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Bioenerg. Res.

(2013) 6:11731182
DOI 10.1007/s12155-013-9303-x

Comparison of Catalytic Characteristics of Biomass


Derivates with Different Structures Over ZSM-5
Shanshan Shao & Huiyan Zhang & Rui Xiao &
Dekui Shen & Jian Zheng

Published online: 9 February 2013


# Springer Science+Business Media New York 2013

Abstract The conversion of three major biomass derivates


was conducted in a quartz tubular fixed bed reactor over a
ZSM-5 catalyst. As the model compounds of polyols, saturated furans and unsaturated furans, ethylene glycol (EG), tetrahydrofuran (THF) and furan were pyrolyzed to find out the
influence of chemical structure on the catalytic characteristics.
The effect of pyrolysis temperature (400650 C), weight
hourly space velocity (2.915.5 h1) and partial pressure
(2.1220.49 Torr) on the feed conversion, product yield and
selectivity were investigated. The hydrogen to carbon effective ratio (H/Ceff) was referred to, to analyze the capacity of
biomass derivates being converted to chemicals (olefins and
aromatics). The results showed that the existence of rings and
C=C had great effect on the catalytic characteristics. The
conversion of furan was much lower (mainly less than
60 %) than that of EG and TH,F which were close to 100 %.
It was also found that the chemical yield of THF was slightly
more than that of EG, which can be attributed to its relative
higher H/Ceff of 1.5. Furan produced the highest coke yield,
which was more than 15 %, whereas that of EG and THF was
only around 5 %. The serious coking of furan led to the lowest
chemical yield, which was less than 35 %. This study paves a
way for the mechanism study on catalytic characteristics of
biomass-derived feedstocks over zeolite catalysts.
Keywords Biomass derivates . Bio-oil . Catalytic
pyrolysis . ZSM-5 . Hydrogen to carbon effective ratio
S. Shao : H. Zhang : R. Xiao : D. Shen : J. Zheng
Key Laboratory of Energy Thermal Conversion and Control,
Ministry of Education, School of Energy and Environment,
Southeast University, Nanjing 210096, China
R. Xiao (*)
Key Laboratory of Energy Thermal Conversion and Control
of Ministry of Education, Southeast University, Sipailou #2,
Nanjing 210096, Peoples Republic of China
e-mail: ruixiao@seu.edu.cn

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.

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Considering the large carbon loss from the initial fast


pyrolysis to the bio-oil upgrading, another applied technology of lignocellulose biomassbiomass fast pyrolysis
(BFP)was developed for the selective production of some
specified products [1418]. In the BFP, furfural and furans
account for over 40 % carbon of the oxygenated products,
and thus the furans were regarded as important intermediates from the BFP of biomass [14, 16, 19].
Adjade et al. [20] investigated the catalytic pyrolysis of
model compounds of bio-oil over ZSM-5 representing the
acid, ester, alcohol, aldehyde and ketone, ether and phenol
chemical groups, with the objective of understanding the
reaction steps involved in the ZSM-5 conversion of the biooil. Various catalysts like ZSM-5, H-mordenite, H-Y, silicalite
and silica-alumina have been used in the upgrading of a fast
pyrolysis bio-oil in a fixed bed micro-reactor, and the former
two were determined to produce more aromatic than aliphatic
hydrocarbons [21]. Cheng et al. [19] reported the catalytic
chemistry of furan conversion for olefins and aromatics, and
identified the influence of reaction conditions on the olefin +
aromatic distribution and the retained composition inside the
zeolite. Products species divergence stem from biomassderivates catalytic pyrolysis that can be clarified with dependence on the chemical structures. Reactants of different unsaturations and aromaticity usually showed product yield and
distribution of great distinctions. Up to now, lots of discussions were reported on biomass fast pyrolysis (BFP) with
different biomass sources like woody and oil plants, and on
the other hand, on the bio-oil catalytic hydrogenation or
cracking performance as quoted above [2230], but there is
little literature focusing on the influence of reagent functional
groups on the product component and selectivity.
In this paper, EG and THF, which were both saturated model
compounds of selective hydrogenation products, and furan,
which was a major intermediate of BFP, have been converted
into olefins (mainly ethylene, propylene and butylene) and
aromatics (mainly benzene, toluene, ethyl benzene). The reaction parameters, including pyrolysis temperature, weight hourly
space velocity (WHSV), and partial pressure, were changed to
discuss their effect on the product carbon yield and selectivity.
The current study was undertaken with the objective to obtain
the effect of chemical structure (straight-chain saturated, saturated cyclic, unsaturated cyclic) on the catalytic characteristics
with the variation of the system working conditions.

