Supporting Information
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2011
Effective Production of Octane from Biomass Derivatives under Mild
Conditions
Wenjie Xu, Qineng Xia, Yu Zhang, Yong Guo, Yanqin Wang,* and Guanzhong Lu*[a]
cssc_201100361_sm_miscellaneous_information.pdf
1. Experimental section
1.1 Synthesis of catalysts
(I) Pt/Co2AlO4
Pt/Co-Al-CO32- hydrotalcite-like (Co-Al-CO32- HT) precursors were prepared by
co-precipitation from an aqueous solution of cobalt and aluminum nitrate (solution A) and a
basic solution (solution B). In solution A, a calculated amount of Pt nitrate was added for the
co-precipitation.[5] The as-prepared precursor was calcined at 300 °C for 4 h with a ramp of 5
°C·min-1 in air to get the corresponded Pt/Co2AlO4 catalyst. The final Pt loading in the
calcined catalyst determined by inductively coupled plasma (ICP-AES) was 1.8 wt.%.
(II) Mesoporous NbOPO4
In a typical synthesis of mesoporous niobium phosphate, 1.18g diammonium hydrogen
phosphate was dissolved in 20mL of distilled water and adjusted to pH = 2 using phosphate.
After that, 20 mL of 0.5 mol L-1 niobium tartaric solution was add to the above solution. Then
the
mixture
was
added
to
the
aqueous
solution
of
cationic
surfactant,
tetradecyltrimethylammonium bromide (CTAB) (which was prepared by dissolving 1.0g
CTAB in 13mL of distilled water at the temperature of 35 °C) and stirred at 35 °C for 60 min.
Finally, the mixture was kept in 80°C oil base for 24h with stirring, and then aged at 100°C
for another 24h. After filtering, washing with distilled water, it was dried at 50°C and
calcined at 500°C for 3h to remove surfactant.
5wt% Pt/NbOPO4 was prepared by incipient-wetness impregnation method.
1.2 Characterization of the catalysts
1
X-ray diffraction patterns (XRD) were recorded with a Rigaku D/max-2550VB/PC
diffractometer using Cu Ka radiation. Nitrogen sorption isotherms were measured at 77 K
with a Micromeritics ASAP2020M sorption analyzer. Before measurements, the samples
were outgased at 280 °C for 6 h. GC–MS was carried out using an Agilent 7890A gas
chromatograph connected to a 5975C mass spectrometer with Triple-Axis Detector.
1.3 Aldol condensation of furfural with acetone
The aldol condensation of furfural with acetone (Scheme 1, step 1) was carried out in a
batch reactor at acetone/furfural = 10-25 (molar ratio) and furfural/catalyst = 6 (weight ratio).
The batch reactor was heated up to the required temperature under magnetic stirring in an oil
bath equipped with an automatic temperature control system. The liquid of reaction was
analyzed by a PerkinElmer Clarus 500 gas chromatography with a SE-54 column. A flame
ionization detector (FID) was used to analyze the final products. The response factors were
calibrated for each reactive agent with pure chemicals.
Under the optimized conditions (140 °C, for 20h), the conversion of furfural reached
99.9% on Pt/Co2AlO4 catalyst. When the molar ratio of acetone to furfural was 10, the yields
of 4-(2-furyl)-3-buten-2-one(I) (F-A, single aldol adduct) and difurfurylideneactone (F-A-F,
double aldol adduct, which can be converted to jet) were 68% and 30%, respectively.
Increases of the molar ratio to 25, their yields were tuned to 85% and 14%, respectively.
1.4 Hydrogenation of 4-(2-furyl)-3-buten-2-one(I)
The hydrogenation reaction was carried out in a stainless autoclave containing 0.4g
4-(2-furyl)-3-buten-2-one(I), 10ml EtOH, and 0.2 g catalyst at the reaction conditions of
P(H2) = 0.5-3 MPa and T = 130-150 °C under magnetic stirring. Hydrogen was consumed
during reaction and more was supplied from time to time to maintain the pressure. After
reaction for 20 h, the reactor was cooled down to room temperature. Then, the catalyst was
separated by filtration, and the liquid was analyzed by a PerkinElmer Clarus 500 gas
chromatography with a SE-54 column and a FID. The conversion and selectivity were
2
determined based on the area normalization method. The structural characteristics of products
were further identified by GC-MS.
