CHAPTER 8

Application of bio-oil derived from plant biomass in petrochemical industry

Melisa Bertero, Marisa Falco, Ulises Sedran*

Instituto de Investigaciones en Catálisis y Petroquímica INCAPE (FIQ, UNL – CONICET)
Santiago del Estero 2654, (3000) Santa Fe, Argentina
*TE: +54(342)452-6082. Fax. +54(342)453-3858, e-mail: usedran@fiq.unl.edu.ar

Abstract

The production of fuels and raw materials for the chemical industry from bio-oils obtained by
the pyrolysis of residual lignocellulosic biomass is an attractive option which deserves sounder
research. Particularly, co-processing bio-oils together with conventional feedstocks in existing
refining processes, that is, taking advantage of present infrastructure, could be feasible, without
the need for extra capital costs. The catalytic cracking of hydrocarbons (FCC) and hydrotreating
processes are certainly possible acceptors for bio-oils, since their catalysts and process
conditions are proper to convert oxygenated compounds in bio-oils into high value products.
However, bio-oils could contribute significantly to coke yields, a fact which could be alleviated
if the boil-oils are previously upgraded by means, for example, of a thermal process. Anyway,
some of the present FCC technologies permit processing residual hydrocarbons feedstocks with
a high coke forming potential, without a negative impact on process performance.

In order to know about reaction mechanisms and products in the conversion of bio-oils over
FCC catalysts, the catalytic cracking of model compounds representing the various chemical
types which can be found in bio-oils, of a synthetic bio-oil assembled with those model
compounds and of crude and upgraded bio-oil from the pyrolysis of pine sawdust was studied
under FCC conditions in a MAT-type reactor. The crude and upgraded bio-oil were also studied
in a CREC Riser Simulator reactor.

It was observed that phenolic and aromatic ethers as well as some cyclic ketones and furans
produce significant amounts of coke (up to 16 %wt.). Starting from all the chemical types it was
possible to produce high value hydrocarbons, particularly light olefins and hydrocarbons in the

1
gasoline range. Moreover, the thermal upgrading of actual bio-oil decreased up to 30 % its
potential to form coke and improved its processability, thus impacting positively on the co-
processing with fossil feedstocks. During co-processing with vacuum gas oil (VGO) under
typical FCC conditions in the CREC Riser Simulator reactor, it was observed that for high
proportions of oxygenated compounds (up to 20 %), the yield of gasoline decreased and the
yield of light olefins increased, but coke yield was lower than that from pure VGO due to the
dilution effect from water in the bio-oil. Following more realistic conditions (addition of 5% of
bio-oil to the VGO), the distribution of products was not changed significantly.

Key Words
Bio-oil, catalytic cracking, hydrodeoxygenation, fuels, FCC

1. General view about co-processing bio-oils in refineries

Partial replacement of fossil feedstocks by other from renewable sources, such as

biomass, in order to produce transportation fuels and raw materials for the chemical
industry is a subject matter which has been steadily gaining interest in academic and
applied research in the last decade (Corma et al., 2007; Elliott et al., 2007; Al-Sabawi et
al., 2012). The decrease in the reserves of oil and the instability in the barrel’s price,
together with social concern about environmental, have all boosted the search for new
sources for liquid fuels. In that sense, the use of biomass as a raw material is interesting
due to its essentially nil CO2 balance, given its reabsorption during its growth, and its
very low content of nitrogen and lack of sulphur and metals (Mohan et al., 2006).
Moreover, biomass is cheap and easily available almost everywhere.
As it was described in Chapter 2, residual lignocellulosic biomass, derived from forest
and agriculture industries, can be pyrolyzed to obtain bio-oil, a liquid with a very high
content of oxygenated compounds and water.

Even though the characteristics of the bio-oils are very different from those of oil
derived fuels (high acidity, high content of oxygenated compounds and water,
immiscibility with hydrocarbons, corrosiveness, thermal and chemical instability, etc.),
the possibility of co-processing them in oil refineries is an attractive option which

2
deserves to be studied soundly. Co-processing bio-oils in refineries would allow
obtaining fuels with essentially no capital costs, as compared to new developments
aimed at using biomass only as the raw material.

The process of catalytic cracking of hydrocarbons (FCC) is one of the most promising
potential receptors to bio-oil co-processing, since the catalysts used, which are mainly Y
zeolite supported on a matrix (either active (alumina or silica-alumina) or inactive
(silica)), is useful to deoxygenate bio-oils and produce hydrocarbons (Adjaye y
Bakhshi, 1995, Corma et al., 2007). Hydrotreating, which requires hydrogen, is also
potentially effective to remove oxygen from bio-oils (Fuminsky, 2000; Elliot et al.,
2007). Concerning these options, large refining companies are studying these
possibilities (Marker, 2005; Biocoup, 2014), analyzing both technical and economy
issues in bio-oil co-processing.

In order to ease co-processing, it is convenient to previously condition the bio-oils, so as

