Fuel 78 (1999) 11471159

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Catalytic upgrading of pyrolytic oils to fuel over different zeolites

S. Vitolo a,*, M. Seggiani a, P. Frediani b, G. Ambrosini a, L. Politi a
a
Dipartimento di Ingegneria Chimica, Chimica Industriale e Scienza dei Materiali, Universita di Pisa, Via Diotisalvi 2, 56126 Pisa, Italy
b
Dipartimento di Chimica Organica, Universita di Firenze, Via Gino Capponi 9, 50121 Firenze, Italy
Received 27 October 1998; accepted 28 February 1999

Abstract
The upgrading of wood pyrolysis oils produced in the ENEL fast-pyrolysis plant located in Bastardo, Italy, and in the Union Fenosa fast-
pyrolysis plant located in La Coruna, Spain, was studied by using HZSM-5 and H-Y zeolites in a fixed-bed laboratory scale reactor, at
different temperatures and residence times. The products of the catalytic upgrading were a liquid fraction, char, coke, tar and gas. While the
upgraded liquid obtained by using the HZSM-5 consisted of easily separable organic and aqueous layers, the liquid obtained by using the HY
zeolite consisted of a single phase in which the organic components were either dispersed or dissolved in the water. The effect of temperature,
catalyst type and residence time in the reactor on the yields of the fractions obtained (oil, char, tar, coke, gas and aqueous fraction) and on the
characteristics of the upgraded oils was examined. q 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Pyrolytic oils; Catalytic upgrading; Zeolites

1. Introduction cracking catalysts (zeolites, silicaalumina and molecular

The bio-oils obtained by fast pyrolysis of wood have
received attention recently as an alternate source of fuel.
The major advantages of these fuels are that these are CO2
neutral [1] and contain a very low fraction of bonded
sulphur and nitrogen. Thus, they contribute very little to
the emission of greenhouse gases or other regulated air
pollutants [2,3]. Pyrolysis oils are complex mixtures of
organic compounds that exhibit a wide spectrum of chemi-
cal functionality, and generally contain some water [46].
Their direct use as fuels may present some difficulties due to
their high viscosity, poor heating value, corrosiveness and
instability [7,8]. Also, they are not always completely vola-
tile and contain high levels of oxygen, this being the major
factor responsible for the high viscosity and corrosiveness.
The upgrading of pyrolytic oils, a necessary process before
they can be used as a regular fuel, essentially involves the
removal of oxygen. Currently, two methods have been
proposed. The first method is a typical catalytic hydrotreat-
ing with hydrogen or hydrogen and carbon monoxide under
high pressure and/or in the presence of hydrogen donor
solvents [810]. As a thermal treatment in the absence of
catalysts does not seem to produce a significant upgrading
[11], alternatively, upgrading may be achieved using
* Corresponding author. Tel.: 1 39-50-511278; fax: 1 39-50-511266.
E-mail address: vitolo@docenti.ing.unipi.it (S. Vitolo)
0016-2361/99/$ - see front matter q 1999 Elsevier Science Ltd. All rights reserved.
PII: S0016-236 1(99)00045-9
sieves). This operation is performed at atmospheric pressure
and hydrogen is not required. The advantages derived from
operating at atmospheric pressure and in the absence of
hydrogen have driven the interest towards this second
upgrading route and some studies have been reported in
literature [1115]. The products obtained depend on the
characteristics of the catalyst used: a mostly aromatic
hydrocarbon product is obtained when strong acid-shape
selective HZSM-5 zeolites are used, whereas mostly alipha-
tic hydrocarbons are produced when HY zeolites and silica
alumina are used. The oxygen in the oxygenated compounds
of biomass pyrolysis oils is mainly converted to CO, CO2,
and H2O [13]. Unfortunately, the yield of hydrocarbons is
generally low because of the high yields of char, coke and
tar. These undesired products, which are deposited on the
catalyst and cause its deactivation, make a periodical or
continual regeneration necessary.
In this work, three different fast pyrolysis oils obtained
from the ENEL plant of Bastardo (Italy) and the Union
Fenosa plant of La Coruna (Spain) were upgraded on a
fixed bed laboratory scale reactor using the HZSM-5 and
HY zeolite type catalysts. While the upgraded liquid
obtained using the HZSM-5 consisted of an organic and
an aqueous layer that are easily separable, the upgraded
liquid obtained when the HY zeolite was used consisted
of a single phase in which the organic components were
both dispersed and dissolved in water. As far as the fuel
1148 S. Vitolo et al. / Fuel 78 (1999) 11471159

Fig. 1. Schematic diagram of the experimental apparatus.

