AIMS Energy, 6(1): 203–215.

DOI: 10.3934/energy.2018.1.203
Received: 20 November 2017
Accepted: 26 February 2018
Published: 02 March 2018
http://www.aimspress.com/journal/energy

Research article

Bio-oil upgrading by cracking in two-stage heated reactors

Lihao Chen1,* and Kunio Yoshikawa2

1
Department of Environmental Science and Technology, Tokyo Institute of Technology, 4259
Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
2
School of Environment and Society, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,
Yokohama 226-8502, Japan

* Correspondence: Email: chen.l.ag@m.titech.ac.jp; Tel: +810459145507.

Abstract: The objective of this research is to explore the possibility to upgrade gasified bio-oil in
bench-scale fixed bed reactors with two heating units using the cracking method. The bio-oil is
derived from Japanese cedars which are widely distributed in Japan. The catalyst is HZSM-5 zeolite,
which is commonly used in bio-oil upgrading. The result showed that by using two heating units,
even without catalyst, the upgrading was achieved as well. The catalytic cracking promoted the
deoxygenation rate and further improved the quality of the upgraded oil compared with the
non-catalytic cracking case. By separating two heating units with different operating condition, the
catalytic effect and the deactivation of the catalyst was clarified. The raw bio-oil and the upgraded oil
were characterized by measuring their element content, water content and the chemical composition
of its organic fraction.

Keyword: cracking; bio-oil upgrading; zeolite catalyst; fixed bed; two-stage reactors

1. Introduction

Biomass sources are widely recognized as a potential future solution to the energy problems
worldwide [1,2]. It provides the only source of renewable liquid fuel [3]. Bio-oil, a liquid product of
biomass pyrolysis, is a complex mixture of several hundreds of organic compounds that exhibit a
wide range of chemical functionality [4]. Characteristic examples of the bio-oil compounds are
single ring containing compounds and polycyclic aromatic compounds [5].
The bio-oil applied in this study is produced from the cedar pollard, a kind of waste biomass. In
order to be used as a liquid fuel, two main problems needs to be solved: high viscosity and high
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oxygen content [6,7]. These two problems lead to undesirable combustion phenomenon such as
insufficient energy density, incomplete combustion and blockage [8].
To solve such problems, the main upgrading methods include the hydrogenation [9,10], the
cracking [11,12], the solvent addition [13], the steam reforming [14,15] and the emulsification [16,17].
However, none of these bio-oil upgrading technologies have been widely commercialized due to high
cost and low fuel efficiency [18]. The cracking method is highly feasible because It can be realized at
the atmospheric pressure and no additives are required [19,20].
The popular cracking methods are fixed bed cracking, moving bed cracking and fluidized bed
cracking [21,22]. The fixed bed cracking is chosen in this study for its simple equipment
requirements.
Many types of catalysts have been studied in the literatures in order to investigate how far the
catalyst can modify the bio-oil composition and the bio-oil quality. Most of these studies are focusing
on the comparison of catalysts but not on the mechanism of catalysts. The control test without
catalyst is considered unnecessary in these studies [23–29].
However, in this paper, the effect of the commonly used catalyst HZSM-5 was discussed
focusing on the comparison with the non-catalytic cracking. Most studies on the catalytic cracking of
bio-oil are using only one heating reactor, where all components of bio-oil are in contact with the
catalyst, including the components that tend to deactivate the catalyst. In this paper, two heating units
were employed so that the raw bio-oil was separated in the first heating unit and the cracking was
done in the second heating unit. The components liable to deactivate the catalyst can be identified by
changing the temperature in the first heating unit. In this way, the catalyst deactivation caused by
different components were analyzed simultaneously, instead of treating the bio-oil as a whole [30,24],
using model components separately [20] or analyzing the deactivated catalyst after the reaction [31].
Some researches reported that bio-oil component separation is difficult under the atmospheric
pressure and side reactions tend to occur due to the poor heat stability of bio-oil [32,33]. But in this
paper, side reactions did not significantly affect the experimental results by employing the two-stage
heated reactors. Indeed, it is difficult to separate all components in bio-oil individually, but the
components can be divided into 4 classes according to the chemical analysis, which was sufficient to
explain the reaction mechanism of the deactivation. Different from the one heating unit process
which is commonly used, the components in the upgraded bio-oil can be divided into 4 classes of
organic components clearly by employing two heating units. By analyzing the reaction trend of these
four classes of bio-oil components, the deactivation principle of the catalyst can be discussed without
using model compounds. Previous studies generally considered that high molecular weight aromatic
and aliphatic compounds are important reasons for deactivation of catalysts [1,34], but in this
research, the effects of phenols and naphthalenes on the catalyst were investigated to show the
importance of their effects.

