Production of a bio-gasoline by

upgrading biomass ash pyrolysis

liquids via hydrogen processing and
catalytic cracking
M. C. Samolada
a
, W. Baldauf
b
and I. A. Vasalos
a
a
Chemical Process Engineering Research Institute, P.O. Box 361, 570 01 Thermi, Thessaloniki, Greece
b
Veba Oel A.G., Pawikerstrasse 30, D-45896 Gelsenkirchen, Germany
(Received 4 April 1997; revised 31 March 1998; accepted 31 March 1998)
A new procedure is proposed for the effective conversion of biomass ash pyrolysis liquids (BFPLs) to
transportation fuels. First, the hydrotreatment of a BFPL was studied, both in a thermal and in a catalytic mode.
The thermal hydrogenation of BFPLs, a modication of the VEBA Combi Cracking process, is a low cost and low
severity hydrogenation process without any operational problems. It has been proved to be the less sensitive
hydrotreatment process with respect to BFPLs. The liquid product of this process cannot be used in the renery
without further upgrading. However, its heavy fraction, mixed with an aromatic hydrocarbonaceous feedstock
(LCO) was considered as a potential FCC feedstock. The direct introduction of BFPLs in the FCC process was so
far infeasible, because of their particularly high tendency to coke formation. Commercially available cracking
catalysts were found to have an acceptable performance. Acceptable levels of coke on catalyst ( 1 wt%) and
gasoline yields (2325 wt%) were obtained. Commercial ReUSY catalysts with a Re
2
O
3
content of 0.6,
characterized by a narrow pore size distribution (D 36 A

), were found to be more appropriate for this

application. The obtained bio-gasoline meets the EU specications and is characterized by a high RON value of
96. 1998 Elsevier Science Ltd. All rights reserved
(Keywords: biomass ash pyrolysis liquids; hydrotreatment; catalytic cracking)
INTRODUCTION
Biomass ash pyrolysis liquids (BFPLs) cannot be used as
transportation fuels directly without a prior upgrading step
due to their high oxygen (4050 wt%) and water content
(1530 wt%) and the low H/C ratios. Their limited stability
under storage conditions due to the presence of a lot of
unsaturated compounds, e.g. aldehydes, and their minor
miscibility with conventional liquid fuels are additional
obstacles. Likely routes for the upgrading of biomass pyrolysis
liquids to improve their quality as fuels reported in the recent
literature include hydrotreatment and catalytic cracking.
Catalytic hydrotreatment of BFPLs is not an economical
approach till now, because of the high process and
equipment costs required to achieve an adequate degree of
de-oxygenation (9095 wt%) into marketable liquid fuels
1
.
Lots of operating problems so far reported, related to reactor
plugging and the almost complete catalysts deactivation,
permit only short pilot plant operation times (maximum
100 h). Mild hydrotreatment was alternatively investigated
in order to achieve bio-oils stabilization with a reduced
hydrogen consumption
2
. BFPLs performance in further
thermal upgrading is thus particularly improved along with
their stability under storage conditions
2,3
. Moreover, a lot of
operating problems were reported using conventional
hydrotreatment catalysts
2
. The development of new effec-
tive catalysts for this process is still an ongoing task
2
.
Fluid catalytic cracking (FCC) of BFPLs was considered
as a cheaper alternative, by converting oxygenated feed-
stocks to lighter hydrocarbons fractions falling particularly
in the gasoline boiling range. HZSM-5 catalyst, initially
developed by Mobil
4
for the MTG process (methanol to
gasoline process), was widely studied, but the results are not
encouraging due to high coking (825 wt%) and the low
quality of the fuels obtained (20 wt% phenolics)
57
. Using
other conventional commercial cracking catalysts, non-
aromatic hydrocarbons are mainly favored but coke
production is even enhanced
8
. The use of hydrogen rich
diluents (e.g. tetralin) do not notably improve the situation,
because coke still remains high for an FCC application (15
20 wt%)
5
, but an essential decrease in the produced
aromatic hydrocarbons can be achieved
8
. The application
of less severe cracking conditions (300400C) reduces
coke yields (415 wt%), but the liquid fuel obtained
contains signicant amounts of oxygenated compounds
8
.
