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Fuel 103 (2013) 683692

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Fuel
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Experimental study on bio-oil upgrading over Pt=SO24 =ZrO2 =SBA


in supercritical ethanol

15 catalyst

Qi Dang, Zhongyang Luo , Jixiang Zhang, Jun Wang, Wen Chen, Yi Yang
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

h i g h l i g h t s
" The effects of reaction conditions on bio-oil upgrading were studied.
" The physical properties and chemical compounds of upgraded bio-oil were analyzed.
" Higher initial hydrogen pressures can inhibit coke formation effectively.
" Rising mass ratio of bio-oil to ethanol is helpful for desired products formation.
" Rising temperature will increase the heating value of upgraded bio-oil.

a r t i c l e

i n f o

Article history:
Received 7 April 2012
Received in revised form 19 June 2012
Accepted 21 June 2012
Available online 5 July 2012
Keywords:
Bio-oil
Catalytic
Upgrading
Supercritical ethanol

a b s t r a c t
The effects of reaction conditions, including the initial hydrogen pressures (0.5 MPa, 2.0 MPa), the mass
ratios of ethanol to bio-oil (5:1, 3:1, 2:1, 1:1) and reaction temperatures (260 C, 280 C, 300 C) on catalytic upgrading of fast pyrolysis bio-oil were investigated in this work. Experiments were carried out in
supercritical ethanol with bifunctional 5%Pt=SO24 =ZrO2 =SBA-15 catalyst. The physical properties and
organic compounds of upgraded bio-oil were compared and the mass and energy balance of certain
upgrading processes were studied. The results showed that higher initial hydrogen pressure (2.0 MPa)
could inhibit coke formation effectively. Increasing mass ratio of ethanol to bio-oil (5:1, 3:1) was helpful
for desired products formation and heating value improvement as well as lower coke yield. With the rising temperature, the heating value of upgraded bio-oil increased, but the amount of desired products
reduced and the formation of coke became much more serious.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, the declining of conventional fossil fuels and
severity of environmental issues have led to a great interest in
exploring renewable and environmentally benign energy resources
to enhance energy security. Biomass has become an increasingly
promising and potential alternative energy source since it is clean,
renewable and zero net CO2 emissions regarding carbon circulation. Biomass can be transformed into gaseous, liquid, and solid
biofuels. Liquid biofuels have gained tremendous attention and
should be vigorously developed due to its important role in replacing traditional fossil fuels and mitigating the transportation fuels
demand. Bio-oil, one kind of liquid biofuels, is commonly derived
from fast pyrolysis of biomass through thermochemical conversion
and a lot of related experimental work as well as mechanism

Corresponding author. Tel.: +86 0571 87952440; fax: +86 0571 87951616.
E-mail address: zyluo@zju.edu.cn (Z. Luo).
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.06.082

investigation on bio-oil production from fast pyrolysis of biomass


have been studied [13].
Bio-oil is very complex and contains a variety of organic compounds, mainly including acids, phenols, aldehydes, ketones,
esters, ethers, alcohols and saccharides [4]. The composition of
bio-oil changes with different raw materials, production conditions
and other inuential factors. However, bio-oil exhibits some unfavorable traits which limit its direct application in engines. Bio-oil is
inferior to traditional fossil fuels owing to its high moisture and
oxygen content and low heating value. A large amount of acids
in bio-oil result in high acidity and corrosion of containers. Aldehydes and phenols are unstable, unsaturated and prone to polymerize into large molecules especially with the existence of acid.
This will lead to an increase of viscosity of bio-oil and poor uidity
in transportation. Hydrogen bonds are formed among acids,
phenols and water in bio-oil and the polarity of bio-oil makes it
rather difcult to separate undesirable compounds and convert
them individually. Consequently, an upgrading process is urgently
required for its efcient utilization as transportation fuels in the
future. Since the reactions in bio-oil upgrading system are very

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Q. Dang et al. / Fuel 103 (2013) 683692

complicated, the mechanisms of bio-oil upgrading are unknown.