to decrease their coke-forming potential and confer higher stability and miscibility with
hydrocarbons (in case it is necessary, like in hydrotreating processes). In this way, for
example, it is possible to attenuate problems in transfer lines due to clogging by
polymerization of oxygenated compounds. Most important efforts in this sense were
aimed at decreasing the concentration of phenolic compounds in bio-oils, which are
considered the main coke precursors in their conversion over acidic zeolites and FCC
catalysts (Srinivas et al., 2000; Gayubo et al., 2010), and compounds which are more
refractory to deoxygenation by hydrotreating (Laurent and Delmon, 1994; Elliott et al.,
2007). Phenolic compounds can be removed selectively out of bio-oils after thermal
treatments (Valle et al., 2007; Gayubo et al., 2010; Bertero et al., 2011; Bertero and
Sedran, 2013a) or by means of liquid-liquid extraction (Chum and Blanck, 1990). In this
last case, once recovered, phenolic compounds could be used as raw materials in the
synthesis of pharmaceutical and polymeric products, to produce adhesive materials and
for the partial replacement of phenol in phenol-formaldehyde resins (Effendi et al.,
2008). Some authors consider that, in order to co-process bio-oils in FCC, it is
necessary that they be miscible with hydrocarbons (Samolada et al., 1998; Marker et al.,
2005; Lappas et al., 2009; Fogassy et al., 2010; de Miguel Mercader et al., 2010) and,
consequently, propose a previous conditioning through hydrotreating to reduce the
3
content of oxygen and remove water. However, under present technologies, bio-oils
could be fed to the process following different configurations which do not require
miscibility with conventional feedstocks and, particularly, considering that the bio-oil to
VGO relationship would not be especially high. Some alternatives for tackling these
points were discussed by Corma et al. (2007). The injection of bio-oil could be
performed, for example, immediately before the injection of VGO, where severity is
extreme as given by the high temperatures and the high catalyst to oil relationships
which can be achieved. Bio-oils could also be injected in the stripper section, where
cracking conditions are moderate, with lower temperatures and reduced activity in the
catalyst particles due to the deposition of coke on their surface. Finally, bio-oils could
be injected together with the VGO, with intermediate conditions in the process. This
conceptual scheme, however, may impose that the setting-up of the co-processing of
bio-oils to the commercial range might require some changes in the present, typical
operative conditions for a given unit, which should be evaluated particularly.

In relation to the high concentration of water in bio-oils, it must be considered the

dilution effect it can produce over the hydrocarbon feedstock and, moreover, water
could affect the heat balance of the process, acting as a heat sink due to its high heat of
vaporization. However, it is common practice in the commercial operation of FCC units
to inject steam at different locations in order to help fluidization and transport of the
catalytic bed. Then, adding bio-oil to the feedstock could complement this effect.
Finally, and considering that the total amount of bio-oil would represent only a fraction
of the current hydrocarbon feedstock, the impact could be indeed irrelevant.

The feasibility of co-processing bio-oils in existing refining processes, with emphasis in

the effect of incorporating oxygenated compounds on the distribution of the products
generated in the FCC and hydrotreating processes.

2. Hydrotreating

Hydrotreating is a process in refineries which is conventionally used with heavy

hydrocarbon mixtures. It comprises a series of reactions involving hydrogenation,
4
deoxygenation and cracking and, in some cases, the removal of nitrogen, sulfur and
metals (Fuminsky, 2000; Elliott et al., 2007). The catalysts used in the process (typically
sulfided CoMo and NiMo supported on γ-alumina) could also be useful to deoxygenate
bio-oils. However, even though hydrotreating to remove sulfur and nitrogen
heteroatoms from hydrocarbons is a well proven refining process, bio-oil
hydrodeoxygenation is still under incipient research. Typical process conditions are
temperatures from 300 to 450 ºC and hydrogen pressures between 35 and 170 bar; it is
clear, then, that in this case the cost of transforming bio-oils into useful fuel components
would be considerably higher than in other options, particularly catalytic cracking, as
discussed in the following sections.

2.1. Model compounds

Using model compounds to study the hydrodeoxygenation of bio-oils is particularly

interesting to understand reaction mechanisms and the consequent distribution of
products in hydrotreating co-processing. One of the most important facts is to know
which are the chemical groups which particularly contribute to the formation of
hydrocarbons or, on the contrary, which are more refractory. Many studies on this
matter were reviewed by Furimsky (2000) and Elliott et al. (2007), where alkylated
phenols, phenolic ethers, furans, aldehydes, ketones and, to a lower extent, acids, ethers
and esters were used. The studies were performed in fixed bed reactors at temperatures
between 250 and 450 ºC and hydrogen pressures between 50 and 70 bars, and they were
focused on catalyst development, given the fact that typical commercial hydrotreating
catalysts did not show the same effectiveness over all the chemical groups present in
bio-oils.

For example, when converting guaiacol (a phenolic ether which is very abundant in bio-
oils) over conventional hydrotreating catalysts under typical process conditions,
conversions were lower than 60 %, with high coke yields, the main products being
cathecol and phenol (still oxygenated products), with benzene and cyclohexane being
observed at low proportions when reaction times were very long (Laurent and Delmon,
1994). Further studies showed that guaiacol is deoxygenated more extensively over
monometallic (Rh) or bimetallic (Pd-Pt), ZrO2 supported catalysts (Gutierrez et al.,
5
2009), or over transition metal phosphites (Ni2P, MoP, WP), SiO2 supported catalysts
(Zhao et al., 2010), with phenol and benzene as the main products. Yet removing the
hydroxyl group from phenol is extremely complicated over all the catalysts tested.

A similar case is that of anisole, an aromatic ether which, alter being converted over
typical hydrotreating catalysts at 250-350 ºC and hydrogen pressures between 20 and 50
bar, produced cresol, phenol and lower amounts of benzene (Huuska and Rintala, 1985).
It was shown later that Ni-Cu supported over CeO2 and ZrO2 was more effective to
deoxygenate this type of compounds; however, phenol is still an important reaction
product (Yakovlev et al., 2009).