Catalytic cracking of BFPLs over conventional FCC
catalysts is not a realistic approach due to extensive
coking, 2035 wt%
3,9
, which cannot be improved by an
appropriate commercial catalyst and conditions selection
3
.
Gasoline yields of almost 30 wt% accompanied by high
coke yields (20 wt%) were reported for the catalytic
cracking of a hydrotreated bio-oil, a product of biomass
liquefaction
10
. Efforts towards blending BFPLs with
petroleum feedstocks prior to catalytic cracking were
Fuel Vol. 77, No. 14, pp. 16671675, 1998
1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0016-2361/98 $19.00+0.00 PII: S0016-2361(98)00073-8
Fuel 1998 Volume 77 Number 14 1667
unsuccessful, because of their minor miscibility with
hydrocarbons
11
.
In this study, the two-step process of thermal hydrotreat-
ment and catalytic cracking of BFPLs is investigated.
Thermal hydrotreatment serves as the stabilization step for
the biomass derived feedstock to FCC. The process reported
is a modication of the VEBA Combi Cracking Process
developed for upgrading of petroleum residues and
wastes
12,13
. It is a process, which can be effectively
operated in a continuous slurry phase reactor. Ordinary
operating problems of catalytic hydrotreatment, such as
reactor plugging, are completely eliminated. Hydrogen
consumption and liquid product quality was measured and
compared to the respective gures of catalytic hydrotreat-
ment. Virgin bio-oil (B-EU-04D), derived from the Union
Fenosa Pilot Plant Unit (Spain) and its organic phase were
both considered as feedstocks. This product cannot be used
in the renery without any additional rening, because of its
particular properties (C/H 8, density: 0.951.00 g/cm
3
).
HBFPL mixed with a commercial light cycle oil, LCO, was
used as a cracking feedstock for the evaluation study of
representative commercial FCC catalysts. Extensive coking
affects the proper operation of the regenerator part of the
FCC unit and should be minimized as much as possible. The
conditions supplying acceptable coke on catalyst were
explored. The quality of the bio-gasoline obtained was
estimated and compared to gasoline EU specications.
EXPERIMENTAL
Catalytic hydrotreating bench scale unit
Catalytic hydrotreating was tested in a continuous
operating bench scale unit with a capacity of 50 to
300 g/h and in a process development unit with a capacity
of 1 to 10 kg/h (Figure 1a). The units are designed for
pressures up to 325 bar and temperatures up to 500C. In
normal operation liquid feed and hydrogen are pressurized
and fed to the top part of the reactor. The reactor (D
i
:
30 mm, L: 1130 mm) is equipped with ve individual
electric heating circuits, which are controlled by thermo-
couples in an internal thermowell. The rst third of the
reactor operates as a preheater, followed by the catalyst
section. The catalyst bed is operated under isothermal
conditions. After leaving the reactor at the bottom, the
products are cooled down, separated into liquids and gases,
and depressurized. Liquid and gaseous products are
collected and sampled. Feedstock and product owrates
together with the equivalent elemental compositions are
used for calculating a closed mass balance.
Production of a bio-gasoline by upgrading BFPLS: M. C. Samolada et al.
1668 Fuel 1998 Volume 77 Number 14
Figure 1 Experimental set-up of hydrotreatment experiments: (a) catalytic hydrotreating bench scale unit (1: xed bed reactor;
2: separator); (b) thermal hydrotreating process development unit (PDU) (1: reactor; 2: hot separator; 3: cold separator)
The ow direction of the bench scale reactor can be
switched from normal downow mode to upow mode.
This mode is sometimes used for testing, but not
commercially applied for standard hydrotreating. The test
program on catalytic hydrotreating covered variation in
temperature and space velocity. Two different catalysts
were tested, which are used in commercial processes.
Additionally the inuence of upow mode was checked
14
.
Thermal hydrotreating process development unit (PDU)
Thermal hydrotreating was performed in a process
development unit for slurry phase operation (Figure 1b).
This process is much less sensible against coking and was
derived for coal liquefaction, petroleum residue upgrading
(VEBA COMBI CRACKING Process) and can also be
applied to plastics and lignin hydrocracking.