Materials and Methods


Materials
EG, THF (purity >99.999 %, reagent grade) and furan
(>99.9 %, ananlyitcal grade) were used as feedstocks without any treatment from Aladdin Company, P.R.China.

Bioenerg. Res. (2013) 6:11731182

The catalyst used in this study was ZSM-5 purchased


from Zeolyst (CBV 3024E, SiO2/Al2O3=30). The ZSM-5
catalyst was sieved to 50200 mesh (74297 m). For a
typical run, 90 mg catalyst was loaded in the quartz plate.
Prior to all reactions, the catalyst was calcined in the reactor
at 600 C in 100 mL/min oxygen flow for 6 h.
Catalytic Conversion of Biomass Derivates
A quartz tubular fixed bed shown in Fig. 1 was built for
catalytic conversion of the feed to olefins and aromatics.
Sieved catalysts were held on the quartz bed. The nitrogen
was applied as carrier gas. The reaction temperature was
measured with a thermocouple inserted from the top of the
reactor. The feeds were injected into the reactor by a spring
pump at the top of the reactor. The feed was then vaporized
and flew down. An ice-water bath was used to keep cold for
trapping heavy products dissolved in the ethanol. The
liquids were captured to be analyzed by gas chromatography/mass spectrometry (GC/MS). The noncondensable gas
products were then collected in the gas sampling bags and
analyzed by GC-Flame-ionisation detector/thermal-conductivity (FID/TCD). After reaction, the reactor continued
flushing with nitrogen of 100 mL/min for 30 min. Then
the spent catalysts were regenerated in 100 mL/min oxygen
gas for another 30 min. During the coke combustion process, CO was converted into CO2 in the copper converter,
which was full of copper oxide, and then trapped by the
ascarite. The coke yield was measured by the weight increase in the CO2 capturer.
Products Analysis and Data Processing
The gas product was analyzed using a Shimadzu 2014 GC
system. A Restek Rtx-VMS capillary column was used to
qualify olefins, while a TDX-01 packed column was used to
analyze methane, CO and CO2. High purity helium was
used as carrier gas. The temperature ramp of oven temperature was as follows: hold at 35 C for 5 min, ramp to 140 C
at 5 C /min, ramp to 230 C at 50 C /min, and hold at 230 C
for 8.2 min.
Liquid products were analyzed with GC/MS (Agilent,
7890A-5975C). HP-5 capillary column (30 m0.25 mm
0.25 m) was used as chromatographic column. And high
purity helium was used as the carrier. The following temperature ramp was employed in the liquid analysis: from
40 C to 50 C at 5 C/min, hold at 50 C for 3 min, ramp to
80 C at 5 C/min, ramp to 280 C at 10 C/min, and hold at
280 C for 2 min.
The following calculations were used in the paper:
WHSV

mfeed
Mcatalyst

Bioenerg. Res. (2013) 6:11731182

1175

Fig. 1 The schematic diagram


of the fixed bed for catalytic
conversion of biomass derivates

Partial pressure

vfeed
 Patmosphere
vfeed vcarrier

nspecified
Carbon yield
 100%
nconverted

CO+CO2 carbon yield (%)

(b)

80
60

EG
THF
Furan

mfeed
Mcatalyst
feed
carrier
nspecified
nconverted
nproducts

40

nspecified
 100%
nproducts

Mass flow rate of feed (g/h)


Mass of catalysts loaded on the plate (g)
Flow rate of feed (mL/min)
Flow rate of carrier gas (mL/min)
Moles of carbon in a specified product
Moles of converted carbon fed in
Moles of carbon in some products.

