5686 r2010 American Chemical Society pubs.acs.

org/EF
Energy Fuels 2010, 24, 56865695
:
DOI:10.1021/ef1009605
Published on Web 09/21/2010
Deoxygenation of Bio-oil during Pyrolysis of Biomass in the Presence
of CaO in a Fluidized-Bed Reactor
Yuyu Lin, Chu Zhang, Mingchuan Zhang,* and Jian Zhang
School of Mechanical Engineering, Shanghai Jiaotong University, Shanghai 200240, China
Received February 3, 2010. Revised Manuscript Received August 30, 2010
The direct deoxygenation effect of CaO on bio-oil during biomass pyrolysis in a fluidized-bed reactor
was studied. Bio-oils were produced from white pine in the presence and absence of CaO at 520 C and a
carrier gas flow rate of 50 L/min (standard temperature and pressure). The results showed that the oxygen
content of the organic components in the bio-oils was 39, 39, 39, 36, 32, and 31 wt % for white pine alone
and white pine accompanied with CaO at CaO/biomass mass ratios of 1, 2, 3, 4 and 5, respectively. At a
CaO mass ratio of 5, the relative reduction of oxygen content in the bio-oil reached 21%. Detailed gas
chromatography-mass spectrometry analysis showed that the relative abundances of high oxygen content
laevoglucose, formic acid, and acetic acid were highly reduced by CaO, indicating direct fixation of
the active quasi-CO
2
intermediates produced during biomass pyrolysis. Furthermore, the relative
abundances of furfural, furfuryl alcohol, etc., mainly derived from dehydration reactions, all increased,
showing that CaO addition could also catalyze dehydration reactions. X-ray diffraction and Fourier
transform infrared analyses of the solid residues prepared by a thermal balance confirmed the direct
fixation of the active quasi-CO
2
intermediates and showed that some organic calcium salts appeared at
350 C, which would decompose below 400 C to form easily regenerated CaCO
3
. This further confirmed
the feasibility of CaO recycling for in situ deoxygenation of bio-oil.
1. Introduction
Increasing concerns over energy security and global climate
change have recently led to an explosion of interest in biomass
energy use.
1,2
In comparison to other usages of biomass, pyrol-
ysis toproduce bio-oil is nowconsideredtobe anadvancedand
promising methodology. However, rawbio-oil usually has very
poor fuel properties, such as high oxygen content, high instabil-
ity, lowcalorific value, highviscosity, andhighcorrosiveness.
3-5
Refining and subsequent purification of the raw oil increase
the production cost and greatly reduce the efficiency of energy
use.
6-8
In work on the effect of alkali and alkaline earth metals on
the product distribution from biomass pyrolysis, Liao et al.
9
discovered that Ca
2
could strongly catalyze the dehydration
reaction in the pyrolysis process. When 2.5 wt % of Ca
2
was
impregnated in cellulose fibers, the water content of the liquid
product increasedby more than10 wt %andthe quality of the
bio-oil was improved. Consequently, modifications to in situ
pyrolysis may be a way toimprove the quality of bio-oil. There
have been several reports on using CaO to remove CO
2
from
the syn-gas produced by coal or biomass gasification.
10-13
Meanwhile, Khan found that a relatively high-quality liquid
fuel with low sulfur, low oxygen and low viscosity could be
produced from coal pyrolysis in the presence of CaO.
14
Yeboah et al. found that calcined dolomite (MgO CaO)
decreased tar yield with some oxygen removal and a modest
increase in the H/C ratio during fluidized-bed (FB) pyrolysis
of coal.
15
Zhuet al. reportedthat the H/Cratiointar increased
and the (ONS)/Cratio decreased in coal pyrolysis in the
presence of CaO.
16
These observations indicate that, in addi-
tion to absorbing CO
2
in the gas phase, CaOcan also fix CO
2
-
like substances directly in the liquid product of coal pyrolysis.
If it was also the case for biomass pyrolysis, the latter, viz.
direct fixation of CO
2
-like substances in the liquid, would be a
superior route for deoxygenation in the biomass-to-liquid
(BTL) conversion process.
On the basis of these considerations, a tentative scheme for
deoxygenation in bio-oil production by fast biomass pyrolysis
with CaO recycle was proposed by the authors.
17
Preliminary
*To whom correspondence should be addressed. E-mail: mczhang@
sjtu.edu.cn.
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K. Energy Fuels 2010, 24 (2), 13801388.
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Eng. 2009, 29 (5), 492496 (in Chinese).
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DOI:10.1021/ef1009605 Lin et al.
studies carried out by the authors on the pyrolysis of biomass
with CaO in a thermal balance and in a drop-tube pyrol-
yzer
17,18
indicated that CaO could extract and fix some active
quasi-CO
2
intermediates directly by semi-liquid to solid con-
tact rather than via the very slow gas-solid reaction. In this
study, a small FB reactor and the related oil-production
system were constructed and a series of experiments were
carriedout toexplore the deoxygenationeffect andthe mecha-
nism of CaO addition. Besides, X-ray diffraction (XRD) and
Fourier transform infrared (FTIR) analyses of the solid
residues from biomass pyrolysis with CaO in a thermal bal-
ance were carried out to obtain more evidence regarding the
mechanism.