Liquid feedstock is mixed with a small amount of ne
ground solids and hydrogen and fed to the bottom of the
reactor, which is built as an empty tube (D
i
: 45 mm, L:
4000 mm). The mixture is preheated to 100C to prevent
coking in the tubings. Final heating to reaction temperature
takes place in the rst half of the reactor. The upper part is
operated iso-thermally. Heating and temperature control are
similar to the catalytic test plants. Bubble ow behavior and
liquid hold-up in the reactor, which inuence the conversion
rates signicantly, can be controlled by the amount of the
solid additive. Product depressurization, collecting, sam-
pling, and balancing are similar to catalytic test plant.
The reactor efuent is fed to a high pressure separator,
which splits the heavy fraction and the solids from the light
product and gases. The hot separator top stream is cooled
down to 2050C. In the cold separator the liquid products
are separated from the gases. The bottom and the liquid
product are collected and measured. Gases are partly
recycled to the feed and partly depressurised in order to
adjust the system pressure. High pressure expansion gases
and dissolved gases from the liquids are collected and
measured by volume meters.
The tests on thermal upgrading concentrated more or less
on long term operability. Two tests were made with only the
organic fraction of pyrolysis oil after water separation, but
with the addition of 15% glycol for improving ow
behavior. One test was made with the virgin pyrolysis oil
without adding alcohol
11
.
The catalytic cracking unit
Catalytic cracking experiments were performed in a
modied MAT xed bed reactor system (MAT, ASTM
D3907-80), shown in Figure 2. Its detailed description can
be found elsewhere
3
. The reactant liquid mixture was fed at
the top of the xed bed reactor using an ISCO 500D pump
(0.110 cm
3
/min). A stream of N
2
(35 cm
3
/min) was
introduced at the top of the reactor to facilitate the
continuous withdrawal of the reaction products. The liquid
products were collected in a cold liquid bath ( 15C) and
their amount was weighted in a glass receiver. The amount
of coke deposited on the catalyst was measured by
combustion using a Leco CHN 800 elemental analyser.
Production of a bio-gasoline by upgrading BFPLS: M. C. Samolada et al.
Fuel 1998 Volume 77 Number 14 1669
Figure 2 The catalytic xed bed reactor system (1: liquid feedstock; 2: syringe pump; 3: injector; 4: catalyst bed; 5: reactor furnace; 6: cold
liquid bath; 7: liquid product receiver; 8: gas collection system
Catalysts were evaluated by performing experiments at a
temperature of 500550C, applying a (C/O)
r
and WHSV
within the range of 26 and 1419 h
1
respectively. The
considered responses are: gasoline and coke yield, coke on
catalyst, conversion and residue conversion. Their denition
is given in the Appendix. Mass balances of 90100 wt%
were normally obtained (Table 1). Poor mass recovery
90% resulted at conditions favouring coke formation.
Normalized results were always used in order to compare
catalysts behavior on a common basis.
The density of the feed used in each cracking experiment
was measured just prior to entering the xed bed reactor
using a DMA-48 PAAR densitometer. The amount of
gasoline, diesel and residue boiling range compounds in the
liquid product was measured by performing a simulated
distillation (ASTM D2887-78) in an HP 5890 GC. The
group type analysis of gasoline and RON evaluation were
performed according to well established procedures
15
. The
Micro Carbon Residue (MCR), being equivalent to the
Conrandson Carbon Residue (ASTM D 189) of heavy
hydrocarbons, was measured according to the ASTM D
4530-85 method.
Feedstocks
A eucalyptus ash pyrolysis liquid (B-EU-04-D) pro-
duced in the Union Fenosa Flash Pyrolysis Pilot Plant Unit
(Spain) was used as a feedstock in the hydrotreatment
experiments. From the thermal hydrotreating test runs, two
fractions of liquid product were sampled, one heavy fraction
boiling above hot separator temperature and one light
fraction boiling from ambient to hot separator temperature.
The heavy fraction produced at low severity hydrogenation
(80% deoxygenation) was the HBFPL used for the
preparation of the cracking feedstock. The cracking feed-
stock was a mixture of HBFPL/LCO (15/85 wt/wt). The
content of HBFPL was optimized by means of an acceptable
nal MCR content, thus approaching the carbon residue in
the feedstock of an FCC unit under a residue mode of
Production of a bio-gasoline by upgrading BFPLS: M. C. Samolada et al.