60

20

50
0

400

500
600
Pyrolysis temperature C

25
20
15

EG
THF
Furan

650

Coke yield (%)

Olefin+aromatic carbon yield


%

(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

Fig. 3 Effect of temperature on the coke yield of ethylene glycol (EG),


tetrahydrofuran (THF) and furan catalytic conversion. Reaction conditions: WHSV, 11.2 h1; partial pressure, 12.3 Torr

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Bioenerg. Res. (2013) 6:11731182

according to the following order: THF>EG>>furan. In


Fig. 2(b), the carbon yield of CO+CO2 of EG showed remarkable increase with the increasing temperature. EG converted
more oxygen as CO and CO2, because of its higher oxygen
content. The CO+CO2 yield of THF and furan were much less
than that of EG, which indicated that the oxygen in THF and
furan tended to be deleted as H2O.
Figure 3 presents the coke yield of EG, THF and furan as
a function of pyrolysis temperature. It is obviously that
furan showed serious coking at lower temperature between
400 C and 500 C. The coke yield of THF without C=C
was almost less than 5 % which was much less than furan.
The alkylation reaction followed C-O-C breaking and the

Results and Discussion


Effect of Pyrolysis Temperature on the Product Yield
and Selectivity
We tested the catalytic conversion of EG, THF and furan at
four reaction temperatures: 400 C, 500 C, 600 C and
650 C. Figure 2 shows the effect of pyrolysis temperature
on the olefin + aromatic and CO + CO2 carbon yield. The total
yield of olefins and aromatics for EG and THF increased
rapidly from 400 C to 500 C and then rose gently after
500 C, whereas that of furan increased persistently with
much lower value. The olefin + aromatic yield decreased

(a)

70

60

Carbon Selectivity (%)

40
C2H4

30

C3H6
C4H8

20

C5

Carbon selectivity (%)

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(%)

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

Carbon selectivity (%)

50

Carbon selectivity (%)

Fig. 4 Product selectivities of


biomass derivates catalytic
conversion as a function of
temperature: a ethylene glycol
(EG); b tetrahydrofuran (THF);
c furan. Reaction conditions:
WHSV, 11.2 h1; partial
pressure, 12.3 Torr

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

Bioenerg. Res. (2013) 6:11731182

70

Olefin+aromatic carbon yield (%)

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

fluctuation in the range of 1 % with the change of WHSV, and


that of THF went through up to a maximum value of 6.50 % at
11.2 h1, and decreased to 3.67 % at 15.5 h1.
Detailed selectivity of olefins from EG, THF and furan
conversion as a function of WHSV were given in Fig. 7(a)
(c). As was shown in the figure, their sensibility on olefin
selectivity to WHSV was found to decrease in the following
order: furan>EG>THF. When WHSV decreased from
15.5 h1 to 2.9 h1, C5 species may have cracked into light
olefins, as demonstrated by the increasing selectivity of
ethylene and propylene shown in Fig. 7(a) and (c), respectively. The hydrocarbon aromatic selectivity of the feedstocks versus WHSV was not given, considering their
slight fluctuation during the selected WHSV range.
25

Effect of WHSV on the Product Yield and Selectivity

20

Coke yield (%)

Figure 5 shows the total yield of olefin and aromatic in the


fixed bed as a function of WHSV at the temperature of 600 C
and the partial pressure of 12.30 Torr. The weight hourly space
velocity varied from 2.9 h1 to 15.5 h1 by using different
amounts of ZSM-5 catalysts from 65 mg to 350 mg in the
reaction. The yields of olefin + aromatic for catalytic conversion of EG and THF were not sensitive to the change of
WHSV in general. With the decrease of WHSV, the retention
time of feed gas in ZSM-5 channels increased, which resulted
in the olefin + aromatic yield of furan increasing from 11.36 %
to 32.03 % and the coke yield increasing from 18.0 % to
22.2 %, as shown in Fig. 6.
In Fig. 6, the curves showed the coke yield of EG, THF and
furan at different WHSV. The coke yield of EG showed minor

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

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Bioenerg. Res. (2013) 6:11731182