qualities of the upgraded oils were concerned, the oils
obtained with the HZSM-5 catalyst type turned out to be
the most interesting and were studied in more detail. The
effect of temperature, catalyst type and residence time in the
reactor on the yields of the fractions obtained (oil, char, tar,
coke, gas and aqueous fraction) and on the characteristics of
the upgraded oils was examined.
2. Experimental
2.1. Raw bio-oils
HZSM-5 having a silicaalumina ratio of 80 (HZSM-5/
80), and (c) H-Y having a silicaalumina ratio of 80 (HY/
80).
The strong acid sites of the HZSM-5 zeolites are located
in a three-dimensional system of intersecting channels,
characterised by intermediate size pore openings (5.5 A),
which restrict the access of branched and cyclic hydro-
carbons but allow the straight-chain and monomethyl
paraffins to enter and be preferentially cracked to the lighter
products (shape selectivity). Of the two HZSM-5
samples, the HZSM-5/50 zeolite is characterised by a higher

Two samples of raw pyrolytic bio-oils were supplied by Table 1

ENEL-CRT, Pisa, Italy. They were produced, respectively, Properties of the raw bio-oils
from the Canadian oak (oil sample A) and a mixture of
Sample
Canadian oak and Swedish pine (oil sample B) in the
ENEL fast-pyrolysis plant located in Bastardo, Italy, A B C
which is based on the ENSYN RTP process. The University
Water content (wt.%) 29 38 30
of Sassari, Italy, supplied one sample of pyrolytic bio-oil;
PH 2.7 3.2 3.5
this was produced from pine (oil sample C) at the Union Density (g/ml) 1.22 1.17 1.22
Fenosa fast-pyrolysis plant located in La Coruna, Spain, Viscosity (cP) 20.3 13.4 122
which uses the Union Fenosa WFPP process. Elemental analysis (wt.%)
C 43.8 37.2 52.9
2.2. Catalysts H 7.5 8.0 4.9
N 0.1 0.2 0.3
Three different zeolites were used as catalysts in order to O (by difference) 48.3 54.2 41.8
Ashes (wt.%) 0.3 0.4 0.1
investigate the influence of pore size and acidity: (a) HZSM- Heating value (kcal/kg) 4859 4541 4383
5 having a silicaalumina ratio of 50 (HZSM-5/50), (b)
 S. Vitolo et al. / Fuel 78 (1999) 11471159
concentration of acid sites than HZSM-5/80 zeolite [16].
The H-Y zeolites have weaker acid sites and parallel
channels whose openings are large enough (7.4 A) to
admit quite large molecules [17].
In general, a high silicaalumina ratio is beneficial both
for cracking heavy feeds and for improving thermal stability
[1719].
Zeolyst International, London, UK supplied the zeolites
in powder form; zeolite (b) and (c) were supplied in H-
exchanged form, while zeolite (a) was supplied as NH4-
exchanged form. To generate the acid sites, the ammonia
was driven off by heating the catalyst in a stream of dry
nitrogen at 5508C for about 4 h.
In order to prevent the elevated pressure losses in the
fixed catalyst bed, the powder was compacted by pressure
(about 680 atm); after crushing, the fraction sieved between
14 and 18 mesh was selected for use.
The granules were conditioned before performing the
upgrading runs by heating at 5508C for about 1 h in order
to eliminate the water present both as humidity and bonded
to the crystals.
In this study, the catalysts were only used once. No
further tests were performed with the regenerated catalyst.
2.3. Equipment and experimental procedure
The experiments were conducted at atmospheric pressure
in a continuous down-flow mode using a fixed bed micro-
reactor. The experimental set-up and procedures were simi-
lar to those adopted by Adjave et al. [11,15]. A schematic
diagram of the upgrading experimental apparatus is reported
in Fig. 1. The reactor was a 700 mm long, 20 mm i.d. quartz
tube placed coaxially in a thermostated furnace (600 mm
long). The reactor was loaded with the catalyst granules
(1418 mesh size), held on a quartz wool plug (bottom
plug, about 0.1 g) which in turn was supported by an inner
quartz tube (280 mm long, 11 mm o.d.) that had the function
Fig. 2. IR spectrum of the raw bio-oil (sample A).
1149
of supporting the catalytic bed in the middle zone of the
furnace, where the temperature was practically constant.
One quartz wool plug (top plug, about 0.2 g) and a bed of
quartz beads (1.9 mm diameter, about 10 g) were placed
above the catalyst. The bed was brought to the reaction
temperature in a stream of nitrogen. When the desired
temperature was reached, the nitrogen flow was stopped
and the raw bio-oil fed into the reactor with a micro-meter-
ing pump (Harvard Apparatus 22 syringe pump). Some of
the bio-oil components formed a solid residue in the upper
section above the catalytic bed due to thermal conversion at
the reactor temperature. This residue was deposited on the
beads and the top plug, while the lighter vapourised fraction
(together with water) flowed down through the catalyst bed
where the upgrading reactions produced coke (deposited on
the catalyst), a heavy organic fraction (condensed on the
catalyst and on the bottom sections of the reactor: bottom
plug, inner tube, inside walls of the reactor), a lighter liquid
fraction (collected into an ice trap at the reactor outlet) and a
gaseous fraction (collected at atmospheric pressure in a
series of vials over dibutylphthalate in order to minimise
the absorption of CO2). The amount of the liquid product
produced was determined by weight difference of the trap
before and after the run. The gas was measured volumetri-
cally. The upgraded liquid product was obtained either in
the form of two layers (an organic and an aqueous layer) or
as a single phase in which the organic components were
both dispersed and dissolved in water. When a double
layer was obtained, the two phases were separated by centri-
fuge at 5500 rpm for about 15 min; afterwards the organic
layer, defined as oil was drawn off with a micropipette.
The amount of oil produced was determined by the differ-
ence in weight of the liquid product before and after draw-
ing off of the organic layer.
After each run, the bed of quartz beads, the top plug, the
catalyst, the bottom plug and the inner tube were all
removed from the reactor. The inner surface of the reactor,
1150 S. Vitolo et al. / Fuel 78 (1999) 11471159