1670 Fuel 1998 Volume 77 Number 14
Table 1 Effect of catalyst type and WHSV on the distribution of product yields (wt%) and selectivities (T: 550C; (C/O)
r
: 6)
WHSV 19 19 19 19 14 14
Run L85C8ST-41
a
L85C8ST-42
a
L85C11ST-5
b
L85C11ST-6
b
L85C8ST-46
a
L85C8ST-50
a
Product yields (wt%)
Liquid 87.8 86.9 85.5 88.5 88.2 89.7
Gasoline 25.5 26.0 23.8 23.8 25.3 27.7
Gas 0.0 0.0 3.2 1.9 0.0 0.0
Coke 6.1 6.3 4.9 5.5 8.7 8.7
Mass balance 102.9 101.6 107.3 106.2 80.7 86.9
Conversion 31.6 32.3 32.7 32.0 34.0 36.4
Residue conversion 67.8 67.7 51.9 49.3 70.4 73.1
Coke/cat (wt%) 1.02 1.05 0.83 0.91 1.5 1.47
Selectivity (%)
Gasoline 80.7 80.6 72.9 74.5 74.4 76.1
Gas 9.8 5.9
Coke 19.3 19.4 15.2 17.0 25.6 23.9
a
ReUSY
st
1
catalyst;
b
ReUSY
st
2
catalyst.
Table 2 Feedstocks characterisation
Property BFPL LCO HBFPL LCO/HBFPL
(85/15 wt/wt)
Elemental analysis (wt%)
C 41.9 88.8 84.4 88.6
H 7.1 10.6 9.4 10.3
S 0.26 1.24 0.01 1.09
O 50.7 0.0 4.9 0.1
MCR 0.01 9.80 0.29
H
2
O 29.0
Simulated distillation (ASTM D 2887-78, wt%)
Gasoline 4.3 3.5
Diesel 71.7 23.0
a
64.5
Residue 24.1 77.0
a
32.0
Chemical composition (ASTM D-2549, wt%)
Saturate HCs 29.5 6.1
Aromatic HCs 69.5 18.6
Polar compounds 1.0 69.1
Undisolved compounds 6.2
a
Results from ordinary distillation.
Table 3 Characterization of catalysts
Characteristic ReUSY
st
1
ReUSY
st
2
BET (m
2
/g) 154.9 141.5
Zeolite 120.1 86.0
Matrix 34.8 55.5
Re
2
O
3
Microporosity (cm
3
/g)
8 D 900 A

0.134 0.133
20 D 46 A

0.0256 0.0425
46 D 900 A

0.0832 0.0664
PV
Hg
(cm
3
/g)
0.01 D 10 (mm) 0.9384 0.6809
0.2 D 2 (mm) 0.152 0.0083
0.02 D 0.2 (mm) 0.039 0.095
0.004 D 0.02 (mm) 0.0998 0.0638
0.003 D 0.007 (mm) 0.0501 0.0463
Subscript st represents steamed form.
operation (i.e. mixing about 15 vol% atmospheric tower
bottom into VGO). The characterisation of all feedstocks
used in the present study is given in Table 2.
Catalysts
Catalysts used for catalytic hydrotreatment tests were
commercially available NiMo and CoMo catalysts
11
for
diesel and vacuum gas oil desulfurization. For thermal
hydrotreatment no catalysts were used.
For the catalytic cracking experiments, two commercial
FCC catalysts (ReUSY
1
, ReUSY
2
) recently used in Greek
reneries were considered for evaluation. Their character-
izations are given in Table 3. Their 75 mm fraction was
used for the cracking experiments, in order to avoid high
pressure drops along the catalyst bed. They were tested after
a steamed deactivation procedure in a uid bed reactor
(T: 688C for 9 h, P 1 atm, 100% steam). The BET
surface area of the catalysts was measured by applying the
t-plot method using a Quantachrome Autosorb I unit. Pore
volume (PV
Hg
) was measured in a Micromeritics Autopore
II 9220 unit.
RESULTS AND DISCUSSION
Production of HBFLP by hydrotreating
Different severities of hydrotreating were achieved by
variation of reaction temperature and space velocity. As a
characteristic measure for severity the deoxygenation rate of
organic oxygen was used. Figure 3 shows the variety of
investigated severities for catalytic and thermal upgrading.