2. Experimental Section
2.1. Materials. A white pine powder of 50-100 m was used
as the biomass feed material. CaOused was of commercial grade
(>95% purity), with particle sizes less than 50 m for the FB
experiments, and of analytical grade (>98% purity), with the
same particle size for the preparation of the solid residue. The
white pine powder was dried for 10 h at 105 C and then mecha-
nically mixed with CaO before feeding. Six mixtures with
different mass ratios, R, of CaO/white pine were used as feeds:
R = 0 (white pine alone), 1, 2, 3, 4, and 5. The proximate and
ultimate analyses of the white pine are given in Table 1.
2.2. Experimental Equipment. Figure 1 shows the FB experi-
mental apparatus and bio-oil system. The apparatus was mainly
composed of a feeding system, an electrically heated FBreactor,
and a filter-cooling system. The feeding system consisted of a
screw feeder driven by a speed-controllable direct-current (DC)
motor and a feeding pipe with a water-cooling jacket to avoid
pyrogenation and caking within the pipe during biomass feed-
ing. The FB reactor was heated by a 3 3 kW tubular electri-
cal furnace. SCR temperature controllers and fast-response
armored thermocouples were used to measure and control the
temperatures of each part of the reaction system. The FB
reaction pipe was made of 65 5 mm thermostable stainless
steel with a total height of 1600 mm, of which 600 mmwas below
the air distribution plate. The lower part was filled with thermo-
stable stainless-steel screens of 200 mesh, working as the pre-
heater of the reactor. The air distribution plate was covered by a
stainless-steel screen of 800 mesh (18 m). An overflowpipe was
installed to keep the dense phase within the FB and maintain
continuous operation of the whole system. A differential mano-
meter was used to monitor the fluidization condition in the
reactor. The cooling system was made up of two parts. The first
part was a shell-and-tube-type heat exchanger cooled by water.
The second part was a copper bottle surrounded by a dry-
ice-acetone mixture, with the temperature of about -40 C.
A scrubbing bottle, filled with pure alcohol, was used at the end
of the system. The scrubbing bottle was checked after each run
to make sure that it remained colorless and transparent, indicat-
ing that the cooling system could entirely cool and collect the
condensable products. In addition, a vacuum pump was set at
the end of the system to adjust the pressure in the reactor.
A nitrogen bottle was used to provide fluidizing gas, and
quartz sand with a particle size of 0.2-0.35 mm was used as the
bed material. After the temperature and pressure in the reactor
and the flow rate of fluidizing gas attained their preset values,
the reactants (biomass and CaO) were fed into the reactor using
the screw feeder. The biomass mixed quickly with the hot sand,
and pyrolysis began. During reaction, the pyrolysis products
passed through the filter, removing solid impurities. Finally, the
pyrolysis product entered the two cooling devices, where the
condensable gas was converted to biocrude. Non-condensable
gas was collected in a gas bag.
A WRT-2P microthermobalance
18
was used to prepare the
solid residues from biomass pyrolysis with CaO.
Table 1. Proximate and Ultimate Analyses of White Pine
item value
proximate analysis (wt %, air-dried basis)
moisture 2.4
ash 0.3
volatile matter 83.0
fixed carbon 14.3
ultimate analysis (wt %, dry ash-free basis)
C 47.3
H 6.1
N 0.1
S <0.1
O 46.4
Figure 1. Schematic of the FB reactor and the experimental system for bio-oil recovery.
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Energy Fuels 2010, 24, 56865695
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2.3. Experimental Conditions. The temperature of the FBreac-
tor was set at 520 C, which was deemed to be suitable for
pyrolysis of wood.
19,20
The carrier-gas flow rate was set at
50 L/min (standard temperature and pressure; 1 atm and
25 C) for good fluidization of the quartz sand. The superficial
gas velocity under this condition was about 0.9 m/s, which is
more than 20 times the minimum fluidization velocity of the
quartz sand (0.04 m/s), resulting in quite high expansion of the
dense bed and enabling smooth feeding of the white pine.
However, the superficial gas velocity was much higher than
the terminal velocities of the white pine and CaO powders,
making them pass through the reactor without extensive back-
mixing. The average residence time of gas in the whole reactor
was close to 1 s, which allowed for complete pyrolysis and
minimized undesiredsecondary reactions. The flowrate of white
pine was controlled at about 3 g/min. Thus, the total feeding
rates of the mixed white pine and CaO were controlled at 3.0,
6.0, 9.0, 12.0, 15.0, and 18.0 g/min for R = 0, 1, 2, 3, 4 and 5,
respectively.