2. Materials and methods

2.1. Materials

2.1.1. Bio-oil

The bio-oil was produced from the pyrolysis of Japanese cedar. The pyrolysis gas produced in

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an updraft gasifier passed through a cooler to remove water and heavy tar and then was introduced to
a centrifuge separator to recover the bio-oil [35].
The elemental content and properties of the bio-oil are listed in Table 1.

Table 1. The element analysis and properties of the raw bio-oil.

Element and properties of bio-oil
C (%) 57.5
H (%) 7.0
N (%) 0.0
O (%) 35.5
S (mg/kg) 0.0
H2O (%) 8.3
Ash (%) 0.0
3
Density (g/cm ) 1.14
HHV (MJ/kg) 23.1
Cetane index <20
2
Kinetic viscosity (mm /s @ 50 °C) 12.7
*Cetane index of bio-oil was unable to measure accurately for its high density.

2.1.2. Catalytic materials

The HZSM-5 catalyst used in the experiment was provided by Tosoh corporation. Prior to the
experiments, the catalytic materials were calcined at 500 °C for 3 h and stored in a desiccator. Its
properties are listed in Table 2.

Table 2. Properties of the catalyst.

Properties of the catalyst
Pore size (Å) 5.8
SiO2/Al2O3 (mol/mol) 40
2
Specific surface area (m /g) 330
Crystal size (μm) 2 ×4
Particle size (μm) 10
NH3-TPD (mmol/g) 1.3

2.2. Experimental set-up

The schematic diagram of the experimental set-up is shown in Figure 1. The raw bio-oil was
firstly introduced to the first heating unit and then gasified into the second heating unit, with or
without packing of the catalyst. As a carrier gas, N2 gas was fed at the flow rate of 10 mL/min from
the top of the first heating unit for the continuous withdrawal of the products and the maintenance of
the inert atmosphere during cracking. The product flowing out from the bottom of the second heating
unit was in gaseous form, and was condensed in a glass receiver submerged in an ice-water bath.
Non-condensable gases were collected in a gas bag. A filter was placed between the ice-water bath

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receiver and the gas bag for recovering condensable vapor which might leak from the condenser.

Figure 1. Schematic diagram of the experimental set-up.

2.3. Experimental procedure and product collection

Initially, the second heating unit was filled with 10 g catalyst (catalytic cracking) or no
catalyst (non-catalytic cracking), while the first heating unit was filled with 30 g of the raw bio-oil.
The first heating unit was heated to a specified temperature. The first heating unit was heated
externally to the different set temperature in different heating time, after the second heating unit was
heated to 500 °C for 60 minutes. Every operation lasted one hour to ensure the reaction is complete.
The operating condition was listed in Table 3.

Table 3. Operating conditions.

Operation Condition Set temperature of the 1st heating unit Heating time
Partial Gasification (PGF) 510 ℃ 15 min
Further Gasification (FGF) 550 ℃ 18 min
Complete Gasification (CGF) 600 ℃ 21 min

As show in Table 3, under the PGF operation condition, both the heated temperature and heating
time was less than the FGF and CGF condition. The liquid products were collected and quantitatively
measured in the pre-weighted glass receiver. When changing the set temperature higher than 600 ℃,
no more liquid was collected than CGF condition. Therefore, all volatile components are considered
to be gasified under the CGF condition. The non-condensable gas products were collected and
measured by difference. The amount of the residue left in the first heating unit was measured by
weighing the first heating unit before and after the experiment. The solid products consisted of the
coke left in the first heating unit and the coke on the catalyst in the second unit. The amount of
condensable vapors recovered in the filter was also weighed by difference and the weight was added
to the liquid products yield.

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2.4. Analysis methods

The following characteristics were determined: the elemental analysis of C, H, O, N, the

moisture content, the ash content, the density, the high heating value (HHV), the cetane index, the
kinetic viscosity and the chemical composition.
The ash content and the elemental analysis of C, H, N were determined by JM10 at 950 °C. The
elemental analysis of O was determined by Vario micro cube at 1150 °C. The moisture content was
measured using Karl Fischer method in accordance with the standards JIS K 2275. HHV was
determined in accordance with the standards JIS K 2279. The kinetic viscosity was measured by the
ostwald viscometer at 40 °C. The cetane index was calculated in accordance with the standards
JIS K 2280-5.
GC-MS is the technique used in the analyses of the product oil composition. A Rxi®-5Sil MS
Column was used in the GC and helium was selected as the carrier gas. The oven heating profile was
set at an increase of 5 °C/min from 30 to 280 °C.

