, 1060-1030 cm-1 and 650 cm-1) and sulfoxide (R-SO-R
at 1070-1030 cm-1) were negligible, because of the result in elemental analysis (vide supra). The nitro compounds
such as amide and imide are not listed up too in the sentences because of low contents (N: 0.5 wt%).
These results indicated that the bio-oil was composed by various aromatic alcohols and variety of alcohol orcarboxylic acid functional groups.

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1000

800

2064

1200

860
812

1400

1124
1073
1049
1033

1600

1800

1270
1235

1514
1452
1429
1363

C-OH

CxHy, C-OH
3500

3255

3383
4000

1713
1647
1602

Absorbance /a.u.

-OH

3000

2500

2000

Wavelength /cm

1500

1000

500

-1

FIGURE 3. FT-IR(ATR) spectrum of the bio-oil with indexes of the estimated functional structure.

13C-NMR spectrum

The 13C-NMR spectrum of bio-oil is shown in Figure 4. The x-axis (chemical shift) was adjusted by the solvent(MeOH-d4; 49.00 ppm) [9]. The indexes in the spectrum were assisted by the previous report for bio-oil analysis [10].
The values were calculated with an integration of the area in the range of 215-163 ppm (carbonyl, C: 15.94%), 163110 ppm (aromatic, C: 34.36%), 110-84 ppm (carbohydrate, C: 12.65%), 84-53 ppm (methoxy/hydroxyl, C: 19.47%)
and 42-0 ppm (alkyl carbons, C: 17.58%) except for solvent in 53-42 ppm (MeOH). It is clearly suggested that thearomatic carbon was the major component (C: 34.36%). According to the another paper [11], aromatic C-O, aromatic
C-C, and aromatic C-H would afford signals at 166.5-142.0 ppm, 142.0-125.0 ppm, and 125.0-95.8 ppm, respectively.
Therefore, aromatic C-O and aromatic C-H accounted a large quantity among aromatic compounds in the bio-oil. The
metoxy/hydroxy O-C-H group, carbonyl group and alkyl carbons were detected as the similar content value of C value(15-20%).
MeOH

Carbonyl

Aromatic

Carbohydrate Methoxy
Hydroxy
CxHy-OCH3, -COH

Alkyl carbons-CH3, -C2H5

FIGURE 4. 13C-NMR spectrum of the bio-oil produced by Auger-reactor with the expected structure.

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GC-MS analysis

Intensity /a.u.

To further examine the structure of the compounds in bio-oil, GC-MS was measured. Figure 5 shows GC chart ofthe bio-oil. The expected structure by MS analysis in the top ten peaks from the largest area were also described in
the Figure 5. As shown with the orange dialogs, phenol, catechol, and methoxy phenols were the main compounds inthe bio-oil. Some furan derivatives, ketone and aldehyde were also detected in top 10 materials (blue dialogs). The
large architectonics of C20H30O (black dialog) was detected at 46.43 min. The wood generally consists of cellulose(40-50%), hemicellulose (20-40%), lignin (18-35%) and others (1-4%) [12]. Therefore, cellulose and hemicellulose,
comparative easily-decomposable sources under pyrolysis, will convert into gases or furans and aliphatic
aldehydes/carboxylic acids detected in bio-oil, whereas the tough lignin was partially decomposed and a lot of
methoxy phenols were remained in bio-oil. These observations agreed well with the previous reports for bio-oil
analyses [13-14].

Retention time /min

FIGURE 5. GC chart of the bio-oil produced by Auger-reactor with the top 10 expected structure by MS spectrum.

FT-ICR MS analysis
Recently, it has been reported that the FT-ICR MS technique well serves the detailed information to characterize
extremely complex mixtures such as heavy oil and bio-oil [15-16]. Thus, we attempted to use the FT-ICR MS for the
bio-oil generated by the new Auger-type reactor. Figure 6 shows the negatively-ion FT-ICR MS broadband spectrumof the bio-oil. On this time, two projecting peaks were observed at m/z = 129.01925 and 143.0349. For instance, thesewere assigned to the composition formula of C5H5O4 and C6H7O4, respectively, by the accurate mass. In total, the 720
expected compounds with CDHEOFNG formula (s1.0 ppm error) were assigned in the sample. The carbon number andoxygen number counted up based on each given compound (CDHEOFNG formula) were described as 2D and 3D poltsin Figure 7. The cohesive distributions exhibited the average around at C = 14-15 and O = 8-9. The 3D polts indicatedthat the main component in the bio-oil had a linearity between carbon and oxygen: i.e. the CDHEOFNG with a larger
carbon number also possessed a larger oxygen number. Therefore, it is suggested that the Auger-type reactor served
a comparatively fine bio-oil in quality.

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129.01925
C5H5O4

Relative Abundance

259.04592
C10H11O8
207.05100
C7H11O7

323.09841
C12H19O10

143.0349
C6H7O4

䢴䢲䢲

200

400

䢴䢷䢲

䢵䢲䢲

600

䢵䢷䢲

800

䢶䢲䢲

1000

䢶䢷䢲

1200

m/z

Frequency

FIGURE 6. Negative-ion FT-ICR MS broadband spectrum of the bio-oil with examples for the estimated composition formula.

0

10
20
30
Carbon number in a compound/numberFrequency

(a)

0

5
10
15
Oxygen number in a compound/number(b)(c)
FIGURE 7. Result of FT-ICR MS analysis; (a) oxygen, (b) carbon, and (c) oxygen-carbon number contributions in
the estimated compounds in the bio-oil.

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SUMMARY
We have been developing the new movable Auger-type reactor for bio-oil production. The produced bio-oil
possessed good calorific value (18.1 MJ/kg) and flow property (17 cSt at 50 oC). Physical, spectroscopic and mass
analyses indicated that the bio-oil was clean, no sulfur and low nitrogen contents, and mainly composed by methoxy
phenols and variety of alcohol or carboxylic acid with fine mixture. The developing movable Auge-type reactor forbio-oil production would be a strong candidate for bio-refinery technology.

ACKNOWLEDGMENTS
This research has been performed under a commissioned project by the Ministry of Agriculture, Forestry and
Fisheries (MAFF), Japan. The authors appreciate our research members of Mr. S. Kitano and Mr. H. Shimizu inMaywa Co. Ltd., Dr. Y. Suzuki and Dr. S. Hosokai in Advanced Industrial Science and Technology (AIST), Prof. Dr.
S. Ted Oyama and Dr. A. Takagaki in The University of Tokyo.

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