The liquid product, the original bio-oil or the biocrude, was
collected in a glass bottle with a ground glass stopper for later
use. The production yields of bio-oil during pyrolysis and the
mixture of char and CaO were readily determined by weighing
their accumulated samples, while the production yields of gas
and char could be calculated by subtraction. To verify the reli-
ability of the subtraction method, several tests were carried out
during the experiments. The concentrations of CO
2
, CO, CH
4
,
and H
2
were determined by a gas chromatograph (GC, Shimadzu
GC14B, Japan), equipped with a packed column (Molecular
Sieve 5A), using heliumas the carrier gas. The injector, detector,
and oven temperatures were 100, 80, and 120 C, respectively. In
combination with the determination of the inert gas volume, the
mass of the inert gas could be obtained by direct measurement,
which showed that the deviation from the subtraction method
was less than 5%. A Vario EL III ultimate analysis apparatus
(Germany Elementary Corporation) was used for elemental
analysis of the biocrude. A KF-1B moisture analyzer, domestic
made, on the basis of the Karl Fischer method, was used to
measure the water content of the biocrude. When the water
content of the biocrude samples was excluded, the final elemen-
tary composition of the organics (or bio-oil) was determined
on a dry ash-free basis. A GC/MS-QP2010 combined system
(Shimadzu, Japan) was used to determine the chemical com-
pounds in the bio-oil samples. A DB-WAX capillary column
(length, 30 m; inner diameter, 0.25 mm) was used as the sepa-
ration unit. The programmed temperature settings for the ana-
lysis were as follows: isotherm at 60 C for 5 min, temperature
increase to 240 C at 10 C min
-1
, and isotherm at 240 C for
30 min.
Total-ion mass spectra of the bio-oils with different CaO/
white pine ratios are shown in Figure 2. The baselines of the
spectra are distinguished clearly, showing that the experimental
method was appropriate for analyzing the bio-oil.
For preparation of the solid residues for XRD and FTIR
analyses, the white pine and R=1 CaO mixed samples were
pyrolyzed on the WRT-2P microthermobalance at different
temperatures from 200 to 650 C, at intervals of 50 C.
The XRD analysis was performed using a Bruker-AXS
diffractometer with a conventional X-ray tube (Cu KR radia-
tion, 35 kV, 30 mA). The XRD patterns were recorded in the
2 range of 5-120, at a 2 step-scan rate of 1 min
-1
and a
2 step width of 0.02.
FTIR spectra of tablets compressed from a mixture of solid
products and KBr powder were obtained using a FTIR spectro-
meter (BRUKER-EQUINOX 55). The transmission mode
between 4000 and 400 cm
-1
with a resolution of 4 cm
-1
and an
averaging of 16 scans was recorded to characterize the surface
properties of the solid products, after subtraction of the scanned
background of KBr. Flat baselines were obtained after baseline
correction to correct spectra that had sloping or curved base-
lines, and a 15-point smoothing was chosen. Finally, the spectra
were all normalized by dividing the absorbances by the largest
absorbance in each spectra.
3. Results and Discussion
3.1. Production Distribution. Figure 3 shows the influence
of CaO addition on the yields of biocrude, char, gas, water,
and organics (bio-oil). With an increase of R from 0 to 5,
the yields of biocrude changed from 55.9 to 62.2 wt %, the
yields of char changed from 25.3 to 27.9 wt %, the yields of
gas changed from 18.8 to 9.9 wt %, the yields of organics
changed from 39.4 to 34.1 wt %, and the yields of water
changed from 16.5 to 28.1 wt %. The water in the biocrude
came mainly from the water in the biomass and dehydration
during pyrolysis. According to the investigation by Liao
et al.,
9
the dehydration reaction has an important role when
a calcium compound is added.
Figure 4 shows the influence of CaOaddition on the yields
of composing gases. With an increase of R from 0 to 5, the
yields of CO
2
changed from 9.5 to 3.2 wt %, the yields of CO
changed from 6.8 to 4.3 wt %, the yields of H
2
changed from
0.3 to 0.8 wt %, and the yields of CH
4
changed from 2.2 to
1.6 wt %. The decreased yields of CO
2
were believed because
of the reactions of CaO with CO
2
or its precursors, the so-
called active quasi-CO
2
intermediates, formed during the
pyrolysis process. The yield variations of H
2
and CO could
be due to the effect of CaO addition on the water-gas shift
reaction.
COH
2
OTCO
2
H
2
The increased yield of H
2
Oand the decreased yield of CO
2
were favorable for moving the reaction to the right side of
this equilibrium, resulting in the depletion of CO and the
formation of H
2
. This mechanism is quite similar to what
happens in the process of so-called enhanced hydrogen
production from biomass in situ carbon dioxide capture
using calcium oxide sorbents reviewed in detail by Florin
and Harris.
21
3.2. C, H, and OAnalyses of the Organics. The C, H, and O
contents and the O/C, H/C, and H/O relative ratios are
shown in Figure 5 for the organics produced using different
R. The figure shows that the O content decreases, the H
content increases, and the C content remains largely un-
changed with increasing R. At R = 5, the oxygen content of
the bio-oil is 8 wt % lower than the original value, resulting
from the pyrolysis of white pine alone (39 wt %), and the
relative reduction of oxygen reached 21%. The requirement
of a relatively high CaO ratio for deoxygenation of bio-oil
may have resulted from a relatively low contact efficiency
between CaO and biomass in the FB reactor working in
once-through mode, as mentioned above.
