Beruflich Dokumente
Kultur Dokumente
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan 030001, PR China
Graduate University of the Chinese Academy of Sciences, Beijing 100039, PR China
c
Synfuels China Co. Ltd, Taiyuan 030001, PR China
b
a r t i c l e
i n f o
Article history:
Received 15 September 2010
Received in revised form
10 November 2010
Accepted 14 November 2010
Available online 21 November 2010
Keywords:
Decarbonylation
Furfural
Furan
Pd/Al2 O3 catalysts
2-Methylfuran
a b s t r a c t
Vapor-phase decarbonylation of furfural to furan was performed on K-doped Pd/Al2 O3 catalysts in a xedbed reactor. A series of K-doped catalysts were prepared by impregnation method with various potassium
salt precursors and different potassium content. The catalyst evaluation results revealed that the doping of
K not only promoted the furfural decarbonylation, but also suppressed the hydrogenation side reaction.
Among the investigated catalysts, PdK2 CO3 /Al2 O3 (K% = 8 wt.%) presented the best performance and
achieved the furan yields up to 99.5% at 260 C. The selectivity of 2-methylfuran would approach zero
at high K content (K% > 4 wt.%). Furthermore, the catalysts were characterized by BET, SEM, ICP, H2 -TPR,
H2 -TPD, H2 -chemisorption, CO-FTIR, furfural-TPSR, and furfural-FTIR experiments. It was shown that the
dopant phase had a remarkable effect on the precursor Pd2+ and the reduced Pd metal particles. FurfuralTPSR and furfural-FTIR exhibited that K-doped catalysts enhanced the furfural adsorption and promoted
the decarbonylation reaction, which was due to the different adsorption mode and intensity of furfural
on K-doped and undoped samples. Besides, the decrease of CO adsorption of furfural (2 (C,O)-furfural)
by K doping is the main reason for suppressing the furfural hydrogenation.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Transformation of non-food biomass to chemicals is an important sustainability issue and has attracted much attention in recent
years [1]. Furfural, as an important chemical readily accessible from
biomass, appears to be the only unsaturated large-volume organic
chemical prepared from carbohydrate resources and is a key derivative for the production of non-petroleum-derived chemicals [2].
One important chemical coming from furfural is furan [15], which
is a useful intermediate and employed primarily in the synthesis of
tetrahydrofuran. Both vapor [3] and liquid phase [5] decarbonylation of furfural can produce furan, but vapor phase decarbonylation
is usually preferred for its simple operation, easy separation, handling and recycling of catalysts.
Some metal oxides such as iron, zinc, manganese, molybdenum,
chromium oxides, or their mixtures [68] and noble metals such as
Pd, Pt, Rh used as supported form [9,10] are employed as the catalysts for decarbonylation of furfural to furan. The main drawback
of the non-noble oxide catalysts is the drastic operating conditions,
which may bring about a signicant breakdown of furan and the for-
72
(1)
O
CHO
-CO
(3)
+2
+H
(4) +H 2 -H O 2
2
(2 )
H
CH3
(5)
O
CH2OH +2H 2
CH 2OH
2. Experimental
2.1. Catalyst preparation
-Al2 O3 , obtained from the Aluminum Co., Ltd, of China (surface
area = 233 m2 /g, 2040 mesh), was used as support. 1 wt.% Pd/Al2 O catalyst was prepared by incipient wetness impregnation.
Firstly, Pd(NO3 )2 solution was impregnated to the Al2 O3 at ambient temperature for 5 h. After that, the sample was dried overnight
at 120 C and then calcined at 450 C for 6 h. The 1 wt.% Pd/Al2 O3 is
referred to as PA.
Five different 11 wt.% for PdK/Al2 O3 catalysts were prepared
using different potassium salts (K2 CO3 , KOH, KCl, KNO3 , CH3 COOK)
as K precursors. Firstly, potassium solutions were impregnated to
the Al2 O3 for 0.5 h before Pd(NO3 )2 solutions were added in. The
subsequent drying and calcination procedures were the same as
those of the Pd/Al2 O3 . The catalysts are designed as PAX, with
X denoting the different potassium salts. For example, PAK2 CO3
designates the K in PdK/Al2 O3 catalyst coming from K2 CO3 .
Surface area
(m2 /g)
Pore volume
(cm3 /g)
Average pore
size (nm)
-Al2 O3
PA
PAK2 CO3
PAKOH
PAKCl
PAKNO3
PAKAc
196.6
191.12
184.34
182.70
178.48
176.42
193.11
0.619
0.611
0.605
0.602
0.601
0.605
0.610
9.07
9.36
9.73
9.59
9.73
9.92
9.26
73
Table 2
Characterization of the catalysts with doping different K content: surface area and pore structure, chemical composition, hydrogen chemisorption and metallic dispersion.