Considering that both phenol and alkylated phenols (particularly cresol) are always
present in bio-oils, they have been the focus of numerous studies (Odebunmi and Ollis,
1983; Shin and Keane, 2000; Yang et al., 2009; Ahmad et al., 2010); moreover, as
already mentioned, phenol is also the product of hydrodeoxygenating other compounds.
When using typical hydrotreating catalysts, hydrogenation and hydrogenolysis being the
most prevalent reactions and cyclohexanol, cyclohexanone, cyclohexane and benzene,
in the case of phenol, and methylcyclohexane, toluene, ethylcyclopentane and xylenes,
in the case of cresol, the most important products. Since acidic supports in hydrotreating
catalysts contribute to the dehydration of alcohols and phenols, the decarbonylation of
aldehydes and ketones and the decarboxylation of acids, some authors claim that the use
as supports of microporous acid structures, such as H-Beta zeolite (Zhu et al., 2011),
would add more acidity and improve deoxygenation. However, these microporous
crystalline materials deactivate very fast by coke deposition.

The acids which occur in bio-oils have been scarcely studied. Şenol et al. (2007) reacted
heptanoic acid over commercial hydrotreating catalysts under typical process conditions
and observed high conversions (between 47 (CoMo catalyst) and 90% (NiMo catalyst)),
the main products being heptanal, 1-heptanol, hepthyl heptanoate, diheptyl ether, 1-
hexanethiol, 1-heptanethiol and the same hydrocarbons. Esters and furans seem to be
the most highly reactive components in bio-oils. For example, methyl hexanoate and
methyl heptanoate esters converted completely at 250-300 ºC and 15 bar of hydrogen
into C5-C7 paraffins and olefins, methanol and carboxylic acids (Şenol et al., 2005 y
6
2007). Furan, benzofuran and dibenzofuran produced C3-C4 paraffins and olefins,
cyclohexane and some oxygenated compounds such as ethylphenol in their conversion
over conventional catalysts at 400 ºC and atmospheric pressure (Fuminsky, 2000). After
these results, these authors estimate that under usual hydrotreating conditions, the
deoxygenation of furans would be complete. Other studies showed that furans can be
completely deoxygenated over Pt/TiO2 catalysts at temperatures between 220 and 280
ºC at atmospheric pressure (Kreuzer and Kramer, 1997); however, the catalysts
deactivated fast as a consequence of coke deposition and poisoning by adsorption of
carbon monoxide from the own process.

Catalysts which differed from conventional ones and very diverse reaction conditions
were used to study the behavior of aldehydes and ketones. For example, benzophenone,
benzaldehyde, 2- and 3-phenylpropionaldehyde, 4-isopropylbenzaldehyde,
cinamaldehyde and heptanal were reacted over Pt supported on Beta and ZSM-5
zeolites in the liquid phase, with hexane at 130 ºC and 60 bar (Bejblová et al., 2005;
Procházková et al., 2007). 2-methyl-2-pentenal was tested on Pt, Pd and Cu supported
on silica at temperatures from 200 to 400 ºC and atmospheric pressure (Pham et al.,
2009). Among the various model compounds tested, only 4-isopropylbenzaldehyde,
benzaldehyde and 2-methyl-2-pentenal showed high conversions (between 33 and 100
%), the main products being other oxygenated compounds (ethers, alcohols), water and
some hydrocarbons (such as toluene and pentanes).

It has been observed in general terms that commercial hydrotreating catalysts are
effective in the conversion of some of the oxygenated compounds in bio-oils, such as
furans and esters, but not for others, such as aldehydes, ketones and phenols (especially
phenolic ethers) which are very abundant in bio-oils. Moreover, in most of the
publications, oxygen-containing compounds remain in the product mixture. This means
that it is still necessary to study more soundly the behavior of these molecules during
hydrotreating and develop new catalysts which are effective in the conversion of all the
chemical groups present in bio-oils.

From the related publications it can be concluded that hydrotreating catalysts deactivate
very fast as the consequence of coke deposition, and the adsorption of water and
7
products from the deoxygenation of bio-oils (mainly carbon monoxide). This is a real
problem, since pyrolysis bio-oils contain large amounts of water (from 15 to 50 %) and
of phenolic compounds (more than 20 %), which are important coke precursors. As it is
well known, the reactivation of hydrotreating catalysts impose their regeneration in air,
with high operation costs and process shut offs.

2.2. Bio-oils

During hydrotreating, the oxygen present in the components of the bio-oils reacts with
hydrogen to form water and hydrocarbons (Corma y Huber, 2007). Then, two organic
phases are formed, one which is soluble in water (which may contain some unreacted
compounds) and one which is insoluble, containing phenols and hydrocarbons. This
shows that not all the oxygenated compounds are converted and that the aqueous phase
contains useful reactants.

Different studies about bio-oil hydrotreating showed that the selection of both the
catalyst and the process conditions strongly depend on their composition. Many
researchers hoped that typical hydrotreating catalysts such as NiMo/Al2O3 and
CoMo/Al2O3 would be proper choices, and obtained very different results. For example,
Zhang et al. (2005) observed deoxygenations in pine sawdust bio-oil from a liquefaction
process, not pyrolysis, of up to 93 % at 345 - 390 ºC and 20 bars, conversions being
about 80 %. However, for bio-oils derived from the pyrolysis of various sawdust
biomasses, two hydrotreating steps were necessary, the first one directed at bio-oil
stabilization (at temperatures lower than 300 ºC, in order to decrease the concentration
of acids and other compounds which tend to polymerize, such as phenolic ethers), and
the second one directed at true deoxygenation (at temperatures between 350 and 400
ºC). This process generated between 37 and 44 % of liquids, with less than 1 % of
oxygen, and consumed about 2300 m3 of hydrogen per feedstock barrel at high
pressures (140 bar) (French et al, 2010). The main problems which were identified,
besides the high consumption of hydrogen, were catalyst deactivation and the formation
of gums in the transfer lines, thus defining issues which need to be solved.