3.3. Component Analysis of the Organics by Gas Chroma-
tography-Mass Spectrometry (GC-MS). Table 2 lists the 38
main compounds in the liquid products in the order of their
(18) Yu, J.; Lin, Y.; Yang, C.; Zhang, M.; Zhang, C. Proceedings of
the Annual Conference on Combustion; Chinese Society of Engineering
Thermophysics: Xi'an, China, Oct 2008; 260 (in Chinese).
(19) Van de Veldan, M.; Baeyens, J.; Boukis, I. Biomass Bioenergy
2008, 32 (2), 128139.
(20) Kang, B.; Lee, K. H.; Park, H. J.; Park, Y.; Kim, J. J. Anal. Appl.
Pyrolysis 2006, 76 (1-2), 3237. (21) Florin, N. H.; Harris, A. T. Chem. Eng. Sci. 2008, 63 (2), 287316.
5689
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oxygen contents from high to low. The relative abundances
of the listed compounds are greater than 1%in at least one of
the six test conditions. The analysis results indicate that the
pyrolysis products of white pine are composed of aldehyde,
acid, alcohol, ketone, ether, ester, furan, phenol, and other
minor components.
The oxygen contents of the first six compounds listed in
the table are all higher than the oxygen content of white pine
Figure 2. Total-ion spectrum of the bio-oils.
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(46.6 wt %); therefore, their contents contribute significantly
to the oxygen in bio-oil. The relative abundances of these
high-oxygen-containing components, viz. formic acid, acetic
acid, D-allose, and laevoglucose (LG), clearly decreased with
increasing CaO. The relative abundance of ethylene glycol
increased, but the values were too small (1.03, 1.05, 1.95,
2.11, 3.96, and 3.91%) to offset the trend for the average
oxygen content to decrease. Therefore, after adding CaO, the
total oxygen content of the organic components in the bio-oil
decreases.
The main products of cellulose pyrolysis,
22
LGand acetol,
were of high interest in the experiment. Figure 6 shows the
changes in LG and acetol with increasing CaO. The relative
abundance of LG decreased slowly with an increase in R
from 0 to 2, while it dropped heavily with an increase in R
from 2 to 5. The variation trend of acetol was opposite that
of LG. Meanwhile, 1-hydroxy-2-butanone and succinalde-
hyde, which mostly arise fromcellulose pyrolysis, were also
increased with increasing CaO. Because the oxygen content
of LG (49.38 wt %) is obviously higher than those of the
other three components (43.24, 36.36, and 37.21 wt %)
and the cellulose content is quite high in white pines, the
authors conclude that this is the main reason for the
decrease in oxygen content of bio-oil in the presence of
CaO. This conclusion is in agreement with our previous
work.
17
Broido and co-workers suggested that active cellulose with
a low degree of polymerization would be formed first during
cellulose pyrolysis, which was subsequently experimentally
verified.
23,24
According to the reports of Richards and Zheng
and others,
22,25,26
active cellulose undergoes the following
competing paths: (1) Glycosidic bonds rupture in active
cellulose with the formation of LG. (2) Ring-opening, de-
composing, and reforming reactions occur within the cellu-
lose monomers to forma number of small volatile molecules,
such as acetol, hydroxyacetaldehyde, and butanedial. At the
same time, a large number of oxygen-rich active groups,
containing carboxyl and carbonyl, for example, are formed
by the second reaction path.
22,26
The reason for reduction of
LG and elevation of these small molecules with the addition
of CaO can be explained as follows. The oxygen-rich active
groups, so-called active quasi-CO
2
intermediates, undergo
collision and reaction with the added CaO particles to form
Figure 3. Yields of biocrude, gas, char, water, and organics as a
function of the mass ratio R.
Figure 4. Yields of CO, CO
2
, CH
4
, and H
2
as a function of the mass
ratio R.
Figure 5. C, H, andOcontent andH/C, O/C, andH/Oof the bio-oils.
(22) Luo, Z.; Wang, S.; Liao, Y.; Cen, K. Ind. Eng. Chem. Res. 2004,
43 (18), 56055610.
(23) Broido, A.; Nelson, M. A. Combust. Flame 1975, 24, 263268.
(24) Boutin, O.; Ferrer, M.; Lede, J. J. Anal. Appl. Pyrolysis 1998, 47
(1), 1331.
(25) Richards, G.; Zheng, G. J. Anal. Appl. Pyrolysis 1991, 21 (1-2),
133146.
(26) Shen, D. K.; Gu, S. Bioresour. Technol. 2004, 100 (24), 6496
6504.
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organic and/or inorganic calcium salts and are then fixed in
the solid phase.
27,28
Because some of the chemical bonds of
these intermediates are temporarily opened during pyrolysis,
they are in a very active state whencontacting CaO. Thus, the
process will function as a chemical sink, and this causes
the transformation of dominance of the parallel competitive
reactions to the path of decomposition and reforming.
Because the reduction of the oxygen content of the oil of
cellulose is through the dominance transformation of these
reactions, the indirect process needs continuous or repeated
contact between the reacting particles. This may also explain
why the deoxygenation process requires a relatively high
CaO/pine ratio R.
The authors did not detect hydroxyacetaldehyde, which is
also one of the main products of the second reaction path
mentioned above.
