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Transformation of levoglucosan over H-MCM-22 zeolite and

H-MCM-41 mesoporous molecular sieve catalysts

M. Käldström a, N. Kumar a, T. Heikkilä b, M. Tiitta c, T. Salmi a, D. Yu. Murzin a,*

a
Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, Åbo Akademi University,
Biskopsgatan 8, FIN-20500 Åbo/Turku, Finland
b
Laboratory of Industrial Physics, Department of Physics, University of Turku, FI-20014 Turku, Finland
c
Neste Oil, Technology Centre, P.O.B 310, 06101 Porvoo, Finland

article info abstract

Article history: Catalytic transformation of levoglucosan (1-6-anhdyro-b-D-glucopyranose) was carried out

Received 19 January 2009 in a fixed bed reactor at 573 K over zeolite and mesoporous material catalysts. Proton forms
Received in revised form of MCM-22-30 and MCM-41-20 catalysts were tested in the conversion, changing also the
21 January 2011 residence time. The yield of the transformation product phases was substantially influ-
Accepted 25 January 2011 enced by the structures, at the same time the formation of the different compounds were
Available online 18 February 2011 dependent on the structures of the acidic zeolite catalysts. Oxygenated species were the
main liquid product, consisting mainly of aldehydes and furfurals (glycolaldehyde, form-
Keywords: aldehyde, acetaldehyde, furfural, 5-methylfurfural, acetic acid). The formation of the liquid
Levoglucosan products was higher over MCM-41-20 than over MCM-22-30 for all the oxygenated species
Zeolites except acetic acid, indicating larger formation of non-condensable products over the
MCM-22 microporous material. By increasing the residence time the formation of acetic acid
MCM-41 increased in transformations over MCM-22, however, such increase also led to generation
Deactivation of more gases with both catalysts. The deactivation due to coking was more severe over the
Pyrolysis zeolite compared to the mesoporous material. It was, however, possible to successfully
regenerate the spent zeolites without changing the structure.
ª 2011 Elsevier Ltd. All rights reserved.

1. Introduction
Biorefining of renewables has an important role in sustainable
supplying of chemicals and energy needed for the society. The
main reason for developing processes for biorefining of
the renewables is the target to reduce CO2 emissions and the
application of sustainable principles. Fossil fuels are a finite
energy source which will be depleted in the future, thus
relying on this source of energy is not sustainable.
However, the cost of processing the renewables to products
is often too high making bio-based products non-competitive
[1]. This is partly due to the fact that the traditional synthesis
routes which were developed and optimized for more than
a century for hydrocarbons to produce chemicals are not well
adapted for renewables which are already deeply
functionalized.
The main difference between fossil fuels and biomass
when looking at the chemical structure is that biomass
contains much higher content of oxygen. For the maintenance
of life on the planet the presence of oxygen is absolutely
necessary but when the oxygenated species gets into the
traditional fuel processes they can be troublesome. One
benefit with biomass when comparing it with fossil fuels is
that it contains very little sulfur. In the utilization of biomass,

* Corresponding author. Tel.: þ358 2 215 4985.