The product yields obtained and the liquid product proper-
ties are shown in Figure 4.
For catalytic hydrotreating, deoxygenation rates of 88 to
99.9% were achieved. At high severities and deoxygenation
rates of 95%, a yellow to white clear liquid could be
obtained, which met the specications for standard crude
oils. Unfortunately, only very short runtimes could be
realized. After 100 h of operation, the repetition of the
starting point showed a severe deactivation of the catalyst
which ended with coking and plugging a short time later.
Variation of catalyst and ow direction did not improve this
behavior. Thermal hydrotreating in a slurry phase reactor
was made at deoxygenation rates of 78 to 85%. A total
runtime of a week could be realized without any operational
problems.
Yields are illustrated in Figure 4a. Organic liquid yields
varied between 30 and 55 wt%, depending on the severity
and the water content of the feedstock. Whereas the
maximum yield for virgin pyrolysis oil reached 40%, the
yield for the organic fraction was higher due to the fact that
a signicant amount of water was separated prior to
hydrotreating. Consequently, the water yield, which is the
sum of feed water and reaction water, reaches the highest
value at high severity (55%) and is still 40% at low severity
for feeding of organic fraction. Gas make is the sum of
hydrocarbon gases, carbon oxide and carbon dioxide. The
yields varied between 8 and 18 wt%. Hydrogen consump-
tion was measured between 3 and 5 wt% related to pyrolysis
oil feed (virgin or organic fraction) and includes both
organic reactions and production of water. There is not an
evident decrease in hydrogen consumption at low de-
oxygenation in the overall evaluation.
Liquid product qualities were described by a variety of
standard petroleum analyses. Three characteristic properties
are illustrated in Figure 4b. For high hydrotreating severity
(99.9% deoxygenation) C/H-ratio, density and oxygen
concentration meet specications, which allow all fractions
to be blended into renery streams with minor or without
further rening. At severities below 95% deoxygenation the
qualities are unacceptable for the renery. C/H 8 and
densities 0.95 g/cm
3
allow only feeding to the crude
distillation with subsequent heavy rening. The most
important fact is the oxygen content of 3 to 8%, which is
accompanied by signicantly increasing water content in
the liquid and increasing problems with separation of water
and organic product phases. These facts inuence the
operating performance of the desalter in the distillation unit
and the downstream processing units of conversion
processes.
Generally, both the light and the heavy fraction could be
used as an FCC feedstock. The characteristics of the
fractions are shown in Table 4. From the boiling behavior it
is evident that the heavy fraction is closer to normal
FCC feedstocks. The light fraction already contains 30%
Production of a bio-gasoline by upgrading BFPLS: M. C. Samolada et al.
Fuel 1998 Volume 77 Number 14 1671
Figure 3 Deoxygenation achieved under various modes of
hydrotreatment
Figure 4 Effect of the type and the extent of hydrotreatment on:
(a) product yields (: oil; B: H
2
O; O: gas; B: H
2
consumption)
and (b) total liquid product properties (B: C/H; O: oxygen content;
: density)
gasoline. The quality differences between organic phase and
virgin bio-oil originated HBFPLs are not signicant (Table
4). For all these reasons, the heavy fraction of thermally
upgraded virgin pyrolysis oil was used for further cracking
investigations.
Evaluation of FCC catalysts
The selection of the cracking conditions for a catalyst
evaluation study using an unconventional feedstock is an
important task, because it affects both conversion and coke
production. Initial experiments over ReUSY
1
catalyst at a
WHSV of 19 h
1
showed that by increasing the reaction
temperature from 500 to 550C, conversion increases
substantially, from 18 to 32 wt%
11
. Meanwhile, coke is
decreased, because the incremental conversion produced
mainly gasoline and light gases. Since conversion of less
than 20 wt% is not desirable, it was decided to perform all
experiments at 550C. Higher temperatures should be
avoided in order to prevent secondary cracking reactions
producing additional coke and/or gases. Furthermore,
conversion does not increase remarkably even under more
severe conditions (WHSV: 14 h
1
, Table 1). The effect on
product yields, particularly coke, is more essential, while
gasoline yield remains almost unchanged (Table 4).