3. Results and discussion

3.1. Effect of catalyst

In order to investigate the effect of the zeolite catalyst, the cracking with catalyst in the second
heating unit was compared with the non-catalytic cracking. In each run, after the second heating unit
was heated to 500 °C and kept for 60 min, the first heating unit was heated under the CGF condition
and kept for 1 h when no more liquid or gas product could be observed, the yield was weighed and
the data was listed in the Table 4.

Table 4. Product yield distribution by weight.

Liquid solid gas
With catalyst 61.3% (water:organic = 16.6:44.7) 19.8% 18.8%
Without catalyst 75.7% (water:organic = 16.8:58.9) 18.3% 14.4%

As shown in Table 4, the gas product from the non-catalyst run was less than the one from the
catalyst run, while the liquid product was more.
The upgraded oil in the liquid product was the target in this experiment. The collected liquid
product was divided into two layers: the water layer and the organic layer. The element analysis data
of the two layers are listed in Table 5.

Table 5. Element analysis of the liquid product.

Element content Without catalyst With catalyst
by weight Water layer Organic layer Water layer Organic layer
C (%) 21.85 67.91 10.11 73.47
H (%) 9.35 7.83 9.73 7.22
O (%) 68.70 24.07 79.93 19.03

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Obviously, some organic matter is soluble in the water layer. That is why C element was also
detected in the water layer.
Though in the non-catalytic cracking, the organic liquid product was more than that in the
catalytic cracking, the C content was lower and the O content was higher, which means that the
heating value of the organic liquid product was lower than the catalytic cracked bio-oil.
Compared with the raw bio-oil properties listed in Table 1, the C content increased by 10% and
the O content decreased by 11% in the non-catalytic cracking, while the C content increased by 16%
and the O content decreased by 16% in the case of the catalytic cracking. The cracking was achieved
without the catalyst, while the zeolite promoted the rate of deoxygenation by 50%.
The possible reason for this promotion was the adsorption and the acidic sites of the zeolite. The
adsorption on the surface of the zeolite extended the cracking reaction time of oxygen-containing
molecules and the acidic sites contributed to enhance the deoxygenation reaction [36,37]. Other
physical properties of the raw bio-oil and the organic liquid products are listed in Table 6.

Table 6. Physical properties comparison of the organic liquid and the raw bio-oil.
Bio-oil Organic liquid from catalytic Organic liquid
cracking from non-catalyst cracking
3
Density (g/cm ) 1.14 1.02 1.03
2
Kinetic viscosity (mm /s@50 °C) 12.7 4.72 4.85
Water content (%) 8.3 8.0 8.2
Cetane index <20 39.76 38.18
HHV (MJ/kg) 23.1 31.8 29.9

Significant improvement in physical properties was observed after the cracking regardless of the
usage of the catalyst. A further improvement was obtained by using the catalyst.
In order to analyze the phenomenon in more details, GC-MS was employed to identify the
chemical compositions of the raw bio-oil and the organic liquid. The result of the raw bio-oil is
shown in Figure 2.

Figure 2. Ion current of the raw bio-oil.

Though hundreds of organics was detected, if picking out the highest 20 peaks, the area of these
20 peaks accounted for 90% of the total area. These 20 organics were listed in Table 7.

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Table 7. The main chemical compositions of the raw bio-oil.