8
Another important aspect to be considered is the need for a careful evaluation of which
is the convenient degree of deoxygenation of bio-oil, considering that if it is too high,
the concentration of useful products would decrease, that is, liquid products would
decrease. For example, if bio-oil from eucalyptus sawdust is hydrotreated on
conventional catalysts, the yield of liquids decrease from 45 to 30 % when
deoxygenation increases from 78 to 100 %, and the yield of water increase from 45 to
55 % (Samolada et al. (1998)).

Some studies also exist which are focused on the development of catalysts specifically
aimed at hydrotreating bio-oils, like that from Wildschut et al. (2009), who used Ru/C,
Ru/TiO2, Ru/Al2O3, Pt/C and Pd/C at temperatures from 250 to 300 ºC and pressures
between 100 and 120 bar. Their results showed that deoxygenation can be high (about
90 % for the Ru/C catalyst), and that mainly aromatic hydrocarbons are obtained, with
the penalty of phenolic compounds being higher than in bio-oil (note that phenol and
alkylated phenols are also products of the reaction of phenolic ethers).

Even though two step hydrotreating seems a promising alternative according to the
degree of deoxygenation achieved, costs associated to the very high hydrogen
consumption impose serious doubts on its implementation in refineries (French et al.,
2009). Moreover, a large number of publications dealing with hydrodeoxygenation of
bio-oils can be found in the last decades, most of them using model compounds, but
many discrepancies between results can be appreciated in relation, for example, to how
much deoxygenation can be obtained, which varied between 10 and 90 %, even when
catalysts and conditions are similar. Since bio-oils derived from different sources differ
in their particular characteristics (for example, a higher content of phenols if the
biomass has more lignin, or a higher content of acids, aldehydes and ketones if the
biomass contains more cellulose and hemicellulose), hydrodeoxygenating these
complex mixtures need to be studied more soundly.

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3. Catalytic cracking on FCC catalysts

The catalytic cracking of bio-oils over acidic zeolites has been extensively studied (for
example, Adjaye and Bakhshi, 1995a; Srinivas et al., 2000; Corma et al., 2007; Valle et
al., 2007; Gayubo et al., 2010). This is particularly true for ZSM-5 zeolite and, to a
lower extent, for Y zeolite, with results which are promising in relation to the degree of
deoxygenation and the distributions of products observed. In general terms, ZSM-5
zeolite produces mainly aromatic hydrocarbons, while Y zeolite leads particularly to a
higher proportion of aliphatic hydrocarbons. Catalyst deactivation due to coke
deposition is the most important problem in all the cases, an issue which can be easily
solved if a continuous regeneration system, such as FCC’s, is provided. In view of the
possible co-processing of bio-oil and conventional FCC feedstocks, this section is
devoted to review the results from the conversion of bio-oil model compounds and true
bio-oil from pine sawdust (both crude and thermally conditioned) over an equilibrium
commercial FCC catalyst; results are compared with the few available in the literature
which used these catalysts, or with other pure zeolites.

In order to gather useful information about the impact of incorporating bio-oil (that is,
oxygenated compounds) to the conventional, hydrocarbon feedstocks in FCC units,
assigning emphasis to the overall product slate, a strategy of increasing complexity was
employed, from model compounds to a synthetic bio-oil to, finally, actual bio-oils (both
crude and previously conditioned through a thermal process).

3.1. Model compounds

The study of the reactivity of bio-oil model compounds representing different chemical
functionalities over actual, equilibrated commercial FCC catalysts, together with the
knowledge of the product distributions observed, could provide useful information to
predict co-processing details and help in producing necessary adjustments. Particularly,
the chemical groups which are responsible of higher coke yields, or which show more
efficiency in being converted into hydrocarbons, could be identified. The conversion of
eight different model compounds and a synthetic bio-oil produced with their mixture
was studied by Bertero et al. on a commercial equilibrium FCC catalyst of the octane-
10
barrel type (Bertero et al., 2013, Bertero y Sedran, 2013a, Bertero y Sedran, 2013b) in a
fixed MAT (MicroActivity Test)-type fixed bed reactor at 500 ºC.

The individual model compounds used and the corresponding group they represented
were acetic acid (acids), methyl acetate (esters), furfural (aldehydes and furans), 3-
methyl-2-pentanone (linear ketones), 2-hidroxy-3-methylcyclopentenone (cyclic
ketones), methanol (alcohols), phenol (phenols), 2,6-dimethoxyphenol (usually named
syringol, phenolic ethers) and 1,2,4-trimethoxybenzene (aromatic ethers). Each of the
reactants was dissolved in water with a concentration of 5 %wt. (except 1,3,4-
trimethoxybenzene, which was dissolved in benzene), as an approximation to the
conditions observed for their respective chemical groups in typical bio-oils. Then, a
synthetic bio-oil was produced by mixing all the model compounds, following
proportions which represented those of each of the chemical groups in bio-oils derived
from pyrolysis. Thus, the synthetic bio-oil included acetic acid (5.7 %wt.), methyl
acetate (3.4 %wt.), furfural (4.1 %wt.), 2-hydroxi-3-methylcyclopentenone (6.4 %wt.),
methanol (7.3 %wt.), phenol (1.7 %wt.), 2,6-dimethoxyphenol, (syringol, 2.8 %wt.) and
1,2,4-trimethoxybenzene (0.5 %wt.,).Water was added at 68.1 %wt.