E-mail address: dmurzin@abo.fi (D.Yu. Murzin).
0961-9534/$ e see front matter ª 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2011.01.046
1968 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 9 6 7 e1 9 7 6
transformation of cellulose plays an important role since it is
the most abundant compound in the eukaryotic cell wall of
plants. Its function is to provide, together with hemicelluloses,
the cell with structural support and protection.
Biomass made of wood is the most abundant source of
biomass in the world. Wood typically consists of about
40e50% cellulose, 23e33% lignin and 25e35% of hemi-
celluloses [2]. The wood can be treated through pyrolysis,
depolymerisation, deligninfication and extraction. All
different methods of treatment yield different compounds.
Conventional pyrolysis of lingo-cellulosic biomass produces
moderate to low amounts of bio-oil, compared with gases
and coke, also formed during the process. Optimized fast
pyrolysis is, however, a commonly used method applied for
production of bio-oil in high yields.The problem with the
bio-oil is that it has poor volality, high viscosity and gives
coking. It also gives rise to corrosiveness and cold flow
problems. In diesel engines the oil is difficult to ignite (due to
low heating value and high water content) it also gives rise
to corrosiveness (acids) and coking (thermally unstable
components). To avoid these problems some catalytic
upgrading is needed [3].
Cellulose can also be found in large fractions in domestic
and industrial wastes. In the utilization of cellulose based
materials for the production of bulk and fine chemicals
catalysis is needed and a significant amount of research in
this area is still to be done [4]. Catalysis and innovative process
design will play an important role in the development and
upgrading of fuels and chemicals originating from biomass.
Zeolites have been important in the upgrading of fossil fuels
and they also might have an application in the upgrading of
biomass. For better understanding of this process trans-
formation of model compounds derived from cellulose, for
instance through pyrolysis, should be studied. Levoglucosan
(1,6-b-D-glucopyranose) is an interesting compound since it is
the intermediate through which cellulose and hemicelluloses
pyrolytically decompose forming lower molecular compounds
[5,6]. Levoglucosan, which has the form of a solid white sugar
at room temperature has a molecular weight of 162 g mol1,
a cross section of about 4 Å, melting point between 446 and
456 K [7] and a boiling point of 558 K [8]. The preparation of
levoglucosan from a broad range of different sources has also
been investigated [9]. The main reason that restrains the
utilization of levoglucosan is its high price, which is a conse-
quence of its production and purification, and different
processes have been suggested for preparation of the anhy-
drous sugar [10,11].
The reaction pathway for the thermal degradation of lev-
oglucosan has also been proposed by several groups [12,13].
These reaction pathways could be altered in the presence of
catalysts. MCM-22 is a zeolite characterized by two non-
intersecting, 2-dimensional, 10-ring channel system [14] and
MCM-41 is a hexagonal shaped mesoporous material that
belongs to the M41S family of molecular sieves discovered at
Mobil in 1992 [15].
In this paper, the influence of mesoporous H-MCM-41 and
H-MCM-22 microporous zeolite catalysts on transformation of
levoglucosan was investigated, changing also the residence
time. The zeolites used in the study were characterized by
different methods.
2. Experimental
2.1. Catalyst synthesis and characterization
The Na-MCM-22 microporous molecular sieve and Na-MCM-
41 mesoporous material were synthesized according to the
procedure described elsewhere [14e18] with some modifica-
tions. The synthesis of Na-MCM-22 followed the subsequent
procedure: water and sodium aluminate (Riedel-de Haën,
purity 95%) was added to sodium hydroxide (Merck, purity
99%) and the mixture was stirred for 10 min. After the stir-
ring hexamethyleneimine (Aldrich, purity 99%) and fumed
silica (Aldrich purity 99.8%) were added and the blend was
stirred for another 20 min. After forming a homogenous phase
the mixture was transferred to teflon cups and inserted into
autoclaves. The synthesis was carried out at 423 K for 7 days.
After completion of synthesis the material was filtered,
washed with distilled water to neutral pH, dried at 373 K and
calcined at 823 K for 8 h.
Na-MCM-22 and Na-MCM-41 were transformed to NH4-
MCM-22 and NH4-MCM-41 by ion-exhange using ammonium
nitrate solution. H-MCM-22 and H-MCM-41 was obtained by
calcination of NH4-MCM-22 and NH4-MCM-41 at 773 K. The
complete name of the H-MCM-22 molecular sieves synthe-
sized is H-MCM-22-30 where the number 30 indicates the ratio
of Si to Al in the structure, thus a large number indicates low
aluminum content and few acid sites. The complete name of
the H-MCM-41 molecular sieve is hence H-MCM-41-20.
The determination of structure and phase purity of the
MCM-22 molecular sieves was carried out by an X-ray powder
diffractometer. The specific surface area of fresh, used and
regenerated H-MCM-22 was measured by the nitrogen
adsorption method (Sorptometer 1900, CarloErba Instru-
ments). The catalysts were out gassed at 473 K prior to the
measurement and the Dubinin equation was used to calculate
the specific surface area.
The zeolites were regenerated in an oven by calcination at
723 K for 120 min. The acidity of the synthesized zeolites was
measured by infrared spectroscopy (ATI Mattson infinity
spectrometer) by using pyridine (99.5%, a.r.) as a probe
molecule for qualitative and quantitative determination of
both Brønsted and Lewis acid sites. The FTIR spectrometer
was equipped with an in-situ cell containing ZnSe windows.
The samples were pressed into thin self-supported discs
(weight 15e20 mg and radius 0.65 cm). Pyridine was first
adsorbed for 30 min at 373 K and then desorbed by evacuation
at different temperatures (523, 623 and 723 K) to obtain
a distribution of acid site strengths. All spectra were recorded
at 373 K with a spectral resolution equal to 2 cm1. Spectral
bands at 1545 and 1450 cm1 were used to identify Brønsted
acid sites (BAS) and Lewis acid sites (LAS). The amounts of BAS
and LAS were calculated from the intensities of corresponding
spectral bands by using the molar extinction coefficients
reported by Emeis [19].
2.1.1. Experimental set-up for catalyst testing
Transformation of levoglucosan (1-6-b-D-glucopyranose) in
gas phase at atmospheric pressure was chosen as the model
test reaction. The catalyst testing equipment is shown in
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 9 6 7 e1 9 7 6 1969