1.5 Dehydration/hydrogenation of C8-diols
The
dehydration/hydrogenation
of
C8-diols
(including
1,7-octanediol
15.5%,
2,5-octanediol 42.0% and 4-(2-tetrahydrofuryl)-butan-2-ol 42.5%) was carried out in a fixed
bed reactor system. The catalyst was pelletized and sieved to 40-60 mesh size. Then, 2.0 g of
catalyst was loaded in the stainless steel tubular reactor with an inner diameter of 6 mm. 3
wt% of C8-diols was fed into the reactor at a flow rate of 1.2-3.6 ml/h by an HPLC pump.
The reaction was operated at 165-185 °C and 2.5 MPa. Gaseous products were analyzed by
an on-line gas chromatograph equipped with FID and TCD detectors and a methanizer. The
liquid products were analyzed by a PerkinElmer Clarus 500 gas chromatography with a
SE-54 column and a FID detector. The conversion and selectivity were determined based on
the area normalization method. For confirmation, the amount of octane in the THF solution
was quantitated by internal standard method, and the final yield was theoretically calculated
based on 4-(2-furyl)-3-buten-2-one(I) in step 2.
3
2. Results
XRD
Pt/NbOPO4
Intensity
fcc Pt
fcc Pt
fcc Pt
10
20
30
40
50
60
70
80
2θ/degree
Figure S1. The XRD patterns of Pt/NbOPO4 catalyst.
300
Volume(cc/g)
250
200
Cumulative pore volume(cc/g)
N2 sorption
0.5
0.4
0.3
0.2
0.1
0.0
0
20
40
60
80
100 120 140 160 180
pore distribution(nm)
150
100
50
0
0.0
0.2
0.4
0.6
0.8
1.0
P/P0
Figure S2. Nitrogen sorption isotherm and pore size distribution of the NbOPO4 support.
4
NH3-TPD
16
14
Single/MW
12
10
8
6
4
2
0
100
200
300
400
Temperture
500
o
600
700
800
C
Figure S3. NH3-TPD of mesoporous NbOPO4.
100
OH
O
90
Products distribution/%
80
70
60
50
OH
OH
40
OH
O
30
20
O
O
10
OH
HO
0
0
2
4
6
8
10
12
14
16
18
20
22
24
Time/h
Figure S4. The time course of the hydrogenolysis of 4-(2-furyl)-3-buten-2-one(I) catalyzed
by Pt/Co2AlO4. Conditions: H2 (1MPa), 140 °C.
5
O
O
O
B
O
A
1MPa H2
Pt-based catalyst
I
A
O
C
III
II
J
OH
OH
OH
B
O
O
E
F
K
OH
O
O
IV
VI
OH
OH
OH
V
Scheme S1. The possible pathway of Proposed reaction pathways in hydrogenolysis of
4-(2-furyl)-3-buten-2-one(I).
MS
OH
o
Abundance
Scan 811 (5.554 min): G90116.D\data.ms (-759) (-)
81
1200000
107
1100000
1000000
900000
800000
700000
122
600000
140
500000
400000
300000
53
200000
39
68
93
27
100000
0
45
15
10
59
33
20
30
40
50
60
74
70
87
80
90
101
100
113
110
134
120
130
140
150
m/z-->
6
OH
o
Abundance
Scan 2014 (11.478 min): G90058.D\data.ms (-1875) (-)
71
2000000
1800000
1600000
1400000
1200000
1000000
800000
43
600000
84
400000
55
200000
0
29
15
10
20
30
40
50
60
93 100
77
65
37
70
80
90
100
116
109
110
120
129
130
143
140
150
m/z-->
o
o
Abundance
Scan 1280 (7.395 min): G90058.D\data.ms (-1266) (-)
87
400000
380000
360000
340000
320000
300000
56
280000
260000
98
240000
220000
200000
180000
127
160000
43
140000
120000
100000
80000
29
112
60000
70
142
81
40000
20000
0
15
10
37
20
30
40
50
50
63
60
105
70
80
90
100
110
120
130
140
150
m/z-->
7
OH
OH
OH
OH
8
O
O
9