Table 2 on the quartz beads, determined by weight difference of the

Compounds identified by GC/MS in the raw bio-oils beads before and after the run, was defined as char. After
Compound Identified compounds (%) a washing the catalyst with acetone, drying in oven at 1008C
for 1 h, and heating in air in a muffle furnace at 6008C for
Sample A Sample B Sample C 1 h, the amount of solid that was determined by weight
Vinyl formate 1.7 2.2 0.2
difference before and after heating the dried washed catalyst
Vynil acetate 3.7 3.7 2.4 was defined as coke.
Acetic acid 0.5 0.6 0.5
2-Furanaldehyde 1.4 2.4 1.5
2.4. Reactor operation
2-Methylbutanol 2.8 3.1 2.8
2(5H)-Furanone 3.5 2.5 3.7
Cyclohexanone 1.4 1.3 1.4
The runs were performed over a temperature range of
Cyclopentenone 0.6 1.4 0.6 4104908C for all the three raw bio-oils and the three cata-
Phenol 1.3 2.2 1.3 lysts. The raw bio-oil flow rate was 5.9 ml/h. Most of the
Methylcyclopentadione 3.0 3.2 3.0 runs were conducted using 2 g of catalyst, corresponding to
2-Methoxyphenol 4.2 3.2 4.3 a residence time of 17 g cat/g oil/min. In order to evaluate
2-Methoxy-4-methylphenol 3.7 2.8 3.8
4-Ethyl-2-methoxyphenol or
the influence of the residence time, 1 g of catalyst HZSM-5/
2-Methyl-1,4-dimethoxybenzene 2.1 1.3 1.8 50 was used at 4508C (residence time 8.5 g cat/g oil/min).
2-Methoxy-5-(1-prop-2- 2.4 2.8 3.5 Each run lasted for about 30 min and was performed in
enyl)phenol triplicate.
2-Methoxy-4-propylphenol 1.2 1.3 1.1
Ethyl butyrate 0.7 0.2 0.2
1-(4-Hydroxy-3- 1.3 0.5 1.1 2.5. Chemical and physical analysis
methoxyphenyl)etanone
1-(4-Hydroxy-3- 1.6 1.3 1.7 Characterisations of both the raw bio-oils and the
methoxyphenyl)propan-2-one products obtained by upgrading were conducted by
1-(4- 1.7 1.7 1.6 performing the analysis described below.
Hydroxymethoxyphenyl)propanol
Hexanoic acid 12.4 7.9 4.7
The Marcusson method [20] was used to determine the
4-Ethyl-2-methoxyphenol 2.2 4.1 11.8 water content of the raw bio-oils. The water content of the
Decanol 2.1 1.1 1.9 upgraded oils was determined by the Karl Fischer titration
a
[21] (Schott Titroline Alpha Automatic Karl Fischer Titra-
The amount (%) of the products were evaluated through the gc-area; no
tor Model 633, Riedel-de Haen Hydranal Reagents: solvent
response factors were introduced.
34800, titrant 2 34811). The calorific value of both the raw
bio-oils and the upgraded oils was determined using the
the surface of the inner tube, the catalyst and the bottom ASTM D 3286 method (Mahler calorimeter). Elemental
plug were washed with acetone and the acetone-soluble analysis of the raw bio-oils was performed using a Carlo
portion, determined gravimetrically by evaporating the Erba DP 200 C, H, N analyser. The elemental analysis of the
solvent, was defined as tar. The solid fraction deposited upgraded oils could not be performed due to their high

Fig. 3. Devolatilisation profiles (TG and DTG) of the raw bio-oils.