H2 He N2

FIC FIC FIC

FIC
TIC

Sample feed Evaporator

Condenser

Reactor

GC
Glycol
solution
Computer Glass balls
Quartz wool
Catalyst
Products Quartz wool
Air FIC

Fig. 1 e Schematic presentation of catalytic testing equipment of levoglucosan transformation.

Fig. 1. It consisted of a quartz mini reactor, an oven, an
evaporator, a condenser, a GC and a PC.
Levoglucosan (Aldrich, purity 99%) was dissolved in
deionised water to make a 1% solution. The solution was fed
through an evaporator operating at 573 K into the quartz fixed
bed reactor with an inner diameter of 9 mm. The quartz mini
reactor was packed with the zeolite catalyst and inserted into
the oven. The particle size of the catalyst was between 150 and
250 mm. In order to get the narrow particle size range for the
zeolite catalyst, pellets of the zeolites powder were pressed
and later crushed and sieved. The temperature of the catalyst
bed was measured using a thermocouple and the temperature
of the reactor was monitored with a temperature controller.
Nitrogen gas with a flow of 58.1 cm3 min1 was used as
a carrier gas. The products were cooled down with
a condenser and collected in a flask. The condenser contained
glycol solution with a temperature of 268 K. The gaseous
products were analyzed online with a gas chromatograph
(Varian) equipped with a capillary column.
The feed of levoglucosan was adjusted to 4 ml h1. The
catalyst testing and the evaporation of levoglucosan in
the evaporator was carried out at temperature 573 K and the
amount of catalyst used was 0.125, 0.25 and 0.5 g. Experiments
with only quartz sand were also done to determine the non-
catalytic conversion of levoglucosan. The amount of quartz
sand used was 0.25 g. The catalyst bed height was measured
before every experiment giving a possibility to calculate the
weight hourly space velocity (WHSV) and residence time
(Table 1). In the experiments the levoglucosan solution was
fed into the reactor for 5 h which gave a total volume of 20 ml
liquid and 200 mg of pure levoglucosan. After each experiment
the total amount of liquid was weighted. The following day
the evaporator was thoroughly washed by passing water
through it to rinse out levoglucosan that was left and could

Table 1 e Residence times for the different catalysts.

Catalyst Catalyst Bed Catalyst Nitrogen WHSV Residence
amount (g) height volym (cm3) flow (cm3/ time (min)
(cm) min)