Catalyst
Surface area
(m2 /g)
Pore volume
(cm3 /g)
Average pore
size (nm)
Pd (wt.%)
K (wt.%)
(K/wt.%)a
H2 chemisorption
(mmol/g)
Pd dispersionb (%)
PA
PAK (0.75%)
PAK (2%)
PAK (4%)
PAK (6%)
PAK (8%)
PAK (10%)
191.12
191.82
186.46
179.77
166.28
146.62
140.10
0.611
0.609
0.590
0.563
0.520
0.497
0.456
9.36
9.42
9.23
9.03
9.09
9.02
9.40
0.86
0.80
0.89
0.89
0.92
0.87
0.88
0
0.66
1.76
3.67
4.93
6.64
8.43
0
0.09
0.24
0.33
1.07
1.36
1.57
0.00988
0.00948
0.01398
0.01644
0.01811
0.01567
0.02379
21.0233
20.1753
29.7578
34.9739
38.5475
33.3399
50.6189
a
b
The difference value of calculated value and true value determined by ICP.
Pd dispersion determined from H2 -chemisorption.
74
Fig. 2. SEM images of the surface of catalyst particles (10 m): (a) PA, (b) PAK(2%), (c) PAK(4%), and (d) PAK(8%).
results indicate that more and more K+ will be interacted with Pd2+
with the increase of K content, which lead to change the reduction
temperature. The behavior up to K/Pd = 4 reects a strong chemical interaction between K+ and Pd2+ species, which may eventually
lead to the formation of a mixed compound (KPdO) even at low K
content [15].
3.1.3. H2 -TPD and H2 chemisorption
The H2 -TPR results exhibit that the dopant phase has already
interacted with the precursor Pd2+ phase. One of the questions is
whether the interaction between K and Pd is still holding on the
reduced Pd metal particles, so the experiments of H2 -TPD and H2
chemisorption were carried out on the reduced Pd particles. The
results are shown in Fig. 4 and Table 2.
It is observed from Fig. 4 that hydrogen desorbs from the samples exhibiting three peaks centered. The low-temperature peak
is due to hydrogen chemisorption on the surface of Pd crystallites, whereas the high-temperature feature can be attributed to
spillover hydrogen associated with the support. The mediumtemperature peak has been assigned to hydrogen adsorbed on the
sites located at the periphery of Pd crystallites, which are contacted with the support [18]. K addition does not appreciably affect
the position of the low-temperature peak (at ca. 85 C). However,
the high-temperature peaks (at ca. 480 C) decrease in intensity
and have a little shift to higher temperature in the presence of
K. The reason is that K can induce the dehydroxylation of support, which is known to suppress the hydrogen spillover. Regarding
the medium-temperature peaks (at ca. 300 C), they decrease in
intensity or overlap with the high-temperature peaks except the
catalyst PA(6%). This implies that the adsorption strength of the
corresponding sites toward hydrogen decreases in the presence
of K. However, it is interesting to see that these effects do not
decrease the quantity of adsorbed hydrogen. On the contrary, the
adsorbed hydrogen is increased as indicated by the results of H2 chemisorption (Table 2), which may be due to the higher dispersion
of Pd metal particles. From the results, we may draw the conclusion that K has interacted with the reduced Pd. Then, CO-FTIR was
carried out as a complement experiment to further investigate this
interaction.
3.1.4. CO-FTIR
FTIR spectroscopy of adsorbed CO is a method for the characterization of the electronic states of supported metals. According to the
binding mode reported by Davydov [19], the carbon monoxide molecules adsorbing on metal atoms or ions interact with their
valence d-elections and the frequency of the stretching vibration
of CO bond of the surface MCO complex depends directly on the
effective charge of the adsorption.
The FTIR spectra of CO adsorbed at 20 C on Pd/Al2 O3 and the
K-doped Pd/Al2 O3 samples are displayed in Fig. 5ag. The spectra of the catalysts show three main peaks from high-frequency
region (20002100 cm1 ) to low-frequency (18002000 cm1 ).
The interpretation of CO absorption bands on supported palladium
catalysts is well dened in the literature [19,20]. The signals in the
range 18501980 and 20502100 cm1 are attributed to bridge
PdCOPd and linear PdCO species. Moreover, the two bridged
adsorption bands, from high-frequency to low-frequency, can be
attributed to the compressed and isolated bridged carbonyls [21]
or the twofold bridged carbonyls on Pd(1 0 0) and Pd(1 1 1) faces
[22], respectively. As shown in Fig. 5, the progressive increase of K
content causes a gradual modication of the CO spectra, suggesting
that the dopant has interacted with the reduced Pd metal particles.