 S. Vitolo et al. / Fuel 78 (1999) 11471159
Fig. 4. Combustion profiles (TG and DTG) of the raw bio-oils.
volatility. The density measurements were made using an
Aston Paar DMA 58 density-measuring cell, while the visc-
osity measurements were conducted using a Contraves STV
rotational viscosimeter. pH measurements were made by a
Hanna Instruments pH meter model 8417.
The raw bio-oils and upgraded oil samples were subjected
to thermogravimetry (TGA) and derivative thermogravime-
try (DTG) using a Mettler TC 10A thermobalance at a gas
flowrate of 32 Nml/min and at a heating rate of 408C/min.
The samples were characterised by the evaporation profiles
(under nitrogen flow) and the combustion profiles (under air
flow).
The raw and upgraded oils were analysed by infrared
spectroscopy (Perkin Elmer FT-IR 1600) and gas chroma-
tography (Shimatdzu GC 17A) employing a fused silica
capillary column SPB1 (30 m 0.25 mm i.d.) and a flame
ionisation detector (FID). The temperature in the gas chro-
matograph oven was programmed from 50 to 2508C (508C
for 10 0 , a heating ramp at 38C/min from 50 to 2508C and a
final isotherm step at 2508C for 5 0 ), the injection tempera-
ture of the sample was 3008C. Chromatographic peaks were
identified by gas chromatograph-mass spectrometry
(Shimatdzu MS QP 5000).
When a double layer was obtained, the COD value of the
aqueous layer was also determined after separation from the
oil using a colorimetric method (HACH DR/2000 spectro-
photometer) after digestion of the sample with standard
reagents (HACH COD Digestion Reagent Vials).
3. Results and discussion
3.1. Characterisation of the raw bio-oils
Table 1 reports the properties of the raw bio-oils studied.
Quite high water and oxygen contents were observed. These
1151
are responsible for the low calorific value and the high
acidity of the oils. The higher viscosity of sample C is an
index of the longer period of storage period this bio-oil was
subjected to before use, compared to the samples A and B
which were studied a few days after their production. A
more detailed characterisation of the bio-oil was conducted
by infrared spectroscopy and gas chromatography-mass
spectroscopic analysis.
As the IR spectra of the three samples were quite similar,
only the IR spectrum of the raw bio-oil A is reported in Fig.
2 for conciseness. The lack of the absorption bands in the
31003000 cm 21 region (aromatic CH stretching vibra-
tion), in the 16001450 cm 21 region (skeletal CC stretch-
ing vibration), in the 13001000 cm 21 region (in-plane
bending vibration of the ArH), and in the 900650 cm 21
region (out-of-plane bending vibration of the ArH) indi-
cate a non-aromatic composition. The presence of oxyge-
nated functional groups is made evident by the large intense
band of the intermolecular hydrogen bonds OH stretching
vibration at 3400 cm 21, by the in-plane bending at
1246 cm 21 and the out-of-plane bending at 668 cm 21 of
the associated OH group. The absorption band at
1066 cm 21, which is due to the CO stretching vibration,
makes it possible to assign the OH absorption to alcohols;
the presence of ketonic functional groups is made evident by
the 1721 cm 21 CyO stretching band. The paraffinic struc-
ture of the oil is confirmed by the 2976 and 2874 cm 21
bands arising from the CH stretching vibrations, and by
the 1461 and 1365 cm 21 bands due to the CH bending,
attributed to methyl and methylene groups. The intense
absorption band at 900 cm 21 may be assigned to the char-
acteristic vibrational mode of the out-of-plane CH bending
in alkenes. The presence of olefinic compounds is confirmed
by the band at 1647 cm 21, arising from the CyC stretching
vibration mode. The IR analysis, therefore, characterises the
raw bio-oil as being composed of aliphatic components,
 1152

Table 3
Overall product distribution for the conversion of the raw bio-oils using HZSM-5/50 and HZSM-5/80 catalysts (average values of triplicate runs)

Sample Catalyst Temperature Residence time Yield (wt.%) Gas evolved

(8C) (g cat/g oil/min)
Oil a Oil b Water Char Coke Tar Nml/g Calculated
of oil yield c
(wt.%)