22,25
The reason for this was mainly that
the retention time of hydroxyacetaldehyde was the same as
that of acetic acid but its quantity was much lower than the
latter.
29
In addition, hydroxyacetaldehyde may undergo the
dehydration of the ketene structure and sequential rehydra-
tion to acetic acid.
26
The evolution of this will be discussed
along with acetic acid later.
Although carboxyl and acyl functional groups, which
will subsequently transform to acids, can be formed from
Table 2. Relative Abundances of Main Components Detected in Various Bio-oils
item relative abundance (%)
number name
molecular
formula O (%) RT (min) R = 0 R = 1 R = 2 R = 3 R = 4 R = 5
1 formic acid CH
2
O
2
69.57 11.8 2.28 0.72 0.65 nd
a
nd nd
2 acetic acid C
2
H
4
O
2
53.33 10.8 10.4 6.31 4.05 3.42 2.8 1.41
3 D-allose C
6
H
12
O
6
53.33 31.8 3.03 2 nd nd nd nd
4 ethylene glycol C
2
H
6
O
2
51.61 13.3 1.03 1.05 1.95 2.11 3.96 3.91
5 levoglucosan C
6
H
10
O
5
49.38 36 13.3 11.2 10.1 7.1 2.88 1.63
6 methyl pyruvate C
4
H
6
O
3
47.06 11 1.76 1.56 1.38 0.88 nd nd
7 acetol C
3
H
6
O
2
43.24 8.3 5.9 7.49 9.62 14.4 23.6 22.7
8 methyl acetate C
3
H
6
O
2
43.24 9.7 1.47 1 2.28 2.42 2.35 2.27
9 5-(hydroxymethyl)dihydro-2(3H)-furanone C
5
H
8
O
3
41.38 18.8 1.34 1.02 0.99 0.87 nd nd
10 2(5H)-furanone C
4
H
4
O
2
38.1 15 1.2 1.15 1.07 1.53 1.59 1.67
11 hydroxy methyl furfurole C
6
H
6
O
3
38.1 22.2 1.88 2.12 3 0.52 1.75 1.48
12 succinaldehyde C
4
H
6
O
2
37.21 10.5 0.77 0.8 1.58 1.61 2.25 2.17
13 butyrolactone C
4
H
6
O
2
37.21 13.4 0.4 0.42 0.58 0.85 1.98 2.1
14 acetoin C
4
H
8
O
2
36.36 7.9 0.13 0.14 0.39 0.6 1.4 1.38
15 1-hydroxy-2-butanone C
4
H
8
O
2
36.36 9.6 0.22 0.24 0.31 0.5 1.08 1.1
16 furfural C
5
H
4
O
2
33.33 11.1 1.88 1.75 2.1 3.38 5.58 5.8
17 avolin C
10
H
10
O
4
32.99 20.5 0.62 0.48 1.02 1.11 1.25 2.05
18 furfuryl alcohol C
5
H
6
O
2
32.65 13.7 0.72 0.75 0.73 0.9 1.12 1.2
19 6-oxa-bicyclo[3.1.0]hexan-3-one C
5
H
6
O
2
32.65 15.1 1.62 1.7 1.1 1.22 0.6 0.61
20 vanillin C
8
H
8
O
3
31.58 22.8 3 3.01 4.27 2.86 2 1.62
21 1-(3-hydroxy-4-methoxyphenyl)ethanone C
9
H
10
O
3
28.92 23.4 1.24 1.63 2.33 1.64 0.96 0.52
22 3-methyl-1,2-cyclopentanedione C
6
H
8
O
2
28.57 15.7 0.86 0.98 1.04 1.31 1.95 2.02
23 4-hydroxy-2-methoxycinnamaldehyde C
10
H
10
O
3
26.97 30.4 1.62 2.6 2.88 1.41 0.22 0.27
24 4-((1E)-3-hydroxy-1-propenyl)-2-
methoxyphenol
C
10
H
12
O
3
26.67 24.2 0.69 1.07 0.95 1.76 0.26 1.11
25 2-ethoxy-6-(methoxymethyl)phenol C
10
H
14
O
3
26.37 27.3 0.77 1.18 1.01 0.52 0.12 0.17
26 guaiacol C
7
H
8
O
2
25.81 16.1 2.31 2.04 1.56 1.6 1.5 1.37
27 creosol C
8
H
10
O
2
23.19 17.1 2.06 2.36 2.23 2.2 1.65 1.61
28 cyclopropyl carbinol C
4
H
8
O 22.22 18.6 2.41 3.34 2.6 1.39 1.01 1.2
29 p-vinylguaiacol C
9
H
10
O
2
21.33 19.5 0.84 2.27 1.21 1.18 0.39 0.27
30 3-(1-ethoxyethoxy)-3-methyl-1-butene C
9
H
18
O
2
20.25 33.3 1.47 2.3 2.71 1.14 0.39 0.35
31 cyclopentenone C
5
H
6
O 19.51 9.2 0.72 0.73 0.73 1.35 2.25 2.32
32 eugenol C
10
H
12
O
2
19.51 19.2 0.55 1.05 0.71 0.67 0.33 0.28
33 trans-isoeugenol C
10
H
12
O
2
19.51 20.9 1.26 3.81 1.88 1.75 0.27 0.25
34 cerulignol C
10
H
14
O
2
19.28 23.1 1.74 1.96 2.27 3.42 0.5 2.17
35 juvabione C
16
H
26
O
3
18.05 24.3 0.31 1.23 0.49 0.47 nd nd
36 phenol C
6
H
6
O 17.6 17.6 0.43 0.45 0.58 0.7 1.58 1.71
37 3-methyl-2-cyclopentenone C
6
H
8
O 16.67 11.9 nd nd nd nd 1.2 1.14
38 4-methyl-2-oxopentanenitrile C
6
H
9
NO 14.41 20.1 1.24 1.89 3.25 2.52 2.1 2.21
a
nd = not detected.