Up till now, model compounds of bio-oil are commonly used to
study the kinetics of bio-oil upgrading [57].
Traditional techniques like hydrodeoxygenation (HDO) [8],
catalytic cracking [9], steam reforming [10,11], esterication [12]
and emulsication [13] were extensively employed in bio-oil
upgrading process. HDO aimed at removing oxygen from bio-oil
through hydrogenation to improve the qualities of products. It usually required high pressure hydrogen. Elliott reviewed the development status of catalytic hydroprocessing of biomass-derived liquid
products [14]. Subsequently the chemical mechanisms of catalytic
hydroprocessing of bio-oil using representative model compounds
were studied by Elliott and Hart [5]. As for cracking, atmosphere
operation was feasible and no hydrogen was needed but serious
coking problem was unavoidable. Steam reforming was to produce
hydrogen rich syngas through the reaction of bio-oil with steam at
a higher temperature and coke formation was also a main
difculty.
Recently, a new method to upgrade bio-oil from fast pyrolysis
using supercritical uids has drawn great attention. This method
makes good use of the unique and superior properties of supercritical reaction media, such as faster rates of mass and heat transfer,
liquid-like density and dissolving power, gas-like diffusivity and
viscosity [15,16]. It aims at transforming undesirable oxygenated
compounds into stable, combustible and desirable ones. Peng
et al. [17,18] did some initial work to upgrade bio-oil in supercritical ethanol under N2 atmosphere with Al2(SiO3)3 catalyst and in
subcritical and supercritical ethanol using HZSM-5 as catalyst. Li
et al. [19,20] upgraded low boiling fraction of bio-oil with different
catalysts, Pt/Al2(SiO3)3, Pt/C and Pt/MgO while high boiling fraction
of bio-oil was upgraded over a series of supported monometallic
and bimetallic catalysts under H2 atmosphere in supercritical
methanol. Tang et al. [21,22] investigated one step reaction of
bio-oil upgrading through hydrotreatment, esterication, and
cracking in supercritical ethanol under H2 atmosphere using
Pd=SO24 =ZrO2 =SBA-15 catalyst. They also used different catalysts
Ru/ZrO2/SBA-15 and Ru=SO24 =ZrO2 =SBA-15 to study catalytic
hydrocracking of pyrolytic lignin to liquid fuel in supercritical
ethanol.
Most of the previous reported work about bio-oil upgrading in
supercritical solvents mainly focused on the study of different catalysts. Little work had been done on investigating important inuential parameters like initial hydrogen pressure, the mass ratio of
solvent to bio-oil and reaction temperature on bio-oil upgrading
process.
In this study, a series of experiments were carried out to
investigate the inuence of experimental parameters on the
upgrading performance. The bio-oil upgrading process was carried out in supercritical ethanol under H2 atmosphere with
bifunctional 5% Pt=SO24 =ZrO2 =SBA 15 catalyst, which was
proved to be a kind of efcient catalyst in our previous work.
The objective of upgrading was to convert these undesired products of crude bio-oil (acids, phenols, aldehydes, sugars) into relatively stable, combustible and desired ones (esters, alcohols,
ketones, ethers) using the combined advantages of supercritical
ethanol and bifunctional catalysts. The inuence of initial hydrogen pressures (0.5 MPa, 2.0 MPa), the mass ratios of ethanol to
bio-oil (5:1, 3:1, 2:1, 1:1) and reaction temperatures (260 C,
280 C, 300 C) were investigated. The upgrading results of these
runs were analyzed. The physical properties and chemical components of crude bio-oil and different upgraded bio-oil were compared. Then the mass and energy balance of certain cases were
calculated, which were very important to illustrate and understand the upgrading process. Finally, some conclusions were
made based on the results.

2. Experimental
2.1. Materials
The crude bio-oil used in this experiment was obtained from
fast pyrolysis of rice husk, which was provided by University of Science and Technology of China. SBA-15 employed was purchased
from Nanjing XFNANO Materials Tech Co., Ltd. Zirconium nitrate
pentahydrate (ZrNO35H2O), cetyltrimethylammonium bromide
(CTAB), chloroplatinic acid (H2PtCl66H2O), sulfuric acid, anhydrous
ethanol were purchased from Sinopharm Chemical Reagent Co.,
Ltd. All these chemicals were used as received without further
purication.
2.2. Catalysts preparation
The catalyst used in this work was bifunctional mesoporous
catalyst with metallic and acid sites. Platinum was loaded on modied SBA-15, designated as 5% Pt=SO24 =ZrO2 =SBA 15 (Pt/SZr),
where 5% was the weight percentage of Pt. ZrO2/SBA-15 and
SO24 =ZrO2 =SBA-15 (designated as SZr) catalysts were prepared
by a two-step wetness impregnation method according to reference [23]. Pt/SZr was prepared by incipient wetness impregnation
method. The obtained catalyst was reduced at 450 C under H2
atmosphere for 3 h with a heating rate of 10 C/min. After purging
with nitrogen when cooling, Pt/SZr catalyst was sealed using ethanol. The ow rates of hydrogen and nitrogen were each held at
50 ml/min.
2.3. Catalysts characterization
An XPert PRO X-ray diffractometer using Cu Ka radiation was
employed to conduct the X-ray diffraction (XRD) measurement
and the diffraction patterns of the catalysts were recorded over a
2h range of 1070 for wide angle.
Nitrogen adsorption/desorption isotherms were acquired from
a Micromeritics TRISTAR 3020 system to determine the textural
properties of SBA-15 support and 5%Pt=SO24 =ZrO2 =SBA-15. The
specic surface areas were obtained from a standard Brunauer
EmmettTeller (BET) equation with a relative pressure of 00.2.
The total pore volume was derived from the adsorption and
desorption branches of the nitrogen isotherms at the single point
of P/P0 = 0.97. The average pore sizes were calculated from the
adsorption and desorption branches using BarretJoynerHallenda
(BJH) method.
2.4. Experimental process
The following series of experiments were carried out in a
100 ml high-pressure autoclave reactor. First, crude bio-oil was upgraded with the mass ratio of ethanol to bio-oil equal to ve at
three different temperatures (260 C, 280 C, 300 C) under two
different initial hydrogen pressures (0.5 MPa, 2.0 MPa). Then the
experiments were conducted with certain mass ratios of ethanol
to bio-oil (5:1, 3:1, 2:1, 1:1) at temperatures (260 C, 280 C,
300 C) with 2.0 MPa hydrogen. As for 5:1, 3:1, 2:1, 1:1, the mixed
reactants consisted of 30 g ethanol and 6 g bio-oil, 27 g ethanol and
9 g bio-oil, 24 g ethanol and 12 g bio-oil, and 18 g ethanol and 18 g
bio-oil, respectively. A total amount of 36 g mixed reactants as well
as 0.3 g catalyst were loaded into the reactor for each catalytic
reaction. The reactor was ushed with nitrogen and then hydrogen
several times to remove the residual air. After adding a certain
amount of hydrogen into the reactor at room temperature, the
reactor was heated to specied reaction temperature with an electrical heating system and the experiments were carried out at that

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Q. Dang et al. / Fuel 103 (2013) 683692

Intensity (a.u.)

steady temperature for 3 h with a stirring speed of 500 rpm. When


the reaction system was heated to 260 C, 280 C and 300 C, the
reaction pressures ranged from about 7.011.8 MPa. The mixed
products taken out from the reactor in each reaction were ltered
under vacuum. The liquid and solid products were separated and
analyzed while the gases were released and not analyzed in this
work (gas products were collected and identied only in three
cases) since our main concern was focused on liquid products.
The detailed experimental conditions of different cases are listed
in Table 1.