When converted on acidic zeolites, acids, esters, aldehydes, ketones and alcohols react
through a mechanism involving decarbonylation, decarboxylation, dehydration,
cracking and aromatization, thus yielding mainly aromatic and aliphatic hydrocarbons
and oxygenated compounds in a wide range of molecular weights (Chang and Silvestri,
1977; Chen et al., 1987; Dao et al., 1987; Hutchings et al., 1994; Adjaye and Bakhshi,
1995b; Horne and Williams, 1996; Srinivas et al., 2000¸ Gayubo et al., 2004). On the
other hand, phenols and aromatic ethers are subjected to cracking, alkylation and
condensation, yielding mainly hydrocarbons and alkylated phenols (Hutchings et al.,
1994; Adjaye and Bakhshi, 1995b; Samolada et al., 2000; Bertero et al., 2011)

The conversions and product distributions observed in the reaction of the model
compounds and the synthetic bio-oils are shown in Table 1. Yields were calculated on a
dry basis, that is, without considering the occurrence of water in the feed. It is to be
noted that under the conditions used the conversions were higher than 50 % in all the
cases, although methyl acetate and 1,2,4-trimetoxybenzene were converted almost
11
completely. Some compounds (furfural, 3-methyl-2-pentanone, phenol and 1,2,4-
trimetoxybenzene) produced hydrocarbons in significant amounts, while others (methyl
acetate and syringol) produced mainly oxygenated compounds. In the case of the
synthetic bio-oil, it is to be considered that conversion can not be assessed strictly,
because some of the initial components of the mixtures are in turn products of the
conversion of other components (Adjaye and Bakhshi, 1995b). This fact can be easily
verified with, for example, methanol, acetone, phenol and alkylphenols. However, most
of the oxygenated compounds which are initially present in the feedstocks decreased
significantly their concentration in the catalytic experiments, thus suggesting that they
reacted extensively (Bertero and Sedran, 2013b).

Among the oxygenated products, methanol and acetone were always present, while
other products were characteristic of the conversion of the various model compounds;
for example, formic acid was particularly present in the case of reacting furfural, acetic
acid in the case of methyl acetate and alkylated phenols the case of syringol. 2-
Hydroxi-3-methylcyclopentenone and 1,2,4-trimethoxybenzene showed the more
extended distribution of oxygenated compounds, comprising ketones (cyclopentenones),
furans (benzofurans and benzophenones) and alcohols. The synthetic bio-oil produced
mainly phenols (phenol and cresols) and methanol, a fact which is consistent with other
reports of the conversion of different mixtures of oxygenated compounds over zeolites
REUSY and HZSM-5 (Adjaye and Bakhshi, 1995b; Samolada et al., 2000).

The yields of coke were very significant in the most of the cases, but very different for
each of the model compounds, ranging from 1.6 %wt. in the case of acetic acid to the
very high yield of 16 %wt. observed with 1,2,4-trimethoxybenzene. These values
indicate a high coke forming potential in these oxygenated compounds, particularly
considering that they were contacted with the catalyst under a high dilution in water, a
factor which should attenuate coke yield (Samolada et al., 2000). The reaction of these
reactants, or structurally similar oxygenated compounds, over HZSM-5 catalysts (Chen
et al., 1987; Horne and Williams, 1996; Gayubo et al., 2004) also produced large
amounts of coke ranging from 3 up to 12 %wt.

12
Different authors stated that the formation of coke in the conversion of bio-oil or
oxygenated model compounds over acidic zeolites is from both thermal and catalytic
sources (Sharma and Bakhshi, 1993; Williams and Horne, 1995; Srinivas et al., 2000;
Valle et al., 20007). When the catalysts are compound, such as those used in the FCC
process, where the main component, which is the Y zeolite, is supported on an
amorphous matrix, the coke from thermal reactions is generally deposited on the matrix,
thus contributing to a lower extent to the deactivation of the active sites in the zeolite,
which is more affected by the coke from catalytic reactions (Gayubo et al., 2005).

In all the cases the yields of hydrogen were considerable, and particularly high in the
cases of 2-hidroxy-3-methylcyclopentenone and acetic acid. All the individual reactants
and the synthetic bio-oil showed that decarboxylation (producing CO2) and dehydration
reactions existed in their catalytic conversions, and furfural and 2-hidroxy-3-
methylcyclopentenone also showed decarbonilation (producing CO). These reactions
accounted for the observed deoxygenation of 86 % in the case of the synthetic bio-oil,
of about 80 % in the cases of individual ketones (2-hidroxy-3-methylcyclopentenone
and 3-methyl-2-petanone), of about 60 % in the case of furfural, methanol and syringol,
of about 45 % in the cases of acetic acid and methyl acetate, and the lowest
deoxygenation of 37 % in the case of phenol. Notably, essentially all the oxygen was
removed from 1,2,4-trimethoxybenzene. The higher deoxygenation noted in the
synthetic bio-oil, as compared to the individual deoxygenation of each of its
components, is due to synergic effects among the different oxygenated species in the
mixture (including both reactants and products). This behaviour was observed in the
conversion of oxygenated model compounds over Y and ZSM-5 zeolites (Adjaye and
Bakhshi, 1995b; Samolada et al., 2000; Gayubo et al., 2005). Deoxygenation had been
coincidently noticed on zeolite ZSM-5 to be due to decarboxylation and dehydration in
the cases of acids and esters (Chen et al., 1987), decarbonilation being observed with
ketones and aldehydes (Adjaye and Bakhshi, 1995b; Horne and Williams, 1996; Graça
et al., 2009). Moreover, Graça et al. (2009) had reported that carbon dioxide and water
were the most important products in the deoxygenation of acetic acid over equilibrium
FCC catalysts; however, this can be contrasted with reports from Domine et al. (2008),
who observed mainly carbon monoxide in the conversion of acetic acid over FCC
catalysts. Other studies showed that over zeolite HZSM-5 methanol and phenol also
13
 deoxygenated mainly through dehydration (Chantal et al., 1985; Chen et al., 1987),
while methoxybenzene yielded mainly carbon oxides and dehydration was nil (Adjaye
and Bakhshi, 1995b; Hutchings et al., 1996).

Table 1. Catalytic conversions and product yields from the model compounds and
synthetic bio-oil over FCC catalyst.