Figure 6. Relative abundances of LG and acetol of the bio-oils.
(27) Yang, X.; Zhang, J.; Zhu, X. Energy Fuels 2008, 22 (4), 2598
2603.
(28) Sotirchos, S. V.; Smith, A. R. Ind. Eng. Chem. Res. 2003, 42 (10),
22452255.
(29) Wang, Z.; Cao, J.; Wang, J. J. Anal. Appl. Pyrolysis 2009, 84 (2),
179184.
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DOI:10.1021/ef1009605 Lin et al.
all three primary components of biomass during pyrol-
ysis,
26,30,31
acetic and formic acids are generally considered
to be the pyrolysis products formed directly from the acetyls
and the uronic acid side chains in hemicellulose.
32
Figure 7
shows the variations in formic and acetic acids detected with
changes in R. It can be seen from the figure that formic and
acetic acids decrease rapidly with increasing R. The experi-
mental results show that other small-molecule acids, such as
propionic acid (not listed in Table 2), also decrease with
increasing R. This indicates that the acid compounds and/or
their precursors, the active quasi-CO
2
intermediates, can
react directly with the added CaO. All of these decreases in
oxygen-rich acid compounds are also important reasons for
direct deoxygenation of the bio-oil with CaO addition.
The representative components of lignin bio-oil, guaiacol
and phenol,
33
were also of high interest in this experiment.
Figure 8 shows that the guaiacol content decreases and the
phenol content increases with increasing R. The variations in
ortho-cresol, para-cresol, and meta-cresol show the same
trends as phenol. Because the oxygen content of guaiacol,
23.19%, is higher than that of phenol, 17.60%, this trans-
formation is also beneficial to the decrease of bio-oil oxygen
content.
As revealed by Amen-Chen et al. and Ferrari et al.,
33,34
there are two main parallel decomposition pathways for
guaiacol. One is the demethylation reaction to formcatechol
and methane, and the other is the demethoxylation reaction
to form phenol. It could be speculated that CaO addition led
to the dominance of the second path. The literature
35
has
shown the cracking mechanism of aromatic ring side chains
by CaO catalysis. Following this, the mechanisms for the
above-mentioned phenomena are hypothesized in Scheme 1
as follows: (1) The aromatic ring with a negatively charged
-electron system is absorbed at the positively charged Ca
2
center in the CaO surface. (2) The hydrogen atom of the
aliphatic side chain is transferred at the oxygen atom center,
thus altering the dehydrogenation properties of the aliphatic
structure. (3) The deprotonated aliphatic side chain repulses
the negatively charged -electron system, which will further
weaken the bond between the aromatic ring and the aliphatic
structure, thus inducing the absorption of the aliphatic side
chain on the CaO surface near Ca
2
. (4) Because the affinity
of the aromatic ring and the proton is much larger than that
between the alkyl and the metal ion, the aromatic ring will be
attached to the hydrogen proton site on the CaO surface.
(5) The side chain is finally detached.
Furfural, furfuryl alcohol, hydroxymethyl furfural, 2(5H)-
furanone, cyclopentenone, 3-methyl-2-cyclopentenone, and
2,3-anhydro-D-mannosan (not listed in the table) are gener-
ally considered to be the products of the dehydration reac-
tions of cellulose and hemicellulose.
26,30
The total relative
abundance of such products increased dramatically after
adding CaO. In accordance with the experimental results
regarding water content in the biocrude, it can be concluded
that CaO addition can fix the active quasi-CO
2
intermedi-
ates and can also greatly promote dehydration reactions
during pyrolysis. The latter is also very important for quality
enhancement of bio-oils.
3.4. Analysis of Solid Products. 3.4.1. XRD Analysis.
Figure 9a shows XRD patterns of white pine alone and its
Figure 7. Relative abundances of formic and acetic acids of the
bio-oils.
Figure 8. Relative abundances of guaiacol and phenol of the
bio-oils.
Scheme 1. Reaction Mechanismof Aromatic Ring Side Chains in the
Presence of CaO
(30) Shen, D. K.; Gu, S.; Bridgwater, A. V. J. Anal. Appl. Pyrolysis
2010, 87 (2), 199206.
(31) Ferdous, D.; Dalai, A. K.; Bej, S. K.; Thring, R. W. Energy Fuels
2002, 16 (6), 14051412.