WHSVs lower than 14 h
1
could not be effectively applied
with (C/O)
r
remaining in the range of 26 due to the
limitations of the experimental set-up. All evaluation
experiments were thus performed at a temperature of
550C and a WHSV of 19 h
1
.
The performance of REUSY
1
and ReUSY
2
in terms of
coke on catalyst content and gasoline yield at different
(C/O)
r
levels is given in Figure 5. Coke on catalyst, rather
than coke yield, is considered as the primary evaluation
criterion of catalysts in this study, in order to select an
acceptable FCC pilot scale operation mode. Coke on
catalyst decreases when (C/O)
r
is increasing and gets its
lower value at the higher (C/O)
r
applied (Figure 5).
REUSY
2
catalyst gives the lowest coke on catalyst,
0.87 wt% at (C/O)
r
6, thus being more attractive
Production of a bio-gasoline by upgrading BFPLS: M. C. Samolada et al.
1672 Fuel 1998 Volume 77 Number 14
Table 4 Liquid product qualities of BFPL thermal hydrogenation
Feed Organic phase Organic phase Virgin oil
High severity
a
Low severity
b
Low severity
b
Product fraction
Light Heavy Light Heavy Light Heavy
Part from total liquid (wt%)
Liquid 69.5 30.5 67.3 32.7 70.1 29.9
Elemental analysis (wt%)
Carbon 79.9 84.2 81.8 82.2 82.2 84.4
Hydrogen 10.3 8.9 10.8 8.6 10.7 9.4
Sulfur 0.02 0.03 0.01 0.17 0.01 0.01
Nitrogen 0.15 0.43 0.14 0.33 1.15 0.42
Oxygen 7.9 5.9 6.2 5.3 6.4 4.9
Properties
Acetone insolubles (wt%) 0.5 n.e. 1.0
H
2
O (wt%) 1.6 1.1 0.99
Density (g/cm
3
) 0.952 1.053 0.928 1.109 0.942 1.036
Distillation data (wt%)
200C 28.7 32.0 27.0
200350C 57.5 24.3 52.2 18.2 55.3 23.0
350500C 13.8 60.1 15.8 65.4 17.8 66.0
500C 15.6 16.4 11.0
a
343C;
b
327C.
Figure 5 Effect of (C/O)
r
and catalyst type on gasoline yield (K,
S) and coke on catalyst (O, ); (S, ): ReUSY
1
; (K, O):
ReUSY
2
Figure 6 Effect of conversion and catalyst type on gasoline yield
(a) and coke yield (b); open symbols: gasoline conversion; solid
symbols: residue conversion; (S, ): ReUSY
1
; (K, O): ReUSY
2
(Figure 5). Gasoline yield does not vary signicantly by
changing either the catalyst type or the (C/O)
r
. A maximum
gasoline yield of 23.8 wt%, was achieved at a (C/O)
r
4
with ReUSY
2
catalyst. REUSY
1
catalyst gives a slightly
higher gasoline yield of 25.0 wt%, at (C/O)
r
4 (Figure 5).
Gasoline and coke yields usually depend linearly on
conversion in VGO catalytic cracking
16
. Over a narrow
conversion range, a linear correlation between gasoline
coke yield and conversion can be detected in the present
study (Figure 6). The variation on both conventional and
residue conversion was considered. The slope of both lines
is positive and depends on the catalyst type rather the
denition of conversion (Figure 6). Similar trends were
also observed by Songip et al.
17
in the catalytic cracking of
a heavy oil from waste plastics over ReY catalysts
at 300450C. An inverse trend of the gasoline yield
was observed at high levels of conversion ( 80 wt%) due
to overcracking
17
.
The observed conversion of LCO/HBFPL is generally
lower than ordinary VGO conversion (6080 wt%), pri-
marily because of the limited crackability of LCO.
Conversion remains unaffected by the introduction of
HBFPL to LCO on both catalysts tested (Figure 7).
Moreover, introduction of HBFPL to LCO results in a
higher residue conversion over ReUSY
2
, thus verifying its
selectivity in converting the heavy parts of the feedstock as
well (Figure 6). The use of ReUSY
1
catalyst results in a
higher residue conversion (Figure 5) and a higher coke
selectivity at the same time (Table 1). This fact is probably a
characteristic of most commercial cracking catalysts
18
.