Name Retention time (min) Area (%)
1-Hydroxy-2-butanone 4.9 1.96
Propanal 5.2 1.26
3,5-Dimethylpyrazole 6.5 1.98
2(5H)-Furanone 8.9 2.36
1,2-Cyclopentanedione, 3-methyl- 12.7 3.90
Phenol, 2-methoxy- 14.6 18.09
2-Cyclopenten-1-one, 3-ethyl-2-hydroxy- 15.5 1.37
Phenol, 2,4-dimethyl- 16.9 1.55
Creosol 17.7 17.07
Phenol, 4-ethyl-2-methoxy- 20.1 12.98
Phenol, 2-methoxy-3-(2-propenyl)- 22.2 2.31
Phenol, 2-methoxy-4-propyl- 22.5 4.51
trans-Isoeugenol 24.8 5.93
Naphthalene, 1,2,4a,5,6,8a-hexahydro-4,7-dimethyl-1-(1-methylethyl)- 25.8 1.98
Naphthalene, 1,2,4a,5,8,8a-hexahydro-4,7-dimethyl-1-(1-methylethyl)- 26.3 3.70
[1S-(1.alpha.,4a.beta.,8a.alpha.)]-
Di-epi-.alpha.-cedrene-(I) 29.0 1.44
2-Naphthalenemethanol, 29.7 2.35
decahydro-.alpha.,.alpha.,4a-trimethyl-8-methylene-
[2R-(2.alpha.,4a.alpha.,8a.beta.)]-
Kaur-15-ene, (5.alpha.,9.alpha.,10.beta.)- 36.3 1.10
Naphthalene, 42.0 1.05
decahydro-1,1,4a-trimethyl-6-methylene-5-(3-methyl-2,4-pentadienyl)-
[4aS-(4a.alpha.,5.alpha.,8a.beta.)]-
Ferruginol 42.9 2.54

The main components could be divided into 4 classes. The first one is oxygen-containing small
molecules with the retention time from 2.5 to 10 min, the main components of which are kinds of
ketone, furan and imidazole. The second class is phenols with the retention time of 10 to 25 min,
whose main components are guaiacol and its homologues. The third class with the retention time
from 25 to 30 min are naphthalenes, which mainly contained naphthalene and naphthol. The fourth
one was the materials whose retention time were later than 30 min, mainly containing long-chain
aliphatic macromolecular and polycyclic macromolecular structural substances. The area proportions
of these four classes are listed in Table 8.

Table 8. Component classification of bio-oil.

Small molecule Phenols Naphthalenes Macromolecule
Rage of retention time (min) 2.5–10 10–25 25–30 >30
Area (%) 8.2% 74.0% 10.8% 7.0%

Figure 3 showed the GC-MS result of the organic liquid products. Two high peaks came out at

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the retention time of 5.1 min and 7.8 min after cracking. According to the data base, these two were
toluene and xylene, which were most likely the product of the phenolic deoxygenation.
In the catalytic cracking, the phenols peak and the naphthalenes peak deceased more evidently
than the non-catalytic cracking, along with more product of toluene and xylene than the non-catalytic
cracking. Therefore, more phenolic deoxygenation happened when catalyst was used for cracking.
Considering the high thermal stability of benzene ring and naphthalenic ring [38,39], the decrease of
naphthalenes shall be interpreted as coking on the catalyst.

Figure 3. Ion current of the organic liquid of catalytic cracking (above) and non-catalytic
cracking (below).

In summary of the above data, the most likely reactions in the second heater unit are the
phenolic deoxygenation and the naphthalene coking on the catalyst. In the non-catalytic cracking, the
phenols and naphthalenes were directly condensed in the ice-water bath receiver without contact with
the catalyst. In order to verify this speculation, different temperatures in the first heating unit were
tested in the following section.

3.2. Catalytic test at different temperatures in the first heating unit

In order to confirm the reaction of the 4 component classes, all 3 types of operation condition in
Table 3 were tested. At each separation temperature, the experiments were repeated three times
without changing the catalyst in the second heating unit, but replacing the residue in the first unit
with new bio-oil. The yield was listed in Table 9.
Although the area percentage does not mean the actual content, the data as a reference can be
used to summarize the reaction trend.
In the first run at each temperature, the yield of small molecules were higher than the second
and the third runs. The yield of phenols in the first run was lower than in the second and the third
runs under the PGF and FGF condition. It can be concluded that at the first run of each temperature,
the catalyst has the highest activity of converting phenols to toluene and xylene. When the catalyst
was reused without regeneration, the activity decreased and more phenols were collected in the
condenser than in the first run.
Under the PGF condition, the distilled ingredients from the first heating unit were mainly the
small molecule components including oxygen-containing heterocyclic compounds, ketones and

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benzenes. From the first run to the third run, the yield of each class did not change significantly,
which shows that the deactivation was not serious. Small molecule components was not the main
reason for the catalyst deactivation.