(32) Demirbas, A. Fuel Process. Technol. 2007, 88 (6), 591597.
(33) Amen-Chen, C.; Pakdel, H.; Roy, C. Bioresour. Technol. 2001,
79 (3), 277299.
(34) Ferrari, M.; Bosmans, S.; Maggi, R.; Delmon, B.; Grange., P.
Catal. Today 2001, 65 (2-4), 257264.
(35) Zhu, T.; Liu, L.; Wang, Y.; Huang, J. J. Fuel Chem. Technol.
2000, 28 (1), 3639 (in Chinese).
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DOI:10.1021/ef1009605 Lin et al.
residual pyrolysis products at different final temperatures.
Two broad peaks at the 2 values of about 16.4 and 22.3
for the white pine were due to the 101 and 002 lattice spacings
of cellulose in wood.
29
Importantly, it was revealed that the
two peaks still exist at 300 C. Consequently, the pyrolysis
products generated below 300 C must originate from hemi-
cellulose rather thancellulose. The twopeaks vanishedat 400
C, showing the extensive structural destruction of cellulose,
in accordance with a sharp weight loss between 300 and 400
C, as shown previously.
18
The chars obtained above 400 C
were virtually amorphous.
Figure 9b shows the XRDpatterns of analysis-grade CaO,
CaCO
3
, R=1 mixture sample of white pine andCaO, andits
residual pyrolysis products at different final temperatures.
As shown in the figure, most of the intensity of the char-
acteristic peaks of inorganic calcium compounds in the solid
samples at 350 C, such as the CaCO
3
characteristic peak at
2=36 (marked with O in the figure), were weakened and
then re-sharpened, becoming stronger above this tempera-
ture. Many amorphous calcium salts, similar to pyrolytic
carbon, or organic calciumsalts that showed tiny differences
in the characteristic peaks with CaO or CaCO
3
could also be
found from the powder diffraction file (PDF) cards. Thus,
the weakest peaks of the solid samples at 350 C could be
attributed to the effect of the amorphous structure, crystal
lattice distortion, and nanostructure that was induced by
the presence of organic calcium salts.
27,36
It may be con-
cludedthat these organic calciumsalts result fromthe active
quasi-CO
2
intermediates directly fixed by CaO. The re-
sharpening of the peaks in the solid samples produced at a
final temperature of 400 C could be due to the decomposi-
tion of the fixed active quasi-CO
2
intermediates to inor-
ganic CaCO
3
.
3.4.2. FTIR Analysis. Panels a and b of Figure 10 show
FTIR spectra of the various solid samples. It can be seen
from Figure 10a that the stretching vibration peak of CdO
(1729 cm
-1
) in the organic structure
29
of the residual solid
sample obtained from the pyrolysis of white pine alone at a
final temperature of 350 C essentially disappeared. How-
ever, the peak still existed for the sample obtained from the
pyrolysis of the R=1 mixed sample at this final temperature
and then essentially disappeared for the temperature pro-
duced at the final temperature of 400 C. It can be concluded
that calcium carboxylates or the aforementioned active
quasi-CO
2
intermediates were generated near the tempera-
ture of 350 C because of the reaction of CaO with some
carboxyl groups formed during pyrolysis of white pine,
resulting in the retention of some organic groups and the
corresponding CdO peak shown in Figure 10b.
As shown in Figure 10b, the peaks located at 1422 and
875 cm
-1
correspond to the asymmetric C-O stretching and
O-C-Oout-of-plane bending vibrations of CO
3
2-
and they
are also characteristic of CaCO
3
.
36,37
The two peaks began to
appear for the solid sample obtained from the pyrolysis of
the R = 1 mixed sample at the final temperature of 400 C,
while the stretching vibration peak of CdO (1729 cm
-1
)
disappeared. It can be concluded that calcium carboxylates
decomposed to CaCO
3
near the temperature of 400 C.
Previous TG results showed that some pyrolysis products
were fixed by CaO below 350 C, and this also indicates that
some organic calcium salts rather than CaCO
3
formed at
350 C during the pyrolysis process.
According to the absorption frequencies of the various
functional groups,
29,38
the peak around 3425 cm
-1
is due to
hydrogen-bonded OH stretching. The peak around 3637
cm
-1
shown in Figure 10b represents the stretching of OH
in Ca(OH)
2
because of water sorption of CaO. The peaks
attributable to aliphatic CH
n
(2924 cm
-1
) and aromatic
CH
3
(2855 cm
-1
) decreased in intensity significantly above
400 C. This result reveals that CH
4
would be generated in
large quantities above this temperature. The peaks 1270,
1156, 1107, and 1060 cm
-1
are related to the C-O-C and
C-O structures, of which 1270 cm
-1
may be consistent with
the C-O vibration of the methoxy groups. The significant
Figure 9. XRDpatterns of various samples and its various pyrolysis residual products at different final temperatures: (a) white pine alone (pine)
and (b) R = 1 (1:1) mixture sample (PWC).
(36) Pokroy, B.; Fitch, A. N.; Marin, F.; Kapon, M.; Adir, N.;
Zolotoyabko, E. J. Struct. Biol. 2006, 155 (1), 96103.