2.5. Products characterization

SBA-15
5%Pt/SZr

10

The chemical compounds in crude bio-oil and upgraded bio-oil


were identied by a Voyager GCMS system with DB-wax capillary
column (30 m  0.25 mm  0.25 lm) using a suitable temperature
programming. The oven temperature was controlled at 40 C for
3 min, and then heated to 180 C at a rate of 4.0 C/min. Subsequently it was heated to 260 C at a rate of 10C/min and kept at
this nal temperature for 10 min. The data were acquired by the
use of NIST mass spectra library. Area normalization method was
used to determine the relative content of specic component.
The ethanol content in liquid product was measured using an
external standard method by Agilent 7890A GC with an Hp-5 column (30 m  0.25 mm  0.25 lm). The GC operational conditions
were the same as that in GCMS. The composition of gas products
was analyzed by Agilent 7890A GC with combined FID and TCD
using an external standard method. The calibration gas mixture
(including H2, CH4, CO, CO2, C3H8, C3H6, C2H4, C2H6, O2, N2) provided by Hangzhou Xinshiji Gases Mixed Co,. Ltd. was used to identify gas products distribution. The solid products were recovered
and considered to be coke deducting catalyst. They were used to
calculate coke deposition. The physical properties such as heating
value, water content and pH value of crude bio-oil and upgraded
bio-oil were measured with bomb calorimeter, Karl Fischer moisture titrator and automatic potentiometric titrator, separately.

20

30

40

50

60

70

2 (degree)
Fig. 1. X-ray diffraction patterns of SBA-15 and 5%Pt/SZr.

3. Results and discussion


3.1. Catalysts characterization results
The XRD patterns of SBA-15 and 5%Pt/SZr in wide angle region
of 1070 are shown in Fig. 1. It was obviously found that there
were new peaks appeared in the diffraction pattern of 5%Pt/SZr
compared with that of SBA-15. The four peaks displayed at
30.12, 34.96, 50.22, 59.74were ascribed to the characteristic
diffraction peaks of ZrO2. It implied the post-incorporation of
ZrO2 on SBA-15 support. But no peaks of Pt oxides were observed,
indicating Pt crystal was highly dispersed on the prepared catalyst.
The N2 adsorption/desorption isotherms of SBA-15 and 5%Pt/SZr
are shown in Fig. 2. According to IUPAC classications [24], these
two isotherms exhibited a type IV pattern and both showed clear
type H1 hysteresis loops in the relative pressure of 0.50.8. The
presence of hysteresis loops due to capillary condensation in mesopores indicated the materials had regular mesoporous channels.
The similar type inferred 5%Pt/SZr retained intact and ordered

Table 1
The physical properties of liquid and solid products in different cases.
Sample

Liquid product
Yliquida

Upgraded bio-oil
Case

Mass ratio
Ethanol/biooil

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Crude
a
b
c
d

5:1
5:1
5:1
5:1
5:1
5:1
3:1
3:1
3:1
2:1
2:1
2:1
1:1
1:1
1:1
bio-oil

Reaction
temperature
(C)

Initial H2
pressure
(MPa)

(wt.%)

260
280
300
260
280
300
260
280
300
260
280
300
260
280
300

0.5
0.5
0.5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0

99.37
99.09
99.06
99.81
99.74
99.75
99.65
99.64
99.48
99.53
99.38
99.36
98.47
97.79
95.47

Ethanol
fraction
(wt.%)

Water
fraction
(wt.%)

Oil
fraction
(wt.%)

pH

66.70
63.85
63.33
66.14
63.31
64.60
60.28
61.26
60.78
54.53
54.49
51.12
38.68
40.43
38.45
0

9.70
9.53
10.20
8.92
9.20
8.97
14.77
15.51
15.51
18.78
19.50
19.49
27.65
25.70
28.21
41.84

23.60
26.62
26.47
24.94
27.49
26.43
24.95
23.23
23.71
26.69
26.01
29.39
33.67
33.87
33.34
58.16

5.41
5.70
5.75
5.42
5.84
5.88
5.14
5.38
5.46
4.88
5.15
5.23
4.50
4.74
4.80
3.22

Yliquid is dened as 100% Ycoke. Gas product was ignored here.


Bomb caloric value deducting ethanol.
Bomb caloric value deducting ethanol and water.
Ycoke is dened as weight of solid product/(the weight of ethanol input + the weight of crude bio-oil input)  100%.

Heating
valueb
(MJ/kg)

Heating
valuec
(MJ/kg)

19.45
20.71
20.68
20.23
20.89
20.92
17.94
17.30
17.87
16.27
16.67
17.35
14.99
15.90
14.18
12.73

27.44
28.13
28.65
27.47
27.88
28.02
28.56
28.86
29.56
27.71
29.17
28.87
27.31
27.97
26.17
21.89

Solid
product
Ycoked
(wt.%)

0.63
0.91
0.94
0.19
0.26
0.25
0.35
0.36
0.52
0.47
0.62
0.64
1.53
2.21
4.53

Q. Dang et al. / Fuel 103 (2013) 683692

Quantity Adsorbed cm3 /g STP

686

600

SBA-15
5%Pt/SZr

500
400
300
200
100
0
0.0

0.2

0.4

0.6

0.8

1.0

Relative Pressure P/P0


Fig. 2. N2 adsorption/desorption isotherms of SBA-15 and 5%Pt/SZr.

