Beruflich Dokumente
Kultur Dokumente
(2013) 6:11731182
DOI 10.1007/s12155-013-9303-x
Introduction
Biomass energy is the only renewable energy that can be
converted into fuels, chemicals and function materials, realizing
fossil energy partial substitution. Biomass is also the only
organic carbon source in the post-fossil period. In the past years,
attention has been paid to the converting solid biomass to
energy, liquid chemicals or synthesis gas by direct combustion,
gasification, pyrolysis and hydrothermal treatment [17]. Due
to the low efficiency in the combustion and gasification process,
technique shortcomings hindered their industrialization process.
Recently, biomass fast pyrolysis (BFP) has been regarded as a
promising technique that can convert biomass into fuels (biooil) with high efficiency. The direct use of bio-oil can only be
found in the boilers, and subsequent upgrading is essential for
further employment as transportation fuel or chemicals, because
of its acidity, high moisture and high oxygen content.
Catalytic hydrogenation and catalytic cracking are considered as two traditional upgrading methods to produce highgrade liquid fuels. At high pressure (1030 MPa), moderate
temperature (250400 C) and H2 supply or hydrogen donor
solvent, the aim of hydrogenation and dehydration to decrease
the content of oxygen is achieved [813]. Both the high price
of hydrogen and the high working pressure will increase the
cost, which is unfavorable for practical application. Another
technology is catalytic cracking with certain catalysts under
atmospheric pressure and high temperature. Both the deep
hydrogenation and catalytic cracking require high temperature, which inversely leads to serious coking and low product
yield. Efficient upgrading methods are expected to realize
high-value utilization of solid biomass and bio-oil. In recent
years, selective hydrogenation has been paid more and more
attention. The hydrogenating is operated under low temperature, low pressure and with appropriate catalyst. The unsaturated composition is converted to platform chemicals, like
polyols, saturated furan ring compounds, like ethylene glycol
(EG), tetrahydrofuran (THF) etc.
1174
mfeed
Mcatalyst
1175
Partial pressure
vfeed
Patmosphere
vfeed vcarrier
nspecified
Carbon yield
100%
nconverted
(b)
80
60
EG
THF
Furan
mfeed
Mcatalyst
feed
carrier
nspecified
nconverted
nproducts
40
nspecified
100%
nproducts
60
20
50
0
400
500
600
Pyrolysis temperature C
25
20
15
EG
THF
Furan
650
(a)
Carbon selectvity
EG
THF
Furan
10
40
30
20
10
5
0
400
500
600
Pyrolysis temperature (C)
650
0
400
450
500
550
600
650
700
Temperature ( C)
Fig. 2 Overall product yield distribution of three feedstocks as a
function of pyrolysis temperature: a total yield of olefin and hydrocarbon aromatic; b CO+CO2 carbon yield. Reaction conditions: WHSV,
11.2 h1; partial pressure, 12.3 Torr
1176
(a)
70
60
40
C2H4
30
C3H6
C4H8
20
C5
60
50
10
0
Benzene
Toluene
Ethyl benzene
Xylene
Others
50
40
30
20
10
400
500
600
400
500
Temperature ( C)
(b)
90
70
C2H4
60
C3H6
50
C4H8
40
C5
30
20
Carbon selectivity(%)
Benzene
Toluene
Ethyl benzene
Xylene
Others
60
70
50
40
30
20
10
10
0
600
Temperature ( C)
80
400
450
500
550
600
400
650
450
500
550
600
650
Temperature ( C)
Temperature ( C)
(c)
C2H4
C4H8
C3H6
C5
60
50
40
30
20
10
0
400
450
500
550
Temperature ( C)
600
650
Benzene
Ethyl benzene
Styrene
50
Toluene
Xylene
Others
40
30
20
10
0
400
450
500
550
Temperature ( C)
600
650
70
subsequent cyclization produced aromatics. The unfavorable aromatics continued dehydrogenation and polymerization resulting in coke formation. The coking tendency of EG
as a function of temperature was similar to that of THF.
Product selectivity of biomass derivates catalytic conversion as a function of pyrolysis temperature is shown in
Fig. 4. There was an inflection point, especially for THF
and furan, at 500 C. The olefin selectivity graph of THF
and furan also showed some similar trends in propylene and
butylene. It was inferred that THF may follow a homologous reaction pathway with furan in olefin production. The
propylene selectivity of THF was relatively higher than that
of furan, but the selectivity of butylene produced by THF
was lower than that of furan. Meanwhile, the distribution
differences of olefins were found between EG and THF, like
ethylene and propylene. The selectivity of ethylene produced by EG was 20 % higher than that of THF, while the
selectivity of propylene produced by EG is relatively lower
than that of THF. In Fig. 4(a), the selectivity of C5 decreased
notably with the increasing temperature, which can be seen
as an intermediate of EG catalytic conversion. Similar distribution trends of aromatic selectivity were found between
EG and THF, with benzene, toluene and xylene as major
aromatic products. With the increasing temperature, the
selectivity of ethyl benzene reduced for the promotion of
its decomposition at high temperature, while the selectivity
of benzene increased because the high temperature was
unfavorable for alkylation reactions. The catalytic pyrolysis
of furan also produced small amounts of styrene, naphthalene and indene. Furthermore, the selectivity of polycyclic
hydrocarbons increased while that of benzene and toluene
decreased with the increasing temperature. It should be
clarified that furan produced considerable amount of benzofuran at low temperature. Also, the yield of benzofuran was
found to decrease with the increasing temperature, which fit
in well with the data from the counterparts [19].