3-Methyl- 2-Hidroxy-3-
Acetic acid Methyl acetate Furfural
2-pentanone methylcyclopentenone
Conversion (%) 50.4 95.1 78.2 79.6 84.5
Yields (%wt.)
Hydrocarbons 4.2 0.9 32.1 37.6 14.0
Oxygenated 5.2 54.5 9.0 20.7 9.4
Hydrogen 6.6 3.7 5.7 0.5 8.1
CO2 22.9 22.2 9.6 1.1 35.7
CO Traces Traces 1.8 Traces 1.2
Water 9.9 6.4 12.8 13.7 2.3
Coke 1.6 7.4 7.2 5.9 12.8
Unknown 1.0
1,2,4-Trimethoxy
Methanol Phenol Syringol Synthetic bio-oil
benzene
Conversion (%) 60.8 54.9 75.0 95.7 -
Yields (%wt.)
Hydrocarbons 7.1 34.9 2.1 47.1 26.8
Oxygenated 4.0 2.0 32.5 0.2 19.3
Hydrogen 3.5 1.6 4.1 2.3 1.3
CO2 12.2 4.0 22.9 29.8 3.6
CO Traces Traces Traces 0.3 Traces
Water 27.0 8.0 4.9 - 34.8
Coke 5.5 4.4 8.5 16.0 14.0
Unknown 1.7 0.2

Reports about the conversion of these model or similar compounds on either FCC
catalysts or Y zeolite, which is the main component over them, are very scarce. For
example, Hutchings et al. (1994) used pure methanol on HY zeolite at reaction
temperatures between 320 and 420 ºC, with conversions up to 78 % and mostly
hydrocarbons among products. Domine et al. (2008) used acetic acid, isopropylic
alcohol and acetone which were added to isooctane at 2 %wt. on a FCC catalyst, and
observed hydrocarbons and carbon monoxide among products. Corma et al. (2007) used
14
glycerol and sorbitol at 50 %wt. in water on FCC catalysts, REUSY and Y zeolite and
reported conversions of up to 80 %, mainly to hydrocarbons and carbon oxides. Other
authors made use of model compounds which were dissolved directly into VGO, with
the aim of co-processing, as discussed in the following sections.

The conversion of a synthetic bio-oil made up from the mixture of various bio-oil model
compounds over acidic zeolites has been scarcely reported in the literature (Fuhse and
Bandermann, 1987; Samolada et al., 2000; Gayubo et al., 2005). It must be mentioned
that the mixtures simulating bio-oils were very different, including, for example, acetic
acid, ethyl butyrate, methanol, cyclopentanol, pentanal, hexanal, heptane-4-one, methyl
isopropylketone, tetrahydrofurane and dipropylic ether (Fuhse and Bandermann, 1987);
propanoic acid, methyl acetate, methylcyclohexanol, methylcyclopentanone, eugenol
and ethoxybenzene (Adjaye and Bakhshi, 1995b); acetic acid, furfural, cyclohexanone,
guaiacol, vainillin and water (Samolada et al., 2000); or acetic acid, acetone, methanol,
2-butanol, phenol, guaiacol and water (Gayubo et al., 2005). The conversions of these
mixtures over zeolite ZSM-5 were higher than 90 % (Fuhse and Bandermann, 1987;
Adjaye and Bakhshi, 1995b; Samolada et al., 2000; Gayubo et al., 2005), hydrocarbons
(mainly aromatics and C4- olefins) and oxygenated compound yields being significant:
between 20 and 40 %wt. and between 9 and 17 %wt., respectively. Deoxygenation
proceeded through dehydration and decarboxylation. Conversion over REUSY zeolite
(Samolada et al., 2000) was considerably lower (63 %), as well as hydrocarbon yield
(about 9 %wt.) and oxygenated compound yield (about 4 %wt.). Moreover, up to the
present, the use of model mixtures over commercial FCC catalysts has not been reported
by other authors.

In order to know the contribution from each of the chemical functions in oxygenated
compounds conforming bio-oils, when taking part of co-processing with conventional
VGO feedstocks, and eventually to improve them, it is important to analyze the
distribution of product hydrocarbons from the model compounds. In this sense, Table 2
shows the selectivities to the main product hydrocarbon groups in the conversion of the
model compounds and the synthetic bio-oil on an equilibrium FCC catalyst (Bertero et
al., 2013, Bertero and Sedran, 2013a, Bertero and Sedran, 2013b).

15
 It can be seen that C1-C4 gases were always present, and that liquid products were also
obtained in the experiments with furfural, 3-methyl-2-pentanone, methanol, 1,2,4-
trimethoxybenzene and the synthetic bio-oil. Particularly acetic acid, methyl acetate,
phenol and syringol produced a significant proportion of C4- hydrocarbons with a high
concentration of olefins, facts which are consistent with reports about the catalytic
conversion of these compounds, or similar, over HZSM-5 zeolite and a FCC catalyst.
(Chang and Silvestri, 1977; Hutchings et al., 1994; Samolada et al., 2000; Graça et al.,
2009).

On the contrary, in the conversion of furfural, the selectivity to liquid products was high
(74.5 %), due to almost exclusively the occurrence of C5 olefins. This distribution is
different from the one observed with HZSM-5, where aromatics (particularly
alkylbenzenes) and naphthalene and alkylated homologous compounds were the most
important liquid products (Horne and Williams, 1996; Chen et al., 1987).

Table 2. Distribution (%wt.) of hydrocarbon products in the conversions of the model

compounds and the synthetic bio-oil over FCC catalyst.