Table 2
Textural properties of catalysts.
Sample

BET surface area


(m2/g)

Pore volume
(cm3/g)

Average pore diameter


(nm)

SBA-15
5%Pt/SZr

530.41
340.96

0.89
0.51

6.47
5.76

mesoporous structure after loading Pt, SO24 and ZrO2 on SBA-15


support. The parameters of textural properties of the catalysts
are summarized in Table 2. The specic surface area and pore volume of 5%Pt/SZr decreased evidently after incorporation while the
average pore diameter was slightly reduced. It implied the incorporation of Pt, SO24 and ZrO2 occupied the surface or inside pore
channels of SBA-15 and the properties of the catalyst were
changed.

3.2. Evaluation of catalytic upgrading process


Crude bio-oil used in this study was a dark brown liquid with
smoky odor. Table 1 shows the physical properties of liquid and solid products in different cases. Crude bio-oil has a high water content of 41.84%, which was a great contributor to high oxygen
content and poor ignition quality of bio-oil. The heating value of
crude bio-oil was 12.73 MJ/kg and it could get to 21.89 MJ/kg after
deduction of water. The pH was as low as 3.22 at room temperature. The liquid product was composed of organic compound (designated as oil), water and leftover ethanol. It was notable that gas
wasnt mentioned here since it only accounted for a very small proportion in mass balance according to the experiments so that it
was ignored. But it will be further illustrated later. After the
upgrading processes, the pH values were elevated from 3.22 of
crude bio-oil to more than 5.41 and 5.14 at the mass ratios of 5
and 3, respectively, which were mainly attributed to the removal
of acids. The pH values at the mass ratios of 2 and 1 were much
lower. It seemed that the heating value of liquid product deducting
ethanol was strongly inuenced by the mass ratio and it decreased
with the mass ratio varying from 5 to 1. The heating values of upgraded bio-oils after deducting the content of ethanol and water
were almost elevated to more than 27 MJ/kg compared with
21.89 MJ/kg of crude bio-oil, which evidently indicated the effectiveness of the upgrading processes. Considering the solid product,
it was observed that almost no coke was detected in the bottom of
the reactor after upgrading with relatively higher mass ratio and
initial hydrogen pressure and it was consistent with the calculated

coke yield. With the mass ratio as low as 1, coke formation was a
major problem in the upgrading process and the coke yield reached
a maximum of 4.53%. Meanwhile it obviously showed the coke
yield was much lower at hydrogen pressure of 2.0 MPa than that
of 0.5 MPa at the same mass ratio of 5. From the simple analysis
of physical indicators, the upgraded bio-oil with the mass ratio of
5 and 3 under 2.0 MPa initial hydrogen pressure (Case 49)
performed much better.
In order to evaluate the catalytic upgrading process, the physical properties should be combined with organic compounds of upgraded bio-oil to analyze. The relative content (GCMS) of typical
organic compounds of crude bio-oil and upgraded bio-oil in chosen
cases (Case 49) are shown much more clearly in Table 3. Bio-oil
was mainly composed of acids, phenols, aldehydes, sugars, esters,
alcohols, ketones and ethers. The composition of upgraded bio-oil
in different cases was similar to some extent and it implied the
similar transformation pathways of typical compounds.
The relative content of undesired and desired products of crude
bio-oil and upgraded bio-oil in different cases were compared in
Fig. 3. It clearly suggested that the amount of desired products increased greatly from 56.09% in crude bio-oil to a maximum of
84.17% with the mass ratio of 3 at 260 C under 2.0 MPa hydrogen
atmosphere. The total proportion of esters, alcohols, ketones and
ethers rose greatly with declining of the content of acids, phenols,
aldehydes and sugars. It demonstrated the validity of upgrading
process. All cases performed well with desired products increased
drastically to higher than 75% except experiments of the mass ratio
of 1, which were in agreement of the results of physical properties.
The results also suggested that the relatively lower temperature of
260 C exhibited much better upgrading performance with the
same mass ratio.
3.2.1. Effect of initial hydrogen pressure
From our previous experimental experiences, it was generally
found that the reaction system under hydrogen atmosphere beneted the upgrading process particularly with the combined effect
of bifunctional catalyst. Therefore, 0.5 Mpa and 2.0 Mpa initial
hydrogen pressures were selected to further testify their inuences
on upgrading performances with the mass ratio of 5 under 260 C,
280 C and 300 C. As shown in Fig. 4, acids were totally removed
at 260 C under both hydrogen pressures mainly due to esterication while more acids were left under 0.5 MPa both at 280 C and
300 C than that of 2.0 MPa. The relative content of aldehydes
was much lower at 2.0 MPa than 0.5 MPa at the same temperature,
which implied hydrogen atmosphere was benecial to the transformation of aldehydes. But from the products distribution, it
was found that aldolization and etherication reactions took place
mainly rather than hydrogenation of aldehydes. Sugars were completely removed at every experimental condition. However, the
amount of phenols showed opposite results that the content of remained phenols under 2.0 MPa was much larger than that under
0.5 MPa at the same temperature. This phenomenon was more
obvious at 300 C. It can be explained by that fact phenols derived
from lignin of biomass were difcult to be hydrogenated under
such circumstances. The hydrogenation of phenols usually took
place at 300500 C with 45 MPa hydrogen along with hydrogenation catalyst [25]. So the larger decrease of phenols in 0.5 MPa
should be attributed to polymerization reactions during the
upgrading process according to higher coke yield in Table 1.
In short, the total amount of desired products increased slightly
under 2.0 MPa (80.36%, 78.40%) in contrast to that of 0.5 MPa
(79.10%, 76.68%) at 260 C and 280 C, respectively. The heating
values of upgraded bio-oil under these two different hydrogen
pressures seemed irregular but all of them were greatly elevated
to more than 27.44 MJ/kg. However, the coke yields under
2.0 MPa were much lower than that under 0.5 MPa with the same