Table 9. The area percentage in GC-MS of 4 component classes in the organic liquid at
different temperatures in the first heating unit.
Main Ingredients 1st Class 2nd class 3rd class 4th class
Small molecules* Phenols Naphthalenes Macromolecules
PGF
First run 52.0% 40.0% 8.0% 0.0%
Second run 44.8% 43.9% 10.8% 0.0%
Third run 48% 41% 7% 0.5%
FGF
First run 49.2% 45.0% 5.8% 0.0%
Second run 33.7% 57.3% 9.0% 0.0%
Third run 37.0% 55.5% 7.6% 0.02%
CGF
First run 34.8% 50.2% 13.6% 1.4%
Second run 18.1% 40.4% 33.4% 7.1%
Third run 11.5% 47.1% 33.1% 8.3%
*The main ingredients of “small molecules” were toluene and xylene.

Under the FGF condition, more phenols were distilled from the first heating unit. That is why
the yield of phenols was higher than the one under the PGF condition. After the first run under the
PGF condition, a significant decrease of the small molecule components was observed, accompanied
by the increase in the yield of phenols. The yields of naphthalene and macromolecules under the FGF
condition were in low level similar as in the case of PGF condition. This proved that phenols were
important cause of the catalyst deactivation.
When the separation temperature in the first unit came to CGF runs, a big amount of
naphthalenes and macromolecules are distilled from the first heating unit. A serious decline happened
in the yield percentage of the small molecules from the first run to the second run. A further decline
was observed at the third run. It clearly showed that naphthalenes and macromolecules coked on the
catalyst, resulting in a serious catalyst inactivation.
Moreover, it should not be considered that the naphthalenes and macromolecules collected in
the ice-water bath came from distillation only. Part of them should be the product of the
polymerization reaction in the heating process.
Small molecules, whose main component was toluene and xylene, did not contain oxygen. This
class of product should be the target product because of the higher heating value. A low separation
temperature and shorter heating time should be used to avoid the contact of naphthalenes and
macromolecules with catalyst.

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3.3. Yield and energy analysis

The yield of the product from the first run in each temperature was listed in Table 10. All
feedstocks were converted to water, liquid, coke and gas. The residue referred to the coke in the first
heating unit and the increased weight after the cracking tests.

Table 10. The product yield in the weight percentage (%).

Water Oil Gas Residue
CGF run 16.6 44.7 18.8 19.8
FGF run 14.1 41.2 17.2 27.0
PGF run 11.8 35.1 12.1 40.0

The oil product under PGF operation performed the lowest oxygen content, while that from
CDF run performed the highest yield. The comparison of these two product were listed in Table 11.

Table 11. Comparison of product oil and raw bio-oil.

Bio-oil Product oil from 300 °C run Product oil from 130 °C run
C (%) 57.5 73.5 72.3
H (%) 7.0 7.2 11.8
N (%) 0 0 0
O (%) 35.5 19.0 15.9
HHV (MJ/kg) 23.1 31.8 38.6
Yield (%) - 44.7 35.1
Heat inputs (kJ/g) - 18.2 16.5
Energy recovery (%) - 34.3 34.3

The heat inputs referred to the heat put into the reactor for average 1g bio-oil. The recovery rate
of the energy was calculated with the Eq 1:
Energy recovery = Energyproduct oil/(Energybio-oil + Heatinputs） (1)
Where Energyproduct oil = mproduct oilHHVproduct oil, Energybio-oil = mbio-oilHHVbio-oil
According to the calculation results, the product oil recovered 34% energy of the energy inputs.
The recovery rate of CGF run was a little higher than the PGF run, but the gap is limited. Since the
catalyst in the PGF run can be reused and the separation temperature was lower than the the CGF, oil
upgrading at a lower separation temperature is a rational choice.

4. Conclusions

The bio-oil can be upgraded in a process with two heating unit with or without zeolite catalyst.
The main reaction of the cracking is deoxygenation of phenols. The zeolite catalyst contributes to
promote the deoxygenation rate. However, utilization of zeolite catalyst results in a decrease of the
liquid product yield. As a liquid fuel, the properties of the catalytic cracked oil were better than the
non-catalytic cracked oil. The hundreds of components in the raw bio-oil can be divided into 4

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classes: small molecules, phenols, naphthalenes and macromolecules. Small molecules are not the
main cause of the catalyst deactivation. Phenols slightly deactivate the catalyst. The contact of
naphthalenes and macromolecules with zeolite is a big problem causing the deactivation. A lower
separation temperature in the first heating unit helps to alleviate the inactivation reaction.

Acknowledgment

This work was supported by the Tokyo Institute of Technology. The authors would like to thank
the cooperation of School of Environmental Science and Engineering of Tianjin University, which
provided a lot of theoretical guidance.

Conflict of interest

All authors declare no conflicts of interest in this paper.

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AIMS Energy Volume 6, Issue 1, 203–215.