H-MCM-22 0.5 1.4 0.89 58.11 1.09 0.015

0.25 0.8 0.51 58.11 1.90 0.009
0.125 0.3 0.19 58.11 5.08 0.003
H-MCM-41 0.5 2.15 1.40 58.11 0.71 0.024
0.25 1 0.64 58.11 1.52 0.011
0.125 0.4 0.25 58.11 3.81 0.004
Quartz sand 0.25 0.2 0.13 58.11 7.61 0.002
1970 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 9 6 7 e1 9 7 6
affect the mass balance. The water used for washing was
always weighted and analyzed for determining the amount of
levoglucosan.
2.2. Product analysis
Gaseous products were detected online with a gas chro-
matograph equipped with capillary column and FI detector.
Liquid samples were analyzed with HPLC and the volatiles
with a gas chromatograph connected to a mass-spectrometer
(GCeMS).
2.2.1. Online GC
Gas samples were injected into the GC online (Varian 3700
equipped with a capillary column 50 m  0.32 mm i.d. alumina
column). Gaseous samples were taken after 10 and 30 min and
thereafter every hour. The following temperature program
was used: dwelling for 5 min at 313 K increase by 20 K min1 to
473 K and dwelling at 473 K for 10 min.
2.2.2. GC-MS-solid phase micro extraction
The volatile compounds were analyzed with GCeMS and
headspace solid phase micro extraction (SPME). 2 ml of the
solution containing the reaction products were transferred into
a small 4 ml flask equipped with a rubber cap. The sample flask
was heated to 320 K. The needle with the fibre was penetrated
through the cap into the bottle and the fibre was exposed to
the headspace of the sample for 30 min. The fibre used for
extraction was coated with carboxen/polymethylsiloxane
(CAR/PDMS). The components were enriched on the surface
and when equilibria were reached between the headspace and
the fibre the syringe was injected into the GCeMS for analysis.
The inlet chamber was set on 543 K were the absorbed and
adsorbed analytes were thermally desorbed in the hot injector
of the gas chromatograph. The GCeMS was equipped with
a capillary column (DB-Petro 50 m  0.2 mm  0.5 mm). The
following temperature program was used: dwelling for 10 min
at 313 K, heating 0.9 K min1 to 348 K followed by heating
1.1 K min1 to 393, heating 10 K min1 to 473 K and dwelling at
473 K for 20 min.
2.2.3. High performance liquid chromatography (HPLC)
The products from the test reaction with levoglucosan were
also analyzed with HPLC equipped with an acid Aminex cation
Hþ column. Low concentrated sulphuric acid (5 mmol dm3)
was used as a mobile phase. The flow was 0.5 ml min1 and
the temperature was set to 338 K. The samples were injected
into the HPLC directly after the experiments without any
pretreatment. Several different concentrations of different
standards were made and analyzed with the HPLC. The
standards were purchased from Aldrich or Fluka and had
a purity of 99%. The HPLC was calibrated with the different
standards and upon the results calibration curves were made
which made it possible to calculate the molar yields of the
achieved products. HPLC was also used to calculate the
conversion rate of levoglucosan.
2.2.4. Total organic carbon
The total organic carbon (TOC) was determined from the
liquid phase after each experiment. The analyses were
performed using a Total organic carbon analyzer, TOC-V CSN
(Shimadzu Corporation).
2.2.5. Coke analysis
Some 2.5 ml of hydrofluoric acid (HFA) was added to 0.15 g of
zeolite for dissolving at 1 h. The mixture was stirred between
short time intervals. 10 ml of dichloromethane was added to
the dissolved mixture. The soluble particles were extracted for
24 h and the non-soluble components were recovered. HFA
and dichloromethane formed two phases which were sepa-
rated with an extraction funnel. The dichloromethane phase
was filtrated and analyzed with GCeMS. The following
temperature program was used: dwelling for 10 min at 373 K,
heating 277 K min1 to 493 K followed by heating 275 K min1
to 573 and dwelling at 573 K for 20 min.
2.2.5.1. Thermo-gravimetric analysis. The amount of coke
formed on microporous H-MCM-22-30 and mesoporous
H-MCM-41 was determined by thermo-gravimetric analysis
(TGA) using a Cahn D-200 digital recording balance under the
flow of synthetic air. The following temperature program for
the oven was used: heating 2 K min1 from 298 K to 873 K and
dwelling at 873 K for 180 min.
3. Results and discussion
3.1. Catalyst characterization results
XRD patterns of Na-MCM-22 and Na-MCM-41 were similar to
those reported in the literature [16e18], indicating the phase
purity of synthesized materials. The XRD pattern of Na-MCM-
22 and scanning electron micrograph are given in Figs. 2 and 3.
The Brønsted and Lewis acidities of the studied catalysts, as
determined by pyridine adsorption (FTIR), are presented in
Table 2. The difference in acidity between H-MCM-41-20 and
H-MCM-22-30 is considerable. The difference is especially
substantial when comparing the Brønsted acid sites of the two
materials.
The surface area for the fresh, spent and regenerated
zeolites was measured with nitrogen physisorption and
calculated with Dubinin (microporous) and BET (mesoporous)
equations (Table 3). The decrease in surface area for the spent
zeolites was more severe in the case of H-MCM-22. It was
6000
5000
4000
Counts
3000
2000
1000
0
0 20 40 60 80
2 Theta
Fig. 2 e XRD pattern of Na-MCM-22-30.
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 9 6 7 e1 9 7 6 1971