3-Methyl- 2-Hydroxy-3-
Acetic acid Methyl acetate Furfural
2-pentanone methylcyclopentenone
C1-C2 47.2 75.8 5.5 0.2 16.4
C3-C4 52.8 24.2 19.3 0.8 51.7
C5-C9 74.5 31.2 13.3
Aromatics 0.7 67.8 18.6
1,2,4-Trimethoxy
Methanol Phenol Syringol Synthetic bio-oil
benzene
C1-C2 2.0 12.8 50.0 0.1 47.7
C3-C4 0.3 82.2 25.0 17.5
C5-C9 38.7 5.0 9.4 8.3
Aromatics 58.9 0.8 23.0 99.9 26.5

Ketones and methanol showed a more extended catalytic pathway, aromatics being the
most important liquid hydrocarbon products. The selectivity to hydrocarbons in the
gasoline range was very high in the case of methanol and 3-methyl-2-pentanone (98 %
and 90 %, respectively), and lower, but still considerable, in the case of the synthetic
16
bio-oil and 2-hidroxy-3-methylcyclopentenone (35 y 32 %, respectively). In all the
cases the main products in the range were aromatics, which represented more than 60 %
of the total; in the case of ketones the main hydrocarbons were naphthalene and
alkylated homologous, while in the case of methanol, xylenes and C9 aromatics
(propylbenzene, methylethylbenzenes and trimethylbenzenes) predominated, in
consistency with the classic observations by Chang and Silvestri (1977). In the case of
the synthetic bio-oil, benzene and alkylated monoaromatics were the main hydrocarbons.

Only aromatic hydrocarbons were produced in the conversion of 1,2,4-

trimethoxybenzene, biphenyl being the most important product. Polyaromatic
hydrocarbons such as naphthalene, flourene, pyrene and their alkylated homologous
compounds were also produced, as also reported for methoxybenzene over HZSM-5
zeolite (Adjaye and Bakhshi, 1995b; Prasomsri et al., 2011).

These studies show that it is possible to convert the oxygenated compounds forming
bio-oils over zeolites and, particularly, FCC catalysts. However, one of the most
important conclusions is that these oxygenated species behave differently when they
converted as a single reactant or taking part of a mixture, due to the synergy between
them and their reaction products. Considering that bio-oils are very complex mixtures of
many compounds, it is likely that a mixture of a number of model compounds is not
completely adequate to study the intrinsic behaviour of bio-oils over FCC catalysts, as also
stated by Adjaye et al. (1995b), who used a mixture of six model compounds over
HZSM-5. These observations suggest that this issue is not depending on the acidic
catalyst used. Another important inference is that, given the noteworthy trend by some
of these chemical species, such as aromatic and phenolic ethers and cyclic ketones, to
produce coke, a treatment of the bio-oil aimed at reducing that potential previous to its
co-processing, might be convenient.

3.2. Bio-oils

It is absolutely necessary to analyze the conversion of bio-oils over FCC catalysts in

order to understand the contribution by these non-conventional feedstocks to the usual
product distribution if co-processed with hydrocarbons. The positive effect of thermally
17
treating the bio-oils previous to their co-processing is obvious in the neat improvement
of their processability characteristics. For example, the potential of coke formation of
the bio-oil used in this work, as expressed by the Conradson Carbon Residue (CCR)
decreased about 60 % and the Effective Hydrogen Index (EHI, a parameter which
indicates how easy it is to crack a feedstock in FCC) increased 30 % after a thermal
treatment at 500 ºC during 10 min, with a heating ramp of 12 ºC/min (Bertero et al.,
2012).

Concerning the laboratory evaluation of commercial FCC catalysts and feedstocks,

today most of the methods are based on the MAT methodology, and particularly by
means of FFB reactors, which are extensively used and can be considered the standard
(Corma and Sauvanaud, 2013). A different, alternative approach is provided by the
CREC Riser Simulator reactor (de Lasa, 1992), specifically designed to mimic the
conditions in an ideal riser reactor, its reactants-catalyst contact being similar to that of
commercial FCC units. Clearly, the contact regimes in the CREC Riser Simulator and
MAT or FFB reactors are completely different. In the simulator reactor the catalyst bed
is fluidized by the recirculation of the reactant hydrocarbons, which “see” the same
catalyst particles through out all the contact time with the properties of a CSTR reactor
(similarly to elemental reactant-catalyst ideal portions of commercial units). Oppositely,
in MAT or FFB reactors, the catalytic bed, which is subjected to continuous changes in
its properties as a consequence of the coke deactivation, receives a fresh reactant feed
continuously. Moreover, for MAT fixed beds, axial coke and activity profiles develop
as a function of contact time (Tsai et al., 1989; Corma and Sauvanaud, 2013), a fact
which is not observed in FFB reactors. As a consequence, also considering that samples
are collected through the experiments (thus imposing experiment durations which are
longer than residence time in commercial units), that the catalyst to oil relationship in
MAT and FFB units are assessed in a cumulative mode (C/O=mass of catalyst / mass
flow of reactant x time on stream), activity and selectivities are not fully representative
of the commercial cases (Passamonti et al., 2009). All these issues are solved properly
in the CREC Riser Simulator reactor.

The product distributions which were generated in the conversion of the bio-oil and the
liquid obtained after its thermal upgrading over the same equilibrium FCC catalyst
18
which was used with the model compounds, in both the MAT and CREC Riser
Simulator reactors, are shown in Table 3. As already described for the synthetic bio-oil
in Section 3.1, conversion can not be assessed following conventional definitions, due
to the fact that some components in the starting mixture are also products from the
conversion of some compounds in the feedstock (Bertero et al., 20103, Bertero and
Sedran, 2013a and b). Yields were calculated on a dry basis, that is, without considering
water in the bio-oil. The composition and the main physicochemical properties of the
crude and upgraded bio-oil can be found in Bertero et al. (2011) and Bertero and Sedran
(2013b).