As implied by the CO-FTIR characterization, the changes in CO
spectra with the increase of K loading can be summarized in three
main phenomena. (1) With the increase of K content, the intensity of adsorption band is increased, especially for the catalyst
PAK(8%), which shows the highest CO adsorption band. (2) The
bands I and II are progressive decrease of the intensity with respect
to the PA catalyst, and a simultaneous increase of band III. At the
8% K loadings, the spectra are dominated by the last band, which is
75
PA
PA-K(0.75)
H2 Consumption (a.u.)
PA-K(10%)
H2-Desorption (a.u.)
PA-K(2)
PA-K(4)
PA-K(6)
PA-K(8)
PA-K(10)
0
100
200
300
400
PA-K(8%)
PA-K(6%)
PA-K(4%)
PA-K(2%)
PA-K(0.75%)
500
Temperature (C)
PA
PA
100
200
300
H 2 Consumption (a.u.)
PA-K(0.75)
600
700
800
PA-K(4)
PA-K(6)
PA-K(10)
-100
100
200
300
400
500
Temperature (C)
Fig. 3. H2 -TPR proles of the investigated catalysts: (a) start at ambient temperature
and (b) start at 80 C.
2000
1900
1800 2200
2100
2000
PA-K(8)
PA-K(6)
PA-K(4)
PA-K(2)
PA-K(0.75)
PA
1900
3.1.5. Furfural-TPSR
Programmed thermodesorption of furfural and the decarbonylation products was done to verify the stability of surface species
occurring during desorption and decomposition on PA and PAK
catalysts. These experiments were performed with the adsorption
of furfural/He ow on reduced catalysts at 40 C for 1.5 h, then
purging the physisorption of furfural, after that, monitoring the
desorbing products with the online MS. Masses characteristic of
different desorption products are shown in Fig. 6, including furfural (C5 H4 O2 , 96 amu), furan (C4 H4 O, 68 amu), carbon monoxide
(CO, 28 amu) and hydrogen (H2 , 2 amu).
1800 2200
2100
2000
1800 2200
2000
2065
1878
(e) PA-K(6%)
2065
2080
1830
1934
1824
(f) PA-K(8%)
(g) PA-K(10%)
1828
1943
1953
2071
2065
2063
1948
1942
2000
1800
1959
1940
1855
1900
(c) PA-K(2%)
1979
1984
2100
2083
(d) PA-K(4%)
2100
1900
(b) PA-K(0.75%)
(a) PA
PA-K(10)
2200
500
PA-K(2)
PA-K(8)
2200
400
Temperature(C)
1900
1800 2200
2100
2000
1900
1800 2200
2100
2000
1900
Wavenumber (cm1)
Fig. 5. FTIR spectra of CO dosed at 20 C on the catalysts.
1800 2200
2100
2000
1900
1800
76
a
C
Intensity (arb.units)
(96 amu)
O
O
Furan
(68 amu)
O
Intensity (arb.units)
Furfural
PA
PA-K(4%)
PA-K(8%)
PA
PA-K(4%)
PA-K(8%)
Al2O3
100
200
300
400
500
Al 2O 3
600
100
Temperature (C)
200
300
400
500
600
Temperature (C)
d
H 2 (2 amu)
Intensity (arb.units)
Intensity (arb.units)
CO (28 amu)
PA
PA-K(4%)
PA-K(8%)
PA
PA-K(4%)
PA-K(8%)
Al2O 3
Al 2O 3
100
200
300
400
500
600
Temperature (C)
100
200
300
400
500
600
Temperature (C)
Fig. 6. Furfural-TPSR on the catalysts: (a) furfural desorption, (b) furan desorption, (c) CO desorption, and (d) H2 desorption.
350 C before the absorption of furfural, so the desorbed hydrogen was mainly coming from furfural. As shown in the gure,
H2 is desorbed more easily from PAK catalysts than from PA
catalyst. In addition, it is obvious that there are no sign of H2 desorption on Al2 O3 , which suggests that the desorbed hydrogen is
formed in the presence of Pd. During the process of reduction,
H2 can be adsorbed dissociatively on the Pd surface and further
spill to the support. As revealed by H2 -TPD, the spillover hydrogen is hardly desorbed completely lower than 350 C (Fig. 4).
Therefore, the rst desorption peak may be due to the hydrogen atoms released to the surface by the decomposition of the
furfural adlayer recombined and desorbed, while the second desorption peak may be due to the combination of two hydrogen atoms
derived from dehydrogenation of furfural and spillover hydrogen,
respectively.