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Q. Dang et al. / Fuel 103 (2013) 683692


Table 3
Comparison of relative content of typical organic compounds in crude bio-oil and upgraded bio-oil (Cases 49).
Compound

Acids
Acetic acid
Esters
Acetic acid, methyl ester
Ethyl acetate
Propanoic acid, ethyl ester
Butanoic acid, ethyl ester
Propanoic acid, 2-(1-ethoxyethoxy)-, ethyl ester
Propanoic acid, 2-hydroxy-, ethyl ester
Butanoic acid, 2-hydroxy-, ethyl ester
Acetic acid, hydroxy-, ethyl ester
2-Furanmethanol, tetrahydro-, acetate
Pentanoic acid, 4-oxo-, ethyl ester
2-Furancarboxylic acid, ethyl ester
Diethyl methylsuccinate
Butanedioic acid, diethyl ester
Butanoic acid, 2-(hydroxymethyl)-, ethyl ester
Butanoic acid, propyl ester
Phenols
Phenol, 2-methoxyPhenol, 2-methoxy-4-methylPhenol
Phenol, 4-ethyl-2-methoxyPhenol, 4-methylPhenol, 2-methoxy-4-propylPhenol, 4-ethylPhenol, 2,6-dimethoxyPhenol, 2-methoxy-4-(1-propenyl)1,2-Benzenediol
1,2-Benzenediol, 4-methylAldehydes
Acetaldehyde
2-Butenal
Acetaldehyde, hydroxyFurfural
Vanillin
Alcohols
Methyl Alcohol
1-Propanol, 2-ethoxy2-Furanmethanol, tetrahydroPropylene Glycol
1,2-Ethanediol
1,2-Butanediol
Ketones
2-Butanone, 3-hydroxy2-Propanone, 1-hydroxy2-Cyclopenten-1-one, 2-methyl2-Cyclopenten-1-one
1-Hydroxy-2-butanone
2-Propanone, 1,1-dimethoxy2-Propanone, 1-(acetyloxy)2(3H)-Furanone, 5-ethyldihydro-5-methyl2-Cyclopenten-1-one, 2-hydroxy-3-methyl2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)Ethers
Ethyl ether
Ethane, 1-ethoxy-1-methoxyEthane, 1,1-diethoxyButane, 1,1-diethoxy2-Ethoxypentane
Furan, tetrahydro-2,5-dimethoxyMethoxyacetaldehyde diethyl acetal
Methane, dimethoxy2-Methoxy-1,3-dioxolane
Propane, 2-ethoxy5-Isopropyl-3,3-dimethyl-2-methylene-2,3-dihydrofura
Sugars
1,4:3,6-Dianhydro-a-d-glucopyranose

Relative content (area%)


Crude bio-oil

Case 4

Case 5

Case 6

Case 7

Case 8

Case 9

10.52

1.25

1.73

2.29

2.12

16.98

16.03

13.54

17.30

1.30
17.12

2.63

1.55
4.25
1.48
1.97
2.99
2.62

2.37

1.85

1.72
5.96
2.36

1.32
5.40
1.77

1.25
1.66

1.71

1.53
1.50

2.22

3.67

4.65
3.03
3.26
1.53
2.31

3.44
2.60
2.45
1.87
1.39

2.44
1.94
1.44
4.89
1.90

2.89

3.40
2.61
2.54
2.05
1.51
1.60
3.15

2.80

1.73

2.21

3.01

1.15
18.04
1.61
0.97
1.42
4.50
1.35
1.90
3.05
2.01
1.00
1.60

1.69
1.44
2.92

2.28

1.83
5.33
2.20
1.36

1.44
5.57
1.94

1.69

1.62
1.14

3.79
2.84
2.77
2.09
1.59
1.90
3.05

3.40
2.58
2.63
1.95
1.52
1.82
2.99

1.08
3.29
2.69
2.79
2.31
1.57
2.01
3.57

2.98
2.12
2.07
1.43
1.10
2.00

1.57

4.26
2.84

2.39

2.34

13.06

16.39

1.48

2.98

2.84

1.08
2.65
1.10
20.29
2.58
2.71
1.37

10.74

1.66
2.97
2.12

1.93
5.33
1.46
1.63
1.51
1.50
2.29

1.43

1.61

1.26

1.46

2.41
21.39

3.46

2.30
28.73
1.33
2.63

2.37

2.41

2.00
23.22

1.59
3.32
1.09

1.31
1.66
1.92

1.16
1.23
4.41
1.94
1.56
2.96
1.29

2.20
23.09

1.85
4.20

1.36
1.69
2.17

1.96

1.82
13.83

1.25
2.33
27.75

6.12
1.63

1.59
1.10
1.17

1.19
2.05
1.53

688

Q. Dang et al. / Fuel 103 (2013) 683692

100

Relative content (area%)

90

Undesired products
Desired products

80
70
60
50
40
30
20
10

C
ru
de

bi
o
C -oi
as l
C e1
as
C e2
as
C e3
as
C e4
as
C e5
as
C e6
as
C e7
as
C e8
a
C se
as 9
C e1
as 0
C e1
as 1
C e1
as 2
C e1
as 3
C e1
as 4
e
15

Fig. 3. Relative content of undesired and desired products of crude bio-oil and
upgraded bio-oil in different cases.