The main deoxygenation pathways in the conversion of bio-oils over acidic zeolites are
the dehydration reaction to water and the formation of carbon oxides (Adjaye and
Bakhshi, 1995 a y b; Huber and Corma, 2007). These products were observed in the
conversion of both the bio-oil and the upgraded liquid over the E-Cat in a MAT-type
fixed bed reactor, with carbon dioxide yields between 2 and 4.2 %wt. and water yields
about 30 %wt. (Bertero and Sedran, 2013b). In order to compare the results from both
reactors, those from the MAT reactor were normalized excluding the yields of carbon
oxides.

Table 3. Product distribution in the conversion of crude (CBO) and upgraded by

thermal treatment (UBO) bio-oil over an equilibrium FCC catalyst at 500 ºC (%wt.,
dry basis). Time on stream, MAT 60 s; reaction time, CREC Riser Simulator 15 s.
CBO UBO
MAT Riser Simulator MAT Riser Simulator
Hydrocarbons 66.6 21.9 76.9 37.5
Oxygenated 15.1 71.2 8.0 57.6
Coke 17.4 4.4 13.2 3.0
Unidentified 0.8 2.5 1.6 1.9

As expected, important differences can be observed in the distribution of products from

each of the reactors. For both feedstocks, the yield of hydrocarbons was much lower and
the yield of oxygenated compounds (including the unconverted reactants) was much
higher in the CREC Riser Simulator reactor than in the MAT reactor. This could be due
19
to the shorter contact time in the first unit, which leads to less deoxygenation and
cracking of the oxygenated compounds in the feedstocks.

The yields of coke in the experiments in the CREC Riser Simulator reactor were
approximately one fourth of the amounts formed in the MAT reactor, resulting similar
to commercial values in FCC units, which are usually between 3.5 %wt. and 8.0 %wt.
(Mandal et al., 1994; Nalbandian et al., 1994). This positive characteristic of the CREC
Riser Simulator reactor was also verified in the conversion of commercial VGO and
resid feedstocks (Passamonti et al., 2009 and 2012; Devard et al., 2009), thus assigning
higher confidence to results obtained with this reactor. The high coke yield in the MAT
reactor (from 13 to 17 %wt.) is the consequence of its operative regime, which also
favours secondary hydrogen transfer reactions. Moreover, the upgraded liquid produced
less coke than the crude bio-oil, this difference being more significant in the CREC
Riser Simulator reactor (30 % less) than in the MAT reactor (20 % less). In the
conversion of bio-oils from wood sawdusts over Y and ZSM-5 zeolites in fixed bed
reactors, coke yields were very high, from 10 to 22 %wt. (Williams and Horne, 1995;
Vitolo et al., 1999; Adjaye and Bakhshi, 1995b; Sharma and Bakhshi, 1993; Guo et al.,
2009).

However, some trends were similar in both setups. It is interesting to confirm that the
upgraded liquid produced more hydrocarbons and less oxygenated compounds and coke
than the parent bio-oil. The differences in the yields of these product groups were more
significant when the experiments were performed in the CREC Riser Simulator reactor,
where the yield of hydrocarbons from the upgraded bio-oil was 30 % larger than that
from the crude bio-oil, and the yield of coke was 30 % smaller. This is a consequence of
the positive changes in the characteristics of the bio-oil after the thermal treatment.

Concerning the oxygenated compounds produced in the conversion of the crude bio-oil
and the upgraded liquid, it was observed in both experimental setups that both
feedstocks yielded significant amounts of acetone and methanol, but selectivities among
oxygenated were much higher in the case of the CREC Riser Simulator reactor (acetone
about 65 % and methanol about 20 %). The conversion of the upgraded liquid showed
higher selectivity to these products than the bio-oil in both reactors, about 15 % in the
20
Simulator reactor and about 25 % in the MAT reactor. Some acids, such as the acetic
and the pentanoic, and furans, such as furfural and benzofurans, were also produced in
all the cases, but in low proportions.

The most significant difference observed between setups was the selectivity to phenols.
Phenol and cresol were the most important oxygenated compounds produced in the
experiments in the MAT reactor, with selectivity about 50 % among oxygenated, while
in the CREC Riser Simulator reactor the selectivity was less than 5 %. Moreover, the
conversion of the phenolic ethers in the feedstock (guaiacol, syringol and their
derivatives) was complete in both reactors. In consistency with the lower hydrocarbon
yield in the CREC Riser Simulator reactor (see Table 3), and according to the reaction
pathway postulated by Adjaye and Bakhshi. (1995b), these observations suggest that in
this reactor the conversion of bio-oil was lower than in the MAT reactor. In that
mechanism, alkylated phenols and aromatic hydrocarbons are secondary products from
the transformation of low molecular weight ketones and alcohols, such as acetone and
methanol produced by the deoxygenation and cracking of high molecular weight
compounds in the bio-oil.

Acetone, methanol, phenol and cresol were the main oxygenated products in the
conversion of different bio-oils from wood sawdusts over Y and ZSM-5 zeolites,
according to authors who used fixed bed reactors at temperatures between 290 and 410
ºC, who reported selectivities from 20 to 60 %wt. for ketones, from 13 to 30 % wt. for
alcohols and about 50 %wt. for phenols (Adjaye and Bakhshi, 1995 a y b; Sharma and
Bakhshi, 1993; Srinivas et al., 2000).

The hydrocarbon product distributions observed in the conversion of the crude and
upgraded bio-oils in both experimental setups are shown in Table 4. Mainly highly
olefinic, light C4- hydrocarbons were produced in all the cases. Liquid hydrocarbons in
the C5-C15 range were also formed to a lower extent, particularly in the experiments in
the CREC Riser Simulator reactor.

21
 Table 4. Selectivities among hydrocarbons in the conversion of crude (CBO) and
upgraded