Fig. 7 Effect of weight hourly


space velocity (WHSV) on the
products selectivity: ac olefin
selectivity of EG, THF and
furan. Reaction conditions:
reaction temperature, 600 C;
partial pressure, 12.3 Torr

(a)

(b)
90
80
70

40
30

Carbon selectivity(%)

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 )

Effect of Feed Vapor Partial Pressure on the Product Yield


and Selectivity
Figure 8 shows the olefin + aromatic carbon yield as a
function of feed vapor partial pressure when the pyrolysis
temperature and WHSV were set at 600 C and 12.3 h1,
respectively. The partial pressure was changed by adjusting

the flow rate of carrier gas. EG and THF produced the


highest yield of olefins and aromatics (about 65 %) at
9.71 Torr and 12.30 Torr, respectively. However, the olefin
+ aromatic carbon yield increased with a larger gradient at
low partial pressure when the volume flow rate of carrier gas
was regulated from 200 mL/min to 2,000 mL/min. It can be
concluded that low partial pressure promote the production

25

EG
THF
Furan

60
20

50
EG
THF
Furan

40
30

Coke yield (%)

Olefins+aromatics carbon yield (%)

70

20

10

10
0

15

10

15
Partial pressure (torr)

20

Fig. 8 Effect of partial pressure on the olefin + hydrocarbon aromatics


carbon yield. Reaction conditions: reaction temperature, 600 C;
weight hourly space velocity (WHSV), 11.2 h1

10

15

20

Partial pressure (torr)

Fig. 9 Coke yield of three different feedstocks as a function of partial


pressure Reaction conditions: reaction temperature, 600 C; weight
hourly space velocity (WHSV), 11.2 h1

Bioenerg. Res. (2013) 6:11731182

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

of chemicals. The influence of partial pressure on the coke


yield of biomass derivates was given in Fig. 9. There were
surprising similarities on the curve trend between coke
yield versus partial pressure and that versus WHSV. The
experiment demonstrated that high partial pressure was
to the benefit of coking prevention for the furans, and
the coke yield of THF reached a maximum of 6.5 % at
12.30 Torr.
A concept H/Ceff has been introduced in biomass-derived
feedstocks by Chen et al. [31] which is defined in Eq. (5)

H  2O
H Ceff
C

(a)

50

40
C2H4

30

C3H6

20

C4H8
C5

Carbon selectivity (%)

Carbon selectivity (%)

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

Carbon selectivity (%)

80

Carbon Selectivity (%)

10

Partial Pressure (torr)

Partial Pressure (torr)

50

40

Benzene
Toluene
Ehyl benzene
Xylene
Others

30

20

10
10

0
5

10

15

20

10

15

20

Partial Pressure (torr)

Partial Pressure (torr)

(c)

45

C H
2 4

C H
3 6

C H
4 8

C
5

40

30

20

10

40

Carbon selectivity (%)

50

Carbon selectivity (%)

Fig. 10 Product selectivities of


biomass derivates catalytic
conversion as a function of
partial pressure: a ethylene
glycol (EG); b tetrahydrofuran
(THF); c furan. Reaction
conditions: reaction
temperature, 600 C; weight
hourly space velocity (WHSV),
11.2 h1

35
30
25
20
15
10

Benzene
Xylene

Toluene
Styrene

Ethyl benzene
Others

5
0
5

10

15

Partial pressure (torr)

20

10

15

Partial pressure (torr)

20

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Bioenerg. Res. (2013) 6:11731182

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

catalytic pyrolysis. The C5 compounds and benzofuran


formed by dehydration + polymerization and Diels-Alder
condensation with two furan molecules. During the
biomass-derivates conversion, the coke was formed by dehydration and polymerization, which limited the olefins and
aromatics formation.
Influence of Operation Parameters on the Conversion of EG,
THF and Furan Catalytic Pyrolysis
Almost no EG and THF were found in the gas and liquid
product; namely, their conversions were closer to 100 %;
nevertheless, the operation conditions had great effect on the
conversion of furan in the micro-reactor, as shown in
Fig. 12. The serious coking at low temperature blocked the
catalysts and led to coverage of active sites [3436].
Figure 12(a) showed that the high temperature was favorable for cracking of coke species and resulted in the furan