50

Relative content (area%)

45
40
35

Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers

30
25
20
15

phenols arrived at a maximum with the mass ratio of 1 whatever


the temperature was. It indicated phenols were much more difcult to be converted with lower mass ratio. The proportion of aldehydes decreased almost with the mass ratio ranging from 5 to 1 at
the same temperature.
The results of relative content showed that the amount of desired products arrived at the lowest level with the mass ratio of
1 (72.24%, 61.28% and 61.54%) although it was still larger than that
of crude bio-oil (56.09%). It suggested that the upgrading process
with the mass ratio of 1 was inferior to higher mass ratios. The
amount of desired products with different mass ratios at different
temperatures was relatively hard to compare. So the average value
was chosen to analyze. It was 77.39%, 79.36%, 79.20% and 65.02%
with the mass ratio of 5, 3, 2 and 1, respectively. The heating values
of upgraded bio-oil deducting ethanol and water with a certain
mass ratio did not vary greatly and the average values were
27.79 MJ/kg, 28.99 MJ/kg, 28.58 MJ/kg and 27.15 MJ/kg of the corresponding mass ratio of 5, 3, 2 and 1. The heating values were
consistent with the amount of desired products that it behaved
worst with the mass ratio of 1 while much better with the mass ratios of 5 and 3. The coke yield implied strict discipline that the coke
formation became much more serious with the decreasing of the
mass ratio from 5 to 1 at the same level of temperature. The cases
of the mass ratio of 1 were the worst and that of 5 performed best.
The coke yields were 0.19%, 0.26% and 0.25% with the mass ratio of
5 at temperatures of 260 C, 280 C, 300 C. In Case 15 with the
mass ratio of 1 at the reaction temperature of 300 C, the recovered
solids were tar-like products. In summary, the upgrading process
of the mass ratio of 3 performed much better considering the average values of physical indicators while the cases of the mass ratio
of 5 presented best results considering the coke yield.

10
5
0

Crude bio-oil Case 1


0.5MPa
260
5:1

Case 4
2.0MPa
260
5:1

Case 2 Case 5 Case 3


0.5MPa 2.0MPa 0.5MPa
280
280
300
5:1
5:1
5:1

Case 6
2.0MPa
300
5:1

Fig. 4. Effect of initial hydrogen pressure on distribution of undesired and desired


products.

condition, which indicated that higher hydrogen pressure inhibited


coke formation evidently. It suggested that high pressure of hydrogen made a good contribution to reaction system by enhancing the
pressure of upgrading system and heat transfer of chemical reactions. Meanwhile, more hydrogen improved the activity of hydrogenation catalyst. Compared with crude bio-oil, the upgrading
process in Case 4 of 2.0 MPa hydrogen pressure at 260 C presented
best result, the proportion of desired products was the highest
80.36% and the coke yield was the lowest 0.19%. The heating value
of upgraded bio-oil was improved to 27.47 MJ/kg from 21.89 MJ/kg
of crude bio-oil.

3.2.2. Effect of the mass ratio of ethanol to bio-oil


Fig. 5 shows the product distribution of different mass ratios at
specied reaction temperature under 2.0 MPa hydrogen pressure.
It was observed that the inuence of the mass ratio on distribution
of products was not entirely the same when the reaction temperatures were 260 C, 280 C and 300 C, but the results could still
illustrate the phenomenon. The amount of acids increased with
the declining of the mass ratios from 5 to 2 nearly at three levels
of temperature. However, esters showed the same discipline. So
we may conclude esters were produced not only by the esterication of acids but from other converting process. The content of

3.2.3. Effect of reaction temperature


The product distribution at different reaction temperatures under 2.0 MPa hydrogen pressure with the same mass ratio is presented in Fig. 6. It was observed that the inuence of reaction
temperature on distribution of products was relatively evident
and similar with different mass ratios. The amount of esters decreased obviously with the increasing of reaction temperatures
from 260 C to 300 C at every mass ratio mainly due to the acceleration of hydrolysis of esters and other converting pathways of esters at higher temperature level. Ketones exhibited the same rule
as esters and the decrease of ketones may not be caused by hydrogenation since corresponding products were not detected in GC
MS analysis. The relative content of alcohols seemed rather complicated with different temperatures even if the mass ratio was
certain. The percentage of ethers increased evidently with the temperature rising at a specic mass ratio. The product distribution of
ethers indicated the participation of ethanol in aldolization and
reactions of ethanol itself in etherication.
The relative content of desired products showed that the proportion of desired product arrived at a maximum at 260 C
(80.36%, 84.17%, 81.54% and 72.24%) with the mass ratio of 5, 3,
2 and 1, respectively. It suggested that upgrading process at
260 C performed much more better. The heating values of upgraded bio-oil without ethanol and water were increased with
reaction temperature raised when the mass ratio was 5 and 3
and it arrived at 28.02 MJ/kg and 29.56 MJ/kg at 300 C. As for
cases with the mass ratio of 2 and 1, the heating values presented
a maximum at 280 C (29.17 MJ/kg and 27.97 MJ/kg). But the heating values at 280 C and 300 C were slightly larger than that of
260 C. It may be explained that at rather higher temperatures,
the content of phenols and ethers were much larger and it made
good contributions to the increasing of heating value. The coke
yield showed strong regularity that reactions at high temperature
directly led to much serious coke formation with this super acid