Conversion of non-conventional feedstocks is a compli-
cated function of their crackability, catalyst type and testing
conditions. Conversion of a coal derived liquid can be
increased from 40 to 80 wt% using HZSM-5 or HY
catalysts, respectively
19
. Crackability can be effectively
described by either aromaticity (H/C ratio) and/or the
(MCR) content of the feedstock. Generally, oxygen rich
aromatic feedstocks are highly polar and characterized by
high carbon residues
17,18
(Table 2) and low H/C ratios,
thus forming a lot of coke (28 wt%) during cracking
1,3,19
.
If catalysts are evaluated in a fresh form rather than
being steamed deactivated, higher conversions, of even
80 wt%
17
, can be generally expected.
Introduction of HBFPL into LCO results in the increase in
both gasoline and coke yields using ReUSY
2
catalyst
(Figure 8). Assuming independent cracking reactions for
the feedstock components, addition of 15 wt% HBFPL to
the feedstock contributes to the gasoline and coke produc-
tion by 32 and 56%, respectively, at the optimum cracking
conditions. Similar trends were observed by Ng and
Rahimi
18
using non-conventional but hydrocarbonaceous
feedstocks, namely co-processing distillate and shale oil.
Low conversions ( 50 wt%) accompanied by low gasoline
yields ( 25 wt%) were obtained. These type of feedstocks
are generally of minor importance for a direct FCC
application at present, but have a lot of potential interest
for future applications
20
.
Catalysts physical characteristics, including the type and
the amount of the contained zeolite, affect essentially their
behavior under cracking, therefore the nal coke produced.
Generally, ReY catalysts are recommended for heavy
feedstocks catalytic cracking
16
. The Re
2
O
3
content of the
catalyst affects the structural characteristics of the catalyst
and therefore the distribution of the nal products during
VGO catalytic cracking. It is generally recommended to be
around 0.5 wt% for maximum gasoline yields
16
. Only
ReUSY
2
contains Re
2
O
3
in the desired concentration
(Table 3). Cracking of large molecular compounds takes
place in the large pores of the catalysts structure produc-
ing additional coke
20
. Based on porosity measurements,
ReUSY
1
catalyst contains meso pores of two different mean
diameters, 36 and 60 A

, respectively, while ReUSY

2
contains only small pores of a diameter of 36 A

(Figure
9). A widely different structure of macropores was also
detected according to PV
Hg
measurements. ReUSY
1
con-
tains more large pores than ReUSY
2
(Table 3). The unique
structure and composition of ReUSY
2
preserves the
conversion of heavy compounds within a limited level,
thus producing low coke and acceptable gasoline yields at
the same time.
Production of a bio-gasoline by upgrading BFPLS: M. C. Samolada et al.
Fuel 1998 Volume 77 Number 14 1673
Figure 7 Effect of (C/O)
r
, catalyst type and feedstock on
conversion and residue conversion; (S, ): ReUSY
1
; (K, O, A,
B): ReUSY
2
; (A, B): LCO
Figure 8 Effect of (C/O)
r
and feedstock type on gasoline and
coke yields under catalytic cracking over ReUSY
2
catalyst; (K, O):
LCO/HBFPL (85/15 wt/wt); (A, B): LCO
Figure 9 Pore size distribution of catalysts ( : ReUSY
1
; :
ReUSY
2
)
Gasoline composition
The effect of the catalyst type and the feedstock chemical
characteristics on gasoline composition is essential
(Table 5). ReUSY
2
gives a higher RON gasoline than
ReUSY
1
due to the high content of total aromatics. The
contents of branched parafns and saturated naphthenes are
also lower in the ReUSY
2
gasoline. Both saturated
naphthenes and aromatics are increased if HBFPL is
introduced into the LCO feedstock (Table 5). Even though
HBFPL contains heavier compounds than LCO (Table 2),
they contribute mainly to gasoline and coke formation
rather than to heavy aromatic compounds formation, C

8
(Table 5). Toluene content increases considerably in the
case of ReUSY
2
bio-gasoline, being threefold compared to
LCO gasoline, but benzene remains almost unaffected
(Table 5).
The fraction of aromatic hydrocarbons and polar
aromatics of HBFPL (Table 2) are the primary sources for
the formation of aromatic hydrocarbons during cracking.