Raw bio-oil sample A HZSM-5/50 410 17 9.6 13.5 42.0 19.6 7.5 2.9 89.1 17.5
450 17 16.1 22.7 37.3 17.0 8.6 1.0 98.2 19.3
8.5 18.8 26.4 38.0 15.8 6.9 3.0 84.5 16.6
490 17 11.8 16.9 37.4 18.6 9.6 0.3 110.0 21.6
HZSM-5/80 410 17 7.9 11.1 43.2 21.4 7.0 3.0 83.5 16.4
450 17 12.8 18.0 37.4 18.1 9.0 1.7 100.8 19.8
490 17 8.4 11.8 37.5 19.9 10.3 0.0 116.6 22.9
Raw bio-oil sample B HZSM-5/50 410 17 7.0 11.3 44.6 19.7 6.9 1.9 90.1 17.7
17 14.5 23.4 38.5 16.9 8.2 1.0 103.3 20.3
450
8.5 16.0 26.6 40.7 15.1 6.8 2.1 92.1 18.1
490 17 10.0 16.1 39.0 18.7 9.3 0.0 117.1 23.0
HZSM-5/80 410 17 7.5 12.0 43.9 22.8 7.3 2.2 75.8 14.9
450 17 12.8 20.6 39.7 18.9 8.5 1.0 90.6 17.8
490 17 9.0 14.5 38.4 20.2 10.2 0.2 108.4 21.3
S. Vitolo et al. / Fuel 78 (1999) 11471159

Raw bio-oil sample C HZSM-5/50 410 17 9.4 13.4 40.0 18.1 7.2 2.3 105.4 20.7
17 15.5 22.1 34.4 16.1 9.0 1.1 114.5 22.5
450
8.5 18.1 25.9 39.7 12.9 6.4 2.1 98.8 19.4
490 17 10.8 15.4 35.4 17.6 10.9 0.1 126.8 24.9
HZSM-5/80 410 17 7.0 10.0 44.8 20.4 7.1 2.4 84.5 16.6
450 17 10.6 15.1 41.0 17.2 8.7 1.3 98.8 19.4
490 17 7.9 11.3 39.3 19.6 9.7 0.1 112.5 22.1
a
With respect to the raw bio-oil as-received.
b
With respect to the water free raw bio-oil.
c
As CO2.
 S. Vitolo et al. / Fuel 78 (1999) 11471159 1153

Table 4
Overall product distribution for the conversion of the raw bio-oils using H-Y catalyst (average values of triplicate runs)

Sample Temperature (8C) Yield (wt.%) Gas evolved

Oil in water Char Coke Tar Nml/g of oil Calculated yield a (wt.%)

Raw bio-oil sample A 410 50.1 24.4 8.8 2.9 69.2 13.6
450 49.2 20.3 10.7 2.0 87.6 17.2
490 45.4 21.5 11.7 0.8 105.4 20.7
Raw bio-oil sample B 410 50.7 24.2 8.8 2.7 67.7 13.3
450 49.4 21.6 10.1 1.7 86.0 16.9
490 46.8 19.5 12.3 1.0 101.8 20.0
Raw bio-oil sample C 410 49.5 23.5 9.3 3.4 70.2 13.8
450 51.4 20.1 10.2 1.8 83.5 16.4
490 46.1 21.0 11.7 0.9 101.8 20.0
a
As CO2.