3.1.6. Furfural-FTIR
To better understand the promoter effects on the decarbonylation reaction, we investigated the interaction of reduced PA and
PAK(8%) with furfural. The in situ FTIR spectra of furfural adsorbed
at different temperature on the samples are displayed in Fig. 7.
Fig. 7a shows the adsorbed acyl species of furfural on PA catalyst. At 30 C, two bands observed at 1888 cm1 and 1695 cm1 can
be attributed to physisorbed and chemisorbed furfural, which are
similar to the adsorption of benzaldehyde on Pd/Al2 O3 [23]. With
increasing the temperature, the physisorbed furfural is decreased
the intensity and the bands shift to lower frequency, while the
chemisorbed furfural only decreases the intensity. In addition, a
new band appeared at 80 C (1957 cm1 ), which is assigned to the
CO adsorption, is progressive increased the intensity with further
increase the temperature. It indicates that the increase of temperature promotes the decarbonylation of furfural.
PA
1676
1807
1695
PA-K(8%)
PA-K(8%)
o
200 C
30 C
30 C
Absorbance
50 C
80 C
80 C
o
100 C 2021 1913
100 C
150 C
150 C
1400
PA
o
30 C
200 C
1600
PA-K(8%)
o
30 C
1800
PA
o
200 C
50 C
2000
1624
1888-1850
1957-1942
77
200 C
2000
1800
1600
1400
2000
1800
1600
1400
Wavenumber (cm-1)
Fig. 7. In situ FTIR of furfural adsorbed on the catalysts at different temperature: (a) adsorbed on PA catalyst, (b) adsorbed on PAK(8%) catalyst, and (c) comparison of
K-doped and undoped catalysts.
78
100
b 100
90
90
80
80
70
60
PA
PA-K 2CO3
50
40
PA-KOH
PA-KCl
PA-KNO 3
30
20
PA-KAc
10
200
220
240
60
PA
PA-K 2CO3
50
PA-KOH
PA-KCl
PA-KNO 3
40
PA-KAc
30
0
180
70
20
260
180
200
100
90
80
70
60
50
PA
PA-K 2CO3
40
20
PA-KOH
PA-KCl
PA-KNO 3
10
PA-KAc
30
220
240
260
Temperature (C)
c
Furan and tetrahydrofuran yield (%)
Temperature (C)
16
PA
PA-K 2CO3
14
PA-KOH
PA-KCl
PA-KNO 3
12
10
PA-KAc
8
6
4
2
0
0
180
200
220
240
260
Temperature (C)
180
200
220
240
260
Temperature (C)
Fig. 8. Catalytic activity of PdK catalysts with doping different K salts in decarbonylation of furfural: (a) conversion of furfural, (b) selectivity of furan, (c) total yield of furan
and tetrahydrofuran, and (d) selectivity of 2-methylfuran. Reaction conditions: atmospheric pressure, WHSV = 0.77 h1 , H2 /furfural = 20 (molar ratio).
79
b 100
100
90
PA-K(0.75%)
PA-K(2)
PA-K(4%)
PA-K(6%)
PA-K(8%)
PA-K(10%)
80
70
90
80
70
60
PA-K(0.75%)
PA-K(2)
PA-K(4%)
PA-K(6%)
PA-K(8%)
PA-K(10%)
50
40
30
60
20
180
200
220
240
260
180
200
Temperature (C)
100
90
80
70
PA-K(0.75%)
PA-K(2)
PA-K(4%)
PA-K(6%)
PA-K(8%)
PA-K(10%)
60
50
40
30
220
240
260
Temperature (C)
20
4
PA-K(0.75%)
PA-K(2)
PA-K(4%)
PA-K(6%)
PA-K(8%)
PA-K(10%)
0
180
200
220
240
260
Temperature (C)
180
200
220
240
260
Temperature (C)
Fig. 9. Catalytic activity of PdK catalysts with doping different K content in decarbonylation of furfural: (a) conversion of furfural, (b) selectivity of furan, (c) total yield of
furan and tetrahydrofuran, and (d) selectivity of 2-methylfuran. Reaction conditions: atmospheric pressure, WHSV = 0.77 h1 , H2 /furfural = 20 (molar ratio).
80
(1)
C H
H Pd
(2)
O
C O
Pd Pd
+ CO
Pd Pd
H
C O
C+
1(C)
Pd
O
C+
Pd Pd
2(C,O)
C O
H
O
1(O)
C O
+ CO
Pd
O
(3)
O
C H
C+
1'(C)
Pd-K
O
O
C+
+ CO
Pd-K
Fig. 11. Adsorption mode of furfural on Pd/Al2 O3 and PdK/Al2 O3 catalysts.
[10]
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81