Table 3 e Surface areas of fresh, used and regenerated

catalysts.
Mesoporous catalyst Surface area
(m2/g), BET

H-MCM-41 fresh 944

H-MCM-41 useda 802
H-MCM-41 usedb 484
H-MCM-41 regenerated 926

Microporous catalyst Surface area

(m2/g), Dubinin

H-MCM-22 fresh 547

H-MCM-22 useda 310
H-MCM-22 usedb 59
H-MCM-22 regenerated 490

a 0.5 g of catalyst used in the conversion of levoglucosan.

b 0.25 g of catalyst used in the conversion of levoglucosan.
Fig. 3 e Scanning electron micrograph of Na-MCM-22-30.

3.2.2.1. Quartz sand. In transformation of levoglucosan over

possible to regain the surface area of the zeolites through
quartz sand two peaks were detected from the liquid sample
regeneration. The main reason for the decrease of the surface
extracted with SPME and analyzed with GCeMS. These peaks
area is the blockage of the pores by large hydrocarbon mole-
were identified as ethyl acetate and 3-methyl-2-butanol (Fig. 4,
cules and carbon deposits, as it is suggested by the corre-
Table 4). It should be noted that these products were not
sponding decrease of the relative volume of micropores, i.e.
visible in HPLC.
pores with diameters less than 2 nm [20].

3.2.2.2. H-MCM-22. The conversion of levoglucosan was

3.2. Product characterization results
100% with all the tested amounts of catalyst. There was
however a significant difference in the product distribution
3.2.1. Gases
with different residence times. Comparing the molar yields,
No products were detected with the online GC equipped with
the main products were glycolaldehyde, formaldehyde and
a capillary column and FI detector from transformation of
acetaldehyde at low residence times and acetic acid and
levoglucosan over quartz sand or the two different types of
acetone at higher residence times (Fig. 5). The minor products
zeolites. The detector was, however, not suitable to detect CO
formed were furfural and succinic acid. As with the major
and CO2, nevertheless the formation of these products is
products the minor products declined in amount with
anticipated.
increasing residence time.
The main volatile product formed over H-MCM-22,
3.2.2. Liquid products
extracted with SPME, and analyzed with GCeMS was furfural
The products detected with HPLC were identified as glyco-
(Fig. 6(I), Table 5). At higher residence time (0.5 g of catalyst)
laldehyde, formaldehyde, acetaldehyde, furfural, 5-methyl-
the main products were ethyl acetate followed by 2-pentanol,
furfural, acetone, acetic acid and succinic acid. The HPX-87H
column used for analysis has been previously demonstrated
suitable for analysis of hydrothermolysis and biomass
1
degradation products [21]. The products were similar to those
2
mentioned in the literature on pyrolysis of levoglucosan in
Quartz sand products
a batch mode [22].
3
A variety of different volatile products were detected with
SPME in combination with GCeMS. The main volatile products 1

were also detectable with HPLC.

1-% levoglucosan solution

Table 2 e Brønsted and Lewis acid sites of the fresh

catalysts studied in the reaction. 1

Catalyst Brønsted acid sites Lewis acid sites Only fiber

(mmol/g) (mmol/g)
0 20 40 60 80 100
523 K 623 K 723 K 523 K 623 K 723 K
RT (min)
H-MCM-22-30 277 242 173 90 40 15
H-MCM-41-20 26 11 3 40 20 12
Fig. 4 e Background spectras and volatile products detected
from transformation of levoglucosan over quartz sand.
1972 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 9 6 7 e1 9 7 6

7
Table 4 e Volatile products extracted with SPME and
I)
detected with GCeMS from transformation of
1
levoglucosan over quartz sand.
Number Library/ID
0.125 g of catalyst
1 Background
5 6
2 Ethyl acetate 6 12 15 19
3 3-methyl-2-butanol 1
7
0.25 g of catalyst