most of which are saturated and show alcoholic, ketonic and
carboxylic functional groups.
The complex composition was also confirmed by the GC-
MS of the bio-oils. The peaks identified by mass spectro-
metry are reported in Table 2. The bio-oils are characterised
by a high percentage of oxygenated groups (hydroxyl,
carbonyl and carboxyl) bonded prevalently to aliphatic
moiety. Aromatic structures were not identified, confirming
the IR analysis.
The thermogravimetric profiles (TGA and DTG) under a
flow of nitrogen (evaporation profile) and air (combustion
profile) flow are reported in Figs. 3 and 4, respectively. The
profiles of the three oils are very similar and present the
typical trend exhibited by pyrolytic oils [22]. The weight
loss in the first part of the evaporation curve (up to 1508C)
may be attributed to the removal of both water and the
lighter organics (DTG peak at about 80 and 1308C); the
weight loss in the second part of the curve, in the range
1503008C, indicates the evaporation of the heavier organic
compounds. After the main devolatilisation, the cracking of
the heavier residue occurs and a slow and continuous degra-
dation proceeds until about 8389% of the oil is devolati-
lised at 8008C.
The thermogravimetric profiles in air are similar to the
evaporation profiles up to 2503008C (volatilisation of
water and organic compounds); between 300 and 4508C,
the weight loss is lower compared to the weight loss in
nitrogen, probably due to the oxidation of the residual
organic compounds; finally, the combustion of the residue
occurs in the 4505508C range. The combustion is practi-
cally completed at 8008C for all the samples.
3.2. Catalytic upgrading of the raw bio-oils
3.2.1. Overall product distribution
When upgrading was carried out with the HZSM-5 cata-
lysts, the liquid fraction consisted of two easily separable
layers: an organic phase and an aqueous phase, at all
temperatures and residence times. When the H-Y catalyst
was used, a single phase was obtained which consisted of a
suspension of oil in water. The products of the conversion
using the HZSM-5 catalysts were oil, water, coke, char, tar
and gas. For the conversion using the H-Y catalyst, a disper-
sion of oil in water, coke, char, tar and gas were produced.
The yield of the different products and the normalised
volumes of the gas are reported in Table 3. By assuming
that the gas consists mainly of CO2 [13], the resulting yields
were calculated and are reported in Table 3; the fairly
good agreement of the calculated yields with the material
balance confirms that the gas evolved is predominantly CO2.
The oil yields are reported both with respect to the raw
bio-oil as-received and with respect to the water-free raw
bio-oil.
The effect of temperature on the distribution of the
products was similar for the two HZSM-5 catalysts used.
The maximum conversion of raw bio-oil to upgraded oil
with the minimum conversion to char was obtained at
4508C. The quantity of gas and coke increased with the
reaction temperature, while the quantity of aqueous fraction
and tar decreased with temperature.
The overall product distribution, as a function of tempera-
ture, can be explained by the reaction pathways proposed in
literature for the acidic zeolite-type catalysts. As soon as the
raw bio-oil was fed to the reactor, it was exposed to a
combination of two processes: a thermal effect before
contacting the catalyst, followed by a thermocatalytic effect
inside the catalyst bed. It has been proposed [14] that the
rapid heating before contacting the catalyst produces the
separation of the bio-oil components in light organics,
heavy organics, and char, the latter being formed by poly-
merisation of some unstable components of the raw bio-oil.
The light and heavy organics enter the catalyst bed and
undergo the thermocatalytic process. In the case of the
acidic zeolite-type catalyst, it is suggested that the heavy
organics are in part cracked to light organics and in part they
deposit on the catalyst surface where they may act as coke
precursors. The light (mainly oxygenated) organics are
cracked, deoxygenated (dehydration is the main route),
decarboxylated and decarbonylated. Through a carbenium
ion mechanism [23], oligomerisation of the cracked
1154 S. Vitolo et al. / Fuel 78 (1999) 11471159

Fig. 5. Upgraded oil yield versus char yield.

fragments, followed by alkylation, isomerisation, cyclisa-
tion and aromatisation together produce a mixture of light
aliphatic (C1 C6) and aromatic (C6 C10) hydrocarbons.
Some of the aromatic hydrocarbons polymerise to form
coke.
The higher char yield obtained below 4508C was prob-
ably due to a lower degree of volatilisation of the bio-oil
above the catalyst bed while above 4508C, a higher deposi-
tion of heavy components above the catalyst bed may be
attributed to an increase in the thermal cracking. Higher
temperatures favoured catalysis of the cracking reactions,
thus increasing the gas production, and of the aromatisation/
polymerisation reactions and resulting in an increasing yield
of coke. In most cases, the increase of temperature favoured
the gasification of the tar that had been formed, hence a
smaller quantity of tar was obtained.
The overall product distribution of products was also
influenced by the zeolite type. Use of the most acidic
HZSM-5/50 catalyst produced the maximum yield of
upgraded oil at 4508C (22.123.4 wt.% yield with respect
to the water free raw bio-oils fed) whereas the H-Y catalyst
generally produced higher yields of char, coke and tar
(Table 4). The lower level of coke formation on the
HZSM-5 catalysts (6.910.9 wt.% of the raw bio-oils fed)
 S. Vitolo et al. / Fuel 78 (1999) 11471159 1155

Fig. 6. IR spectra of the upgraded oils (sample A, HZSM-5/50 at 4508C) at different residence times and comparison with the IR spectrum of the raw bio-oil.

was probably due to the more limited formation of coke
precursors (polycyclic compounds, aromatics and polyalk-
ylnaphtalenes) inside the HZSM-5 structure. As the pore
size limited the upper dimension of the products that
could be formed, this meant that the coke formation became
a shape-selectivity reaction [23,24].
The influence of the residence time on the overall product
distribution was studied by performing the upgrading runs at
a residence time reduced by half using the HZSM-5/50
catalyst at 4508C; using these operating conditions, the
maximum yields of the upgraded oil were obtained at
17 g cat/g oil/min.
As the residence time was reduced, an increase of the oil
fraction yield, a significant reduction of the coke formation,
a slightly lower fraction of char and gas yield and an
increase of the tar yield was observed (Table 3). Lower