689

Q. Dang et al. / Fuel 103 (2013) 683692

Relative content (area%)

45
40
35

(b) 50

Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers

45
40

Relative content (area%)

(a) 50

30
25
20
15
10
5
0

35

Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers

30
25
20
15
10
5

Crude bio-oil

Case 4
5:1
260
2.0MPa

Case 7
3:1
260
2.0MPa

(c)

Case 10
2:1
260
2.0MPa

50

Relative content (area%)

45
40
35

Case 13
1:1
260
2.0MPa

Crude bio-oil

Case 5
5:1
280
2.0MPa

Case 8
3:1
280
2.0MPa

Case 11
2:1
280
2.0MPa

Case 14
1:1
280
2.0MPa

Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers

30
25
20
15
10
5
0

Crude bio-oil

Case 6
5:1
300
2.0MPa

Case 9
3:1
300
2.0MPa

Case 12
2:1
300
2.0MPa

Case 15
1:1
300
2.0MPa

Fig. 5. Effect of the mass ratio of ethanol to bio-oil on distribution of undesired and desired products ((a) 260 C; (b) 280 C; (c) 300 C).

catalyst. The cases of 260 C performed comparatively well at various mass ratios and the coke yields were 0.19%, 0.35%, 0.47% and
1.53% with the mass ratio of 5, 3, 2 and 1. In short, the performances of upgrading process suggested that the coke yields were
much lower at 260 C and the amount of desired products reached
the maximum at 260 C. But the upgrading behaved slightly better
at 280 C and 300 C when the heating values of upgraded bio-oil
were taken into account.
3.3. Mass and energy balance
From the discussion above, the upgrading performances with
the mass ratio of 5 under 2.0 MPa were relatively much better.
So in our experiments, gas products in these three cases were identied and listed in Table 4. As can be seen from Table 4, gas products detected here included H2, CH4, CO, CO2, C2H4, and C2H6, and
the majority of gas after reaction was H2. Zhao and Lercher also
found that 99% of gas products were H2 in pyrolysis oil upgrading
under hydrogen atmosphere [26]. The H2 proportion in gas products slightly decreased from 260 C in Case 4 to 300 C in Case 6,
which meant that more H2 participated in the bio-oil upgrading
process with higher reaction temperature. Other gas products,
including CH4, CO, CO2, C2H4 and C2H6, increased with rising temperature, and it indicated more gas products were produced at
higher reaction temperature. Table 5 showed the results of mass
balance of Case 46. It was worth noting that the solid and gas

products were measured while the content of liquid product were


obtained by difference method because the difculty of liquid
product mass loss caused by collection could be solved in this
way. From the gas analysis of Case 46, it was observed that the
amount of gas input and output were very close and it accounted
for a very small proportion in the mass balance calculation, so in
order to simplify the problem, gas products in the reaction system
were not considered in oil yield analysis.
Table 6 was a summary of the mass ratio of consumed ethanol
to oil, oil yield and energy efciency in different cases. From the results, it was found that the mass ratios of consumed ethanol to oil
were greatly inuenced by the mass ratio input in the reaction system. With the mass ratio of ethanol to bio-oil ranging from 5 to 1,
the mass ratio of consumed ethanol to oil decreased regularly from
about 2 to 0.4. It also suggested that when the mass ratio of ethanol
to bio-oil was certain, the mass ratio of consumed ethanol to oil
were relatively larger at higher reaction temperature. The results
of oil yields exhibited that with the mass ratio of 5 under
2.0 MPa hydrogen, the oil yields were the highest and all of them
were above 90%. The energy efciencies were calculated based
on the mass and heating value of upgraded bio-oil and consumed
ethanol. The energy efciencies seemed irregular at different reaction temperatures within the same mass ratio of ethanol to bio-oil.
But the results still implied that most of the energy efciencies
were close and above 90% with certain mass ratios. The average value of the energy efciencies was highest for Case 46 with the

690

Q. Dang et al. / Fuel 103 (2013) 683692

50
45

Relative content (area%)

(b) 50

Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers

40
35
30
25
20
15
10
5

Crude bio-oil

50

Case 4
260
5:1
2.0MPa

Case 5
280
5:1
2.0MPa

35
30
25
20
15
10

35

Crude bio-oil

(d) 50

30
25
20
15
10
5

Case 7
260
3:1
2.0MPa

Case 8
280
3:1
2.0MPa

Case 9
300
3:1
2.0MPa

Case 13
260
1:1
2.0MPa

Case 14
280
1:1
2.0MPa

Case 15
300
1:1
2.0MPa

Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers

45

Relative content (area%)

40

Case 6
300
5:1
2.0MPa

Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers

45

Relative content (area%)

40

(c)

Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers

45

Relative content (area%)

(a)

40
35
30
25
20
15
10
5

0
Crude bio-oil

Case 10
260
2:1
2.0MPa

Case 11
280
2:1
2.0MPa

Case 12
300
2:1
2.0MPa

Crude bio-oil

Fig. 6. Effect of reaction temperature on distribution of undesired and desired products ((a) 5:1; (b) 3:1; (c) 2:1; (d) 1:1).