2 14 20
phenol and 2-methyl phenol. The main products detected 18
13
with lower residence time (0.25 g of catalyst) were furfural, 3
benzofuran and 2-butanone. The main products with the 0.5 g of catalyst
lowest residence time (0.125 g of catalyst) were furfural, 1 4
9 18
5-methylfurfural and 3-butane-2-one. The results from
GCeMS are consistent with HPLC. At high residence times
there is no furfural present but the amount increases with
decreasing residence time. The amount of 5-methylfurfural in II) 1
7
the experiment over 0.125 g was so low that it was not
detectable with HPLC, being however visible with GCeMS
12 0.125 g of catalyst
which is more sensitive.
The analysis made with SPME is more qualitative than 8 11 15 17 21 23

quantitative in its nature, which means that it is not very

1
7
straightforward to report the amount of the volatile products
0.25 g of catalyst
detected with GC. For example, due to preferential extraction
of some compounds, the data from SPME might not corre- 12
16 18 22 24
spond to the concentrations in the liquid phase. Nevertheless,
7
one cannot neglect the fact that by far the largest peak 1
detected with SPME was from furfural. The quantitative 0.5 g of catalyst
amount of furfural was furthermore determined with HPLC, 9 10 18
and taking into account the large difference in peak areas
0 20 40 60 80 1 00
between furfural and the other compounds it is possible to
RT (min)
conclude that all the other products were formed in minor
quantities. Fig. 6 e Volatile products detected from transformation of
levoglucosan over I) H-MCM-22-30 and II) H-MCM-41
3.2.2.3. H-MCM-41. The products detected over H-MCM-41 catalysts.
were quite similar to the products over H-MCM-22 but with
the former catalyst 5-methylfurfural was also detected. The
main products were glycolaldehyde, formaldehyde and acet-
aldehyde (Fig. 7) which diminished in amounts with

Table 5 e Volatile products extracted with SPME and

Molar yield
detected with GC from transformation of levoglucosan
0.2
over H-MCM-22-30 and H-MCM-41 catalysts.
0.18 Glycolaldehyde
Number Library/ID Number Library/ID
0.16
1 Background 14 Benzofuran
0.14
2 2-Butanone 15 2-hydroxy benzaldehdye
0.12 Formaldehyde Acetic acid 3 Ethyl acetate 16 2-ethyl hexanol
4 2-pentanol 17 Acetophenone
0.1
5 Heptane 18 2-methyl phenol
0.08 Acetaldehyde
6 Toluene 19 2-furanmethanol
0.06 7 Furfural 20 2-methyl napthalene
Acetone 8 4-cyclopenten-1,3- 21 Benzodifuran
0.04
dione
0.02 9 Phenol 22 4-methyl-1-indanone
0 10 2-methyl-2- 23 1,2,3,4-tetrahydro-6,7-
0 0.004 0.008 0.012 0.016 cyclopentene-1- methyl-napthalene
one
0.125 g Residence time (min) 0.5 g 11 2-acetylfuran 24 1,2,3,4-tetrahydro-1,1,6-
12 5-methylfurfural trimethyl napthalene
Fig. 5 e Main products formed over different residence
13 Benzaldehyde
times of H-MCM-22 catalyst.
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 9 6 7 e1 9 7 6 1973

Molar yield naphthalene. At lowest residence time 0.125 g of catalyst

the main products were furfural followed by 5-methylfurfural,
Glycolaldehyde
0.3
4-cyclopenten-1,3-dione, 2-acetylfuran, 2-hydroxy-benzalde-
hyde, acetophenone, benzodifuran and 1,2,3,4-tetrahydro-6,7-
methyl-naphthalene.
There was a considerable difference in the amount of
0.2 products formed with H-MCM-22 and H-MCM-41 catalysts.
Glycolaldehyde and furfural were formed in much higher
Formaldehyde extent over H-MCM-41 than over H-MCM-22 catalyst (Fig. 8).
0.1 Acetaldehyde The current study with lower formation of furfural over
microporous zeolites compared to mesoporous materials
agrees well with our previous work [25].
The formation of acetic acid was higher over H-MCM-22
0
0.002 0.008 0.014 0.02
than over H-MCM-41 catalyst (Fig. 9). Similar results with high
formation of acetic acid from woody biomass over zeolites
0.125 g 0.5 g
Residence time (min)
with high acidity have also been reported elsewhere [26]. The
Fig. 7 e Main products formed over different residence amount of acetic acid increased with increasing residence
times of H-MCM-41 catalyst. time over H-MCM-22 catalyst while the opposite was valid for
H-MCM-41.