Table 5
Compounds identified by GC/MS in the oils obtained by upgrading of the raw bio-oil sample A at different temperatures (residence time 17 g cat/g oil/min)
using HZSM-5/50 and HZSM-5/80 catalysts

Compound Identified compounds (%) a

HZSM-5/50 HZSM-5/80

4108C 4508C 4908C 4108C 4508C 4908C

Benzene 2.0 1.2 1.5 0.0 1.3 1.5

Toluene 4.7 3.1 7.1 2.8 2.5 4.5
Ethylbenzene 3.0 2.6 3.7 2.3 1.0 4.4
1,3-Dimethylbenzene 10.5 9.4 17.0 10.3 9.6 13.7
Propylbenzene 0.2 0.2 0.0 0.2 0.1 0.4
1,2,4-Trimethylbenzene 10.0 11.8 13.9 9.9 5.7 11.6
Butylbenzene 0.2 0.3 0.3 0.2 0.1 0.3
2-Methylphenol 2.0 3.3 1.6 5.4 9.2 3.6
1-Methyl-4-(2- 2.3 2.4 0.8 2.0 0.8 5.7
propenyl)benzene
1,2,3,5-Tetramethylbenzene 0.4 0.5 0.2 0.0 0.1 0.6
Naphtalene 5.7 6.2 11.0 4.4 5.9 7.1
Methylnaphtalene 8.1 9.2 14.8 5.2 6.2 7.2
1-Ethylnaphtalene or 2- 3.2 3.4 2.7 1.2 2.2 3.7
ethylnaphtalene
2,3-Dimethylnaphtalene 5.8 6.3 15.4 4.3 5.3 6.5
Methylanthracene 1.7 2.6 2.1 0.5 1.0 1.0
Dimethylanthracene or 0.5 0.5 0.7 0.2 0.3 0.6
dimethylphenantrene
a
The amount (%) of the products were evaluated through the gc-area; no response factors were introduced.
1156 S. Vitolo et al. / Fuel 78 (1999) 11471159
Table 6
Low heating values of some upgraded oils obtained at 4508C
Oil sample Low heating value (kcal/kg)
A B
Upgraded by HZSM-5/50 8901 8710
(residence time 17 g cat/g oil/min)
Upgraded by HZSM-5/50 8281 7410
(residence time 8.5 g cat/g oil/min)
Upgraded by HZSM-5/80 9120 9312
(residence time 17 g cat/g oil/min)
coke formation associated with lower residence times is
probably due to a reduction in the condensation/polymerisa-
tion reactions inside the catalyst bed because there is not
enough time to convert the bio-oil compounds to the heavi-
est and final products of the thermochemical treatment. The
extent of the gasification of both the tar and the char was
also reduced. If a lower residence time seemed to produce
beneficial effects in terms of reducing the cokification on the
catalyst, and hence in terms of reducing its deactivation, the
degree of deoxygenation of the oil was much lower, as
discussed in the following section.
Generally, the oil yield may be related to the char yield,
as reported in Fig. 5.
3.2.2. Characterisation of the upgraded oils
The water content of the oil fractions ranged from 1.3 to
1.8 wt.% and was substantially due to the method of separa-
tion of the two phases by the micropipette.
The IR spectra of the upgraded oils showed a different
composition compared with the raw bio-oils. A significant
aromatisation and a decrease of the amount of oxygenated
functional group content occurred by using both the HZSM-
5/50 and the HZSM-5/80 zeolite at all the temperatures and
residence times. In Fig. 6, the IR spectra of sample A
upgraded at 4508C with HZSM-5/50 at different residence
times are reported and compared with the IR spectrum of the
raw bio-oil. The aromatisation is evidenced by the absorp-
tion bands in the 31003000 cm 21 region (aromatic CH
stretching vibration), in the 16001450 cm 21 region
(skeletal aromatic CyC stretching vibration), in the 1300
1000 cm 21 region (in-plane bending vibration of the ArH),
and in the 900650 cm 21 region (out-of-plane bending
vibration of the ArH). The presence of paraffinic
compounds is evidenced by the 30002840 cm 21 absorp-
tion bands arising from the CH stretching vibrations, and
by the 1450 and 1375 cm 21 bands of CH bending of the
methyl and methylene groups, while the absorption bands
that can be attributed to alkenes, observed in the raw bio-oil,
did not appear to be present. The bands of the free and
associated OH stretching vibration (broad bands at 3545
and 3400 cm 21) of the OH group in-plane bending
(1246 cm 21) and out-of-plane bending (668 cm 21), the C
O stretching vibration (1066 cm 21) and the CyO stretching
C
7155
8196
of the ketonic functional groups (1721 cm 21) appear as a
weak band with respect to the IR spectrum of the raw bio-
oil. The higher relative intensity of the absorption bands of
the oxygenated functional groups in the oil upgraded using a
lower residence time indicates that a higher yield of oil is
obtained in this operating condition, but it contains a larger
amount of oxygenated compounds. The gas chromato-
graphic analysis of the upgraded oils, obtained using the
HZSM-5 zeolites, were quite similar for the three samples
and confirm the IR analysis. The products identified by the
mass spectrometry are reported in Table 5. The bio-oils are
characterised by an elevated percentage of aromatic
compounds, prevalently toluene, ethylbenzene, xylene and
trimethylbenzenes.
The upgraded oils showed quite a significant increase in
the heating value, which may be considered as an index of
the deoxygenation of the oils; as the yield of the oil
increases, a decrease of the heating value may be observed
(Table 6).
The degree of deoxygenation can also be observed from
the characterisation of the aqueous phase by COD analysis.
A higher COD value may be explained by a higher amount
of non-upgraded polar oxygenated hydrocarbons, which
remained dissolved in the aqueous phase resulting from
the thermocatalytic treatment. By observing the results
summarised in Fig. 7, the HZSM-5/80 zeolite seemed to
perform a better deoxygenation treatment at 4108C. As the
temperature was increased, the upgrading by HZSM-5/50
resulted in a higher level of deoxygenation. Reducing the
residence time resulted in a considerably higher COD value
of the aqueous phase, confirming that a lower level of deox-
ygenation is achieved at these operating conditions.
The combustion profiles (TGA and DTG) in air flow of
the upgraded oils did not show substantial differences by
changing the raw bio-oil sample. Generally, the TGA curves
show a major loss up to 2003008C, and a minor loss at
5006008C due to evaporation of the light fractions and
combustion of the carbonaceous residue, respectively, as
reported by the DTG curves. The intermediate cracking
phase is practically absent. This behaviour indicates that
the deoxygenated oil produced, compared to the raw bio-
oil, is characterised by a higher content of light fractions,
easily vaporised at temperatures lower than 2008C, so that
 S. Vitolo et al. / Fuel 78 (1999) 11471159