Fig. 11 General pathway of


biomass derivates converting
over HZSM-5 a ethylene glycol
(EG); b furan

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

Bioenerg. Res. (2013) 6:11731182

(a)

(b)

50
60

Conversion (%)

40

Conversion(%)

Fig. 12 Conversion of furan


catalytic pyrolysis as a function
of operating parameters: a
temperature; b weight hourly
space velocity (WHSV); c
partial pressure

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

Partial pressure (torr)

conversion from 10.5 % to 42.7 %. The low WHSV


corresponding to high retention time of furan vapor on the
catalysts gave high conversion, as shown in Fig. 12(b). The
conversion of furan improved from 20.6 % to 77.6 %, which
can be attributed to the increasing retention time and furan
vapor concentration.

to the existence of C=C and led to the serious coking. Future


work may aim at the investigation of the detailed formation
mechanism of coke in the catalytic conversion of biomass
derivates.
Acknowledgements This work is financially supported by the National Natural Science Foundation of China (Grant No. 51076031) and
the National Basic Research Program of China (973 Program) (Grant
No. 2010CB732206).

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

Bioenerg. Res. (2013) 6:11731182


24. Huber GW, Corma A (2007) Synergies between bio- and oil
refineries for the production of fuels from biomass. Angew Chem
Int Ed 46:71847201
25. Vispute TP, Zhang HY, Sanna A, Xiao R, Huber GW (2010)
Renewable chemical commodity feedstocks from integrated catalytic processing of pyrolysis oils. Science 330:12221227
26. Zhang HY, Carlson TR, Xiao R, Huber GW (2012) Catalytic fast
pyrolysis of wood and alcohol mixture in a fluidized bed reactor.
Green Chem 14:98110
27. Arstad B, Kolboe S, Sang O (2005) Theoretical study of the
heptamethylbenzenium ion. intramolecular isomerizations and
C2, C3, C4 alkene elimination. J Phys Chem A 109:89148922
28. Zhang HY, Xiao R, Wang DH, He GY, Shao SS, Zhang JB, Zhong
ZP (2011) Biomass fast pyrolysis in fluidized bed reactor under
N 2 , CO 2, CO, CH 4 and H 2 atmosphere. Bioresour Technol
102:42584264
29. Zhang HY, Xiao R, Huang H, Xiao G (2009) Comparison of noncatalytic and catalytic fast pyrolyisi of corncob in a fluidized bed
reactor. Bioresour Technol 100:14281434
30. Fulle D, Kiefer JH (1998) Pyrolysis of furan at low pressure:
vibration relaxation, unimolecular dissociation, and incubation
times. J Phys Chem A 102:74807486
31. Chen NY (1986) Liquid fuel from carbohydrates. Chem Tech
16:506
32. Zhang HY, Cheng YT, Vispute TP, Xiao R, Huber GW (2011)
Catalytic conversion of biomass-derived feedstocks into olefins
and aromatics with ZSM-5: the hydrogen to carbon effective ratio.
Energy Environ Sci 4:22972307
33. Chen NY, Degnanand JTF, Koenig LR (1986) Liquid fuel from
carbohydrates. Chem Tech 16:506
34. Gayubo AG, Aguayo AT, Atutxa A, Prieto R, Bilbao J (2004)
Deactivation of ZSM-5 zeolite catalyst in the transformation of the
aqueous fraction of biomass pyrolysis oil into hydrocarbons. Energy Fuel 18:16401647
35. Arabiourrutia M, Olazar M, Aguado R, Lopez G, Barona A,
Bilbao J (2008) ZSM-5 and HY zeolitr catalyst performance in
the pyrolyisi of tires in a conical spouted bed reactor. Ind Eng
Chem Res 47:76007609
36. Lin XY, Fan Y, Shi G, Liu HN, Bao XJ (2007) Coking and
deactivation behavior of ZSM-5 zeolite-based FCC gasoline
hydro-upgrading catalyst. Energy Fuel 21:25172524