1177
50
EG
THF
Furan
40
30
20
10
2
10
12
14
16
-1
WHSV (h )
Fig. 5 Effect of weight hourly space velocity (WHSV) on the olefin +
aromatic carbon yield. Reaction conditions: reaction temperature, 600 C;
partial pressure, 12.3 Torr
20
60
15
EG
THF
Furan
10
10
12
14
16
-1
WHSV (h )
Fig. 6 Effect of weight hourly space velocity (WHSV) on the coke
yield of biomass derivates catalytic conversion. Reaction conditions:
reaction temperature, 600 C; partial pressure, 12.3 Torr
1178
(a)
(b)
90
80
70
40
30
Carbon selectivity(%)
50
C2H4
C3H6
20
C4H8
C5
10
60
C2H4
50
C3H6
40
C4H8
C5
30
20
10
10
12
14
16
-1
10
12
14
16
-1
WHSV (h )
WHSV (h )
(c)
Carbon selectivity (%)
40
30
20
10
C2H4
C3H6
C4H8
C5
0
2
10
12
14
16
-1
WHSV (h )
25
EG
THF
Furan
60
20
50
EG
THF
Furan
40
30
70
20
10
10
0
15
10
15
Partial pressure (torr)
20
10
15
20
1179
Zhang et al. [26, 32] have found that the yield of usable
petrochemical products from zeolite conversion of different
biomass-derives is a function of the H/Ceff ratio of the
feedstock. If this is the case, then the higher the hydrogen
to oxygen effective ratio, the higher the ability of chemical
production of biomass derivates. According to Eq. (5), the
hydrogen to carbon effective ratio of EG, THF and furan
were calculated as 1, 1.5, and 0.5, respectively. Thus, the
chemical yield of THF was higher than that produced by
EG, as shown in Fig. 8. Chen et al. [33] indicated that it is
difficult for feedstocks with H/Ceff less than 1 to catalytically convert for chemicals, due to serious coking and
deactivation of zeolites. It has been confirmed in Figs. 8
(a)
50
40
C2H4
30
C3H6
20
C4H8
C5
50
10
0
10
15
40
20
10
20
Benzene
Toluene
Ethyl benzene
Xylene
Others
30
(b)
15
20
60
90
70
60
C2H4
50
C3H6
C4H8
40
C5
30
20
80
10
50
40
Benzene
Toluene
Ehyl benzene
Xylene
Others
30
20
10
10
0
5
10
15
20
10
15
20
(c)
45
C H
2 4
C H
3 6
C H
4 8
C
5
40
30
20
10
40
50
35
30
25
20
15
10
Benzene
Xylene
Toluene
Styrene
Ethyl benzene
Others
5
0
5
10
15
20
10
15
20
1180
and 9 that the low H/Ceff ratio of furan for the existence of
C=C resulted in the lower chemical yield and high coke
yield compared with EG and THF.
Figure 10 shows the detailed product selectivity of different feedstocks as a function of partial pressure. In Fig. 10
(c), the plot of the selectivity of olefins and aromatics
species versus partial pressure of furan conversion differed
greatly from that of EG, THF; especially the products distribution on the sides of 12.30 Torr show discriminative
characteristics. The effect of partial pressure on the olefins
selectivity for THF catalytic pyrolysis was found to be less
sensitive than that of EG conversion. In Fig. 10(a), toluene
and xylene produced by EG conversion were two important
aromatic products of 37 % 41 % and 31 % 42 %,
respectively.
The possible conversion pathway can be illustrated as
Fig. 11. C5 compounds from EG and benzofuran from
furans were regarded as two important intermediates during
OH
H2O
C5
main products
dehydration+polymerization
olefins
decarbonylation
decarboxylation
OH
dehydrogenation
coke
aromatics
target products
CO+CO2
(a) EG
dehydration
H2O
main products
H2O
O
dehydrogenation
Diels-Alder condensation
coke
olefins
(b) furan
aromatics
target products
(a)
(b)
50
60
Conversion (%)
40
Conversion(%)
1181
30
20
50
40
10
30
0
400
450
500
550
600
650
Temperature ( C)
10
12
14
16
WHSV (h-1)
(c)
80
Conversion (%)
70
60
50
40
30
20
0
10
15
20
Conclusions
Catalytic conversion of biomass derivates, such as linear
polyols (EG), saturated furans (THF) and unsaturated furans
(furan), was investigated over ZSM-5 in a gas-solid phase
reactor. Three operation parameters, pyrolysis temperature,
WHSV and partial pressure were introduced to study the
effect of chemical structures on the catalytic characteristics.