Fig. 7. COD value of the aqueous phase separated from the upgraded oil obtained at different temperatures and residence times, over HZSM-5 zeolites.
1157
1158 S. Vitolo et al. / Fuel 78 (1999) 11471159

Fig. 8. Combustion profiles (TG and DTG) of the upgraded oil (sample B upgraded at 4508C and residence time 17 g cat/g oil/min) over the HZSM-5/50 and
HZSM-5/80.

the upgraded oils may be classified in the gasoline hydro-
carbon range. The influence of the catalyst is shown in Fig. 8
for the sample B, as an example. When a more acidic cata-
lyst (HZSM-5/50) was used, the combustion profiles
showed a slightly wider range of evaporation temperature
and a shift of the peak towards higher temperatures. These
are both an index of the presence of heavier compounds in
the upgraded oils, whose formation is favoured at these
operating conditions. As the residence time in the catalyst
bed is reduced, the combustion profiles of the upgraded oil
reveal the presence of a wider range of molecular weight
compounds and some amount of heavy residue which
underwent combustion at about 6008C, as shown in Fig. 9
for sample C. This behaviour reveals that the upgrading of
the raw bio-oil was not complete at the lower residence
time, and it produced an oil having characteristics similar
to the raw bio-oil.
4. Conclusions
The catalytic upgrading of pyrolytic oils to fuel is
obtained over HZSM-5 zeolites, by which the upgraded
oil may be easily separated from the aqueous phase. The
higher yields of oil were obtained at 4508C with HZSM-5/
50. The catalytic upgrading produced a highly deoxyge-
nated oil having a quite elevated heating value and a good
combustibility. The formation of coke on the catalyst was
not negligible and hence, may be the cause of a rapid deac-
tivation. By reducing the residence time, less amount of

Fig. 9. Combustion profiles (TG and DTG) of the upgraded oil (sample A upgraded at 4508C over HZSM-5/50) at 17 and 8.5 g cat/g oil/min residence time.
 S. Vitolo et al. / Fuel 78 (1999) 11471159 1159

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