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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
684
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
685
Intensity (a.u.)
SBA-15
5%Pt/SZr
10
20
30
40
50
60
70
2 (degree)
Fig. 1. X-ray diffraction patterns of SBA-15 and 5%Pt/SZr.
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
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
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
Table 2
Textural properties of catalysts.
Sample
Pore volume
(cm3/g)
SBA-15
5%Pt/SZr
530.41
340.96
0.89
0.51
6.47
5.76
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
687
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
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
100
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
45
40
35
Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers
30
25
20
15
10
5
0
Case 4
2.0MPa
260
5:1
Case 6
2.0MPa
300
5:1
689
45
40
35
(b) 50
Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers
45
40
(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
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
690
50
45
(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
40
Case 6
300
5:1
2.0MPa
Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers
45
40
(c)
Acids
Phenols
Aldehydes
Sugars
Esters
Alcohols
Ketones
Ethers
45
(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
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
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
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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