From the statistical analyses, THF produced much more
chemicals than furan, with the highest yield of around
65 % and 33 %, respectively. Compared to other feedstocks
evaluated, furan showed several times higher yield of coke
during the catalytic conversion. The selectivity of propylene
from THF was 1.5 times higher than that of EG. Meanwhile,
furan produced considerable amounts of benzofuran, which
cannot been found from EG and THF. H/Ceff was introduced
to represent the ability of catalytic conversion for the chemicals, which explains the remarkable gap of chemical yields
from three feedstocks. The lower H/Ceff of furan attributed
References
1. Bridgewater AV (2012) Review of fast pyrolysis of biomass and
product upgrading. Biomass Bioenergy 38:6894
2. Huber GW, Iborra S, Corma A (2006) Synthesis of transportation
fuels from biomass: chemistry, catalysts, and engineering. Chem
Rev 106:40444098
3. Zhang X, Tu MB, Paice MG (2011) Routes to potential bioproducts from lignocellulosic biomass lignin and hemicelluloses. Bioenerg Res 4:246257
4. Christopher LP (2011) Biomass processing. Bioenerg Res 3:223224
5. Schwaiger N, Feiner R, Zahel K et al (2011) Liquid and solid products
from liquid-phase pyrolysis of softwood. Bioenerg Res 4:294302
6. Bulusheva DA, Rossa JRH (2011) Catalysis for conversion of biomass
to fuels via pyrolysis and gasification: a review. Catal Today 171:113
7. Toor SS, Rosendahl L, Rudolf A (2011) Hydrothermal liquefaction
of biomass: a review of subcritical water technologies. Energy
36:23282342
8. Choudhary TV, Phillips CB (2011) Renewable fuels via catalytic
hydrodeoxygenation. Appl Catal A Gen 397:112
1182
9. Sharma RK, Bakhshi NN (1993) Catalytic upgrading of pyrolysis
oil. Energy Fuel 7:306314
10. Mortensen PM, Grunwaldt JD, Jensen PA, Knudsen KG, Jensen
AD (2011) A review of catalytic upgrading of bio-oil to engine
fuels. Appl Catal A Gen 407:119
11. Peng J, Chen P, Lou H, Zheng XM (2009) Catalytic upgrading of
bio-oil by ZSM-5 in sub- and super-critical ethanol. Bioresour
Technol 100:34153418
12. Sharna RK, Bakhshi NN (1991) Upgrading of wood-derived biooil over ZSM-5. Bioresour Technol 35:5766
13. Zhang Q, Chang J, Wang TJ, Xu Y (2006) Upgrading bio-oil over
different solid catalysts. Energy Fuel 20:27172720
14. Calson TR, Vispute TP, Huber GW (2008) Green gasoline by
catalytic fast pyrolysis of solid biomass derived compounds.
ChemSusChem 1:397400
15. Calson TR, Jae J, Lin YC, Tompsett GA, Huber GW (2010)
Catalytic fast pyrolysis of glucose with ZSM-5: the combined
homogeneous and heterogeneous reactions. J Catal 270:110124
16. Calson TR, Tompsett GA, Conner WC, Huber GW (2009) Aromatic production from catalytic fast pyrolysis of biomass-derived
feedstocks. Top Catal 52:241252
17. Mullen CA, Boateng AA (2011) Production and analysis of fast
pyrolysis oils from proteinaceous biomass. Bioenerg Res 4:303311
18. Carlson TR, Cheng YT, Jae J, Huber GW (2011) Production of
green aromatics and olefins by catalytic fast pyrolysis of wood
sawdust. Energy Environ Sci 4:145161
19. Cheng YT, Huber GW (2011) Chemistry of furan conversion into
aromatics and olefins over ZSM-5: a model biomass converaion
reaction. ACS Catal 1:611628
20. Adjade JD, Bakhshi NN (1995) Catalytic conversion of biomassderived oil to fuels and chemical I: model compound studies and
reaction pathways. Biomass Bioenergy 8:131149
21. Adjade JD, Bakhshi NN (1995) Production of hydrocarbons by
catalytic upgrading of a fast pyrolysis bio-oil. Part I: conversion
over various catalysts. Fuel Process Technol 45:161183
22. Williams PT, Horne PA (1995) The influence of catalyst type on
the composition of upgraded biomass pyrolysis oils. J Anal Appl
Pyrol 31:3961
23. Corma A, Huber GW, Sauvanaud L, Connor PO (2008) Biomass
to chemicals: catalytic conversion of glycerol/water mixtures into
acrolein, reaction network. J Catal 257:163171