(37) Chen, L.; Hu, F.; Zhou, Q.; Sun, J.; Zhang, H. Cryst. Res.
Technol. 2009, 44 (12), 12891292.
(38) Williams, D. H.; Fleming, I. Spectroscopic Methods in Organic
Chemistry; McGraw-Hill Professional: New York, 1989.
5694
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DOI:10.1021/ef1009605 Lin et al.
reduction of such peaks in the range of 400 and 450 C is in
agreement with the formation of CO and phenols. The
aromatization may occur mainly by ether cleavage before
most methoxy groups are extensively broken from lignin.
The intensity of the peaks 1460, 1426, and 1380 cm
-1
relating
to the C-H deformation or bending of aliphatic or methoxy
groups decreased rapidly above 400 C. This result also
indicates the appearance of CH
4
and CO.
3.4.3. Application to the FB Reactor. XRD and FTIR
analyses of the solid residues prepared by a thermal balance
showed that some organic calcium salts appeared at 350 C,
which would decompose below 400 C. However, the differ-
ent operating conditions in the thermal balance and FB
reactor should be considered.
The lower heating rate and the longer residence time in the
thermal balance allow all of the changes or transforms
mentioned above to be quite complete. In the FB reactor,
because of its very high heating rate and relatively short
residence time, the transforms would be delayed to some
extent regarding the temperature and incomplete more or
less. The formation of organic calcium salts and the later
decomposing to CaCO
3
would occur at higher temperatures.
Then, it is difficult to determine whether these transforms
take place in the initial stage of heating of the biomass
particles or in the constant temperature region of the FB
reactor.
Nevertheless, in the double-circulating FBs, the final
transform to CaCO
3
would be completed in the combustion
chamber at an even higher temperature before the calcina-
tion for CaO recycle takes place. This further confirmed
the feasibility of CaO recycling for in situ deoxygenation of
bio-oil.
4. Conclusions
White pine fast pyrolysis in the presence of CaO in a FB
reactor and XRD and FTIR analyses of the solid residual
pyrolysis products of biomass with CaO in a thermal balance
were carried out to investigate the direct deoxygenation effect
on bio-oil. The main conclusions are as follows: (1) In
comparison to the original value of the bio-oil from white
pine powder alone (39 wt %), the oxygen content of
the organic components of the bio-oil from pyrolysis in the
presence of CaO decreased to 31 wt % for a CaO/white pine
Figure 10. FTIR spectra of various samples and its various pyrolysis residual products at different final temperatures: (a) white pine alone
(pine) and (b) R = 1 (1:1) mixture sample (PWC).
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DOI:10.1021/ef1009605 Lin et al.
mass ratio of R = 5, i.e., a relative change of -21%. (2) With
increasing R, the oxygen-rich compounds in the bio-oil, such
as LG, formic acid, acetic acid, and D-allose, decreased
dramatically, decreasing the total oxygen content of the bio-
oil. (3) Withregardtothe mainproducts of cellulose pyrolysis,
the relative abundance of LG decreased and the relative
abundance of acetol increased dramatically with increasing
R, indicating a dominant transformation of the parallel
competitive reactions from the glycosidic bond rupture route
to the decomposition and reforming (D-R) route. The direct
fixation of the active quasi-CO
2
intermediates by CaO
functions as a chemical sink in the D-R route for this
transformation. (4) With increasing R, all acidic compounds,
especially the formic and acetic acids largely formed from
hemicellulose pyrolysis, decreased greatly. This indicates that
the acidcompounds and/or their precursors, the active quasi-
CO
2
intermediates, can react directly with the added CaO.
(5) With increasing R, guaiacol decreased and phenol,
ortho-cresol, para-cresol, and meta-cresol all increased. This
result indicates that the pyrolysis products of white pine lignin
tendtowardthe side-chain-detachment reactionpathway inthe
presence of CaO. (6) Furfural, furfuryl alcohol, hydroxymethyl
furfural, 2(5H)-furanone, and 3-methyl-2-cyclopentenone,
which are recognized as the products from dehydration reac-
tions, increased with increasing R. This reveals that CaO
addition can not only fix the active quasi-CO
2
intermediates
but also greatly promote the dehydration reactions during the
pyrolysis. (7) As shown in XRD patterns from the R = 1
mixture sample of white pine and CaO and its slow pyrolysis
residual products, most of the intensity of characteristic peaks
of inorganic calciumcompounds in the solid samples at 350 C
were weaker than the others. This can be explained by the
formation of organic calcium salts originating from the reac-
tion of CaO and the active quasi-CO
2
intermediates, which
emergedduringthe pyrolysis process. (8) As showninthe FTIR
spectra of the R=1 mixture sample of white pine andCaOand
its slow pyrolysis residual products, the retention of the peak
assigned to CdO stretching (1729 cm
-1
) for the 350 Csample
confirmed the existence of calcium carboxylates. The appear-
ance of the characteristic peaks of CaCO
3
for the 400 Csample
illustrates that calcium carboxylates had been decomposed
below this temperature.
Acknowledgment. This research was financially supported by
the National Natural Science Foundation of China (50676062).