GC/MS analysis of the polar fraction proved that it contains
large molecular polyphenols and aromatic acids. If ReUSY
2
bio-gasoline is going to be compared with an ordinary FCC
gasoline, the main deviations in composition are the
following (Table 5). Bio-gasoline contains lower amounts
of olens and naphthenes, while the content of total
aromatics is especially higher, contributing to a higher
RON (Table 5). Nevertheless, the ReUSY
2
bio-gasoline
composition is compatible with the EU specications for
environmental gasoline
21
.
CONCLUSIONS
Thermal hydrotreatment of BFPLs can be effectively
operated producing liquid products which can be effectively
upgraded in a renery. The heavy liquid product of this
process (HBFPL) can be used as a co-feed of the FCC
process for the production of transportation fuels using
commercial FCC catalysts. The produced bio-gasoline is
characterized by a high RON value (96) and meets the EU
specications. Although the economics of the proposed
process are not fruitful at present (the price of HBFPL is ve
times the price of common VGO
11
), the proposed upgrading
sequence of BFPLs is a positive step considering the on
going EU policy towards a higher biomass contribution to
the net energy balance. The zero content of heavy metals
and sulfur (0.01 wt%) of HBFPL, which are the major
factors responsible for FCC catalysts deactivation, are
additional advantages for the partial substitution of ordinary
feedstocks with bio-oils. Pilot scale experiments will simulate
the real case for this application and will give enough data for a
technoeconomic evaluation of the whole process.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the EC funding for
the completion of this project under contract AIR2-CT92-
1086. The role of Union Electrica Fenosa (Madrid, Spain) as
a program co-ordinator and a prompt supplier of bio-oil
samples is greatfully acknowledged. Professor R.
Bertolacini (Delaware University, USA) is acknowledged
for a lot of useful discussions on FCC catalysts testing and
applications. The staff of the Environmental Fuels Lab of
CPERI, particularly Miss E. Stergioula, is thanked for their
prompt collaboration.
APPENDIX
The denitions of the symbols used in this study are given
below.
(1) Weight Hourly Space Velocity, WHSV
WHSV (h
1
)
60Q
f
d
f
W
(2) Catalyst to Oil ratio, (C/O)
r
(C=O)
r

W
Q
f
d
f
t
r
(3) Coke on catalyst %C
(4) Conversion (%) 100 (RD)=(R
f
LUn)
(5) Residue conversion (Conversion
r
): percentage of the
residue cracked
Conversion
r
(%) 100
R
p
R
f
L
where: Q
f
is the liquid feed ow rate (cm
3
/min); d
f
is the
liquid feed density (g/cm
3
); W is the catalyst weight (g); r
t
is the reaction time (min); C is the carbon content (wt%);
R is the residue content (wt%); D is the diesel content
(wt%); L is the liquid yield (wt%); Un is the unconverted
amount of the feedstock (wt%); and the subscripts p and f
represent product and feed, respectively.
Production of a bio-gasoline by upgrading BFPLS: M. C. Samolada et al.
1674 Fuel 1998 Volume 77 Number 14
Table 5 Effect of catalyst and feedstock type on gasoline composition
Chemical group ReUSY
1
(LCO/HBFPL) ReUSY
2
(LCO/HBFPL) ReUSY
2
(LCO) FCC
a
(VGO)
n-Parafns 2.3 2.3 2.5 3.11
Branched-parafns 20.6 16.5 16.7 26.4
Saturated naphthenes 5.4 4.2 3.8 6.6
Unsaturated naphthenes 1.2 1.2 1.4 3.4
Normal olens 5.3 5.4 6.2 11.8
Iso olens 9.1 8.8 10.3 15.4
Di-olens 0.7 0.5 0.7 1.8
Naphtheno-aromatics 8.1 7.3 7.9 3.5
Aromatics 47.3 53.8 50.5 28.0
Aromatics
Benzene 1.00 1.19 1.13 0.69
Toluene 4.9 12.9 5.2 3.7
C

8
41.2 39.4 43.8 23.1
RON 94.1 95.8 94.7 92.2
a
A commercial FCC catalyst for VGO catalytic cracking.
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Production of a bio-gasoline by upgrading BFPLS: M. C. Samolada et al.
Fuel 1998 Volume 77 Number 14 1675