Table 4
Volume fraction of gas products of Case 46.

Case 4
Case 5
Case 6

H2

CH4

CO

CO2

C2H4

C2H6

99.42
98.78
97.37

0.07
0.22
0.52

0.15
0.25
0.49

0.34
0.55
0.99

0.02
0.06
0.22

0.02
0.14
0.40

mass ratio of 5 under 2.0 MPa hydrogen. It was noticeable that in


Case 14, the energy efciency calculated was very high may due
to a relatively small amount of consumed ethanol and water produced in the reactions. But the upgrading performance of Case 14
was rather bad considering other indicators such as lower pH value
and lower proportion of desired product, which can be seen from

Table 1 and Fig. 3. Meanwhile in Case 15, the energy efciency


was lowest because of serious coke formation.
It should be addressed that in the calculation of energy balance
in Table 7, the heating values of oil were measured by bomb calorimeter while higher heating value (HHV) of other products were
chosen since bomb caloric values were very close to HHV from
calculation. As can be seen, the energy of oil increased dramatically
after reaction compared with that before reaction due to the great
increase of the mass of oil content in upgraded bio-oil since a certain amount of ethanol participated in the upgrading reactions. The
energy of gas products remained the same level as that before reaction, which was in agreement with the mass balance. It was noteworthy that the energy difference of the upgrading process was
minus and it indicated the complicated reactions of the upgrading
system were exothermic overall. It may be owed to exothermic

Table 5
Mass balance of Case 46.
Input (g)

Case 4
Case 5
Case 6

Output (g)

Ethanol

Water

Oil

H2

Ethanol

Water

Oil

Coke

Gas

30
30
30

2.51
2.51
2.51

3.49
3.49
3.49

0.09
0.09
0.09

23.76
22.72
23.18

3.20
3.30
3.22

8.96
9.87
9.48

0.07
0.09
0.09

0.10
0.11
0.13

691

Q. Dang et al. / Fuel 103 (2013) 683692


Table 6
Oil yield and energy efciency in different cases.
Case
a

Mass ratio
Yoilb (%)
Eec (%)

10

11

12

13

14

15

1.76
87.68
89.59

2.07
88.64
91.86

2.12
86.57
91.23

1.79
92.15
94.15

2.08
91.77
94.23

1.95
92.21
95.58

1.03
84.37
93.26

0.96
81.22
91.17

1.00
81.12
93.01

0.64
83.58
92.92

0.65
81.03
94.76

0.82
82.82
94.13

0.41
80.88
91.43

0.36
83.76
97.81

0.46
75.12
80.81

The mass ratio of consumed ethanol to oil.


Yoil is dened as the mass of oil after reaction/(the mass of consumed ethanol + the mass of oil before reaction)  100%.
c
Ee means energy efciency, dened as the mass of oil after reaction  the heating value of upgraded bio-oil/(the mass of consumed ethanol  the heating value of
ethanol + the mass of oil input  the heating value of oil)  100%.
b

Table 7
Energy balance of Case 46.
Input (kJ)

Case 4
Case 5
Case 6

Output (kJ)

Difference (kJ)

Ethanol

Water

Oil

H2

Ethanol

Water

Oil

Coke

Gas

890.40
890.40
890.40

0
0
0

76.38
76.38
76.38

12.90
12.90
12.90

705.14
674.44
687.84

0
0
0

246.05
275.28
265.72

2.30
2.95
2.95

12.88
12.90
12.97

reactions such as hydrogenation although esterication and cracking reactions were endothermic. The mechanism of upgrading process and the coupled reactions were still unclear.
4. Conclusions
In this study, crude bio-oil was upgraded in supercritical
ethanol with 5%Pt=SO24 =ZrO2 =SBA-15 catalyst under hydrogen
atmosphere with different reaction conditions. The pH values and
heating values of all the upgraded bio-oil were improved after
the upgrading process and the total proportion of desired products
increased greatly compared with crude bio-oil. The inuence of initial hydrogen pressures (0.5 MPa, 2.0 MPa), the mass ratios of ethanol to bio-oil (5:1, 3:1, 2:1, 1:1) and reaction temperatures
(260 C, 280 C, 300 C) were investigated.
From the inuence of initial hydrogen pressures, we concluded
that the coke yields under 2.0 MPa were much lower than that under 0.5 MPa with the same condition and it implied that higher
hydrogen pressure inhibited coke formation obviously. The effect
of the mass ratio suggested that the upgrading process behaved
better at higher mass ratio of 5 and 3 while it was worst at the
mass ratio of 1. The upgrading process with the mass ratio of 3 performed much better considering the average amount of desired
products and the heating values while the cases of the mass ratio
of 5 showed best results due to its lower coke yield. As for the
inuence of the reaction temperature, the performances of upgrading process indicated that the coke yields were much lower at
260 C and the amount of desired products reached the maximum
at 260 C. But the heating values of upgraded bio-oil at higher temperatures seemed slightly higher. In addition, the mass and energy
balance were calculated and analyzed based on the Case 46. The
oil yield and energy efciencies of different cases showed that
the cases of the mass ratio of 5 under 2.0 Mpa performed best
and it was in agreement with the above conclusions.
More progress is under investigation to search for optimal
reaction conditions for bio-oil upgrading system. And much more
work needs to be carried out to study the reaction mechanisms
in such a complicated reaction system.
Acknowledgment
We gratefully acknowledge the nancial support from the
National Science and Technology Supporting Plan through contract
(Grant No. 2011BAD22B07).

13.32
14.10
10.20

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