3.2.3. Reaction pathway

increasing residence time. Similar products have also been
reported in the pyrolysis of biomass in the presence of
Al-MCM-41 type catalysts [23]. The amount of the products
varied substantially between H-MCM-22 and H-MCM-41. The
concentrations of all products except acetic acid were higher
with H-MCM-41 than with H-MCM-22 catalyst.
The products detected in lower amounts were furfural,
acetic acid and 5-methylfurfural. Similar to the other products
these ones also decreased with increasing residence time.
Analogous results have also been reported in the literature
with glucose as a model compound [24].
The main volatile product detected over H-MCM-41 was also
furfural (Fig. 6(II), Table 5). At high residence time (0.5 g of
catalyst) the main products were furfural followed by phenol, 2-
methyl-2-cyclopentene-1-one, 4-methyl phenol, 2,3-dimethyl-
2-cyclopentene-1-one, 2-methyl phenol. The main products at
lower residence time (0.25 g of catalyst) were furfural followed
by 5-methylfurfural and 2-methyl phenol, 2-ethyl hexanol,
4-methyl-1-indanone and 1,2,3,4-tetrahydro-1,1,6-trimethyl
The products obtained in the transformation of levoglucosan
over H-MCM-22 and H-MCM-41 catalysts and the reaction
pathways proposed in the literature through which some of
the main and minor products have been formed is shown in
Fig. 10. Different catalysts promote different pathways,
which is shown in the figure. Levoglucosan gives furfural
and formaldehyde through some dehydration of the levo-
glucosan molecule [22]. Another path leads to 2 mol of
acetaldehyde and carbon monoxide. Glyceraldehyde is sug-
gested to be the intermediate through which glycolaldehyde
and formaldehyde is formed [13]. Glycolaldehyde is further
suggested to react into methanol and carbon monoxide.
Acetone and acetic acid are also formed through some
pathways for which the details are not yet known. Glycer-
aldehyde has not been detected as a product over H-MCM-22
or H-MCM-41 catalysts indicating that it has reacted further
into glycolaldehyde and formaldehyde, or that the reaction
mechanism is different and glycolaldehyde is not formed
through the intermediate glyceraldehyde. Glycolaldehyde

Molar yield
Molar yield
0.35
H-MCM-22

0.3 0.1

0.25

0.2 Glycolaldehyde

0.15 0.05
H-MCM-41
0.1

0.05 Furfural

0 0
0 0.005 0.01 0.015 0.02 0.025 0 0.005 0.01 0.015 0.02 0.025
Residence time (min) Residence time (min)

Fig. 8 e Formation of glycolaldehyde and furfural over Fig. 9 e Formation of acetic acid over H-MCM-22 and
H-MCM-22 (>) and H-MCM-41 (6) catalysts. H-MCM-41 catalysts.
1974 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 9 6 7 e1 9 7 6

H3C CH3
CH3
O
O
H3C O Acetone O
OH
II) 5-methyl furfural

Acetic acid
I) O
HO O
O
HO O +
HO O H H
OH II)
OH Furfural Formaldehyde
O
Levoglucosan
O
Succinic acid
O

HO H
II) Experimental
OH
Glyceraldehyde
Literature
O
HO
+ H3C O +
CO H
O Glycolaldehyde H
Acetaldehyde Formaldehyde

O O

H H H H + MeOH + CO
Formaldehyde Formaldehyde

Fig. 10 e Products formed from levoglucosan. Experimental reaction pathways and reaction pathways mentioned in the
literature [13,22]. I) Pathways prominent in transformations over MCM-22, II) pathways prominent in transformations over
MCM-41.

has further seen to react into formaldehyde and into
a product which, when analyzed with HPLC, has exactly the
same retention time as acetaldehyde. Glycolaldehyde has in
some previous work been suggested not to be formed from
levoglucosan but rather through the diversion of the reaction
channels prior to the formation of levoglucosan from cellu-
lose [27,28]. These results contradict with the observations in
the present study since glycolaldehyde has been seen as the
main product produced directly from levoglucosan in the
presence of acid catalyst.
[29]. It has also been stated that polyaromatic compounds
are the main products in hydrocarbon reactions above 700 K
whereas at lower temperature (400 K) the products gener-
ally results from condensation of the reactant without any
significant loss of hydrogen atoms [20]. It has been, for
example, shown that the nondesorbed products formed
from transformation of propene over H-ZSM-5 at 400 K
mainly are C12-C35 aliphatic hydrocarbons with no, one or
two unsaturated bonds.
3.4. Mass balance

3.3. Coke characterization results

The products detected from the coke analysis after dissolv-
ing the zeolites were mainly long hydrocarbon chains like
dodecane, 1-octadecene and eicosane and one aromatic
compound, 2,4-bis(1,1-dimethylethyl)-phenol (Table 6). This
product distribution corresponds well with literature data on
coke formation from catalytic pyrolysis of woody biomass
Table 6 e Products from coke analysis detected with
GCeMS.
Detected peaks Library/ID
1 Dodecane
2 1-pentadecane
3 Tetradecane
4 2,4-bis(1,1-dimethylethyl)-phenol
5 1-octadecene
6 Hexadecane
7 Eicosane
The mass balance was calculated based on the increase of the
reactor weight, the amount of left-over levoglucosan in the
pre-reactor and the measured TOC in the liquid phase (Table 7).
The sum of the masses of the different products was compared
with the total amount of input levoglucosan (200 mg). The
values for TOC were determined by dividing the measured
values of the total amount of organic carbon detected in the
liquid by the total amount of carbon in the input levoglucosan.
This ratio was then multiplied with the input levoglucosan
(200 mg). The total amount of coke was calculated based on
TGA measurements, whereas the amount of left-over levo-
glucosan in the pre-reactor was determined by analyzing the
water used for rinsing it with HPLC. The reason for the increase
in the weight of the reactor was due to coke formation on the
catalyst as well as tar formation on the reactor walls beneath
the catalyst bed. The amount of coke in percentage of the
catalyst mass was given by the TGA, which enabled a calcula-
tion of the total amount of coke formed on the specific amount
of catalyst in mg. The amount of coke increased on micropo-
rous MCM-22 with increasing residence time whereas the
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 1 9 6 7 e1 9 7 6 1975

Table 7 e Mass balance calculated for microporous H-MCM-22-30 and mesoporous H-MCM-41.
Levoglucosan left in pre-reactor Reactor weight increase TOC Total Mass
Residence mass balance
time (s) Total Coke

(mg) (mg) (mg) (mg) (mg) (%)

H-MCM-22-30
0.23 30 37 6 52 119 60
0.46 34 31 18 22 87 44
0.9 37 33 20 12 82 41
H-MCM-41
0.3 28 32 11 100 160 80
0.56 27 43 12 40 130 65
1.44 25 60 10 18 103 52

amount on the mesoporous MCM-41 was rather constant. The references

mass balance was closest to being complete with 0.125 g of
mesoporous MCM-41 catalyst (residence time 0.3 s) indicat-
ing that a smaller part (ca 20%) can be attributed as non-
condensable gases. With increasing residence time the value
for the mass balance decreased, indicating subsequently
higher formation of gases. Microporous MCM-22-30 being
more acidic than mesoporous MCM-41 generated more gases,
which can be seen as lower values of the total mass balance
closure compared to the corresponding amounts of the pillared
catalyst.
4. Conclusions
The catalytic activity of H-CMM-22-30 and H-MCM-41-20-F
was investigated in the conversion of levoglucosan at 573 K.
Thermal transformations were negligible. The yields of the
main products, the different oxygenated species (glyco-
laldehyde, formaldehyde, acetaldehyde, furfural, 5-methyl-
furfural, acetic acid), varied depending on residence time. The
main catalytic processes proceeding in transformation of
levoglucosan were thought to be combinations of catalytic
cracking and reforming and at high residence time the
amount of liquid products was very low indicating that there
is an increase in the formation of non-condensable products.
There was also a significant difference in the amount of
formed products between H-MCM-41-20 and H-MCM-22-30
catalysts. The former one yielded higher amounts for all the
main liquid products except acetic acid. H-MCM-22-30 is
much more acidic than H-MCM-41-20, and thus more active,
thereby splitting most of the bonds in levoglucosan into
products that were non-condensable. The degree of deacti-
vation of MCM-22 catalyst was more severe than of the mes-
oporous material, but both catalysts were regenerated
successfully recovering fully the surface area.
Acknowledgement
This work is part of the activities at the Åbo Akademi Process
Chemistry Centre within the Finnish Centre of Excellence
Programme (2000e2011) by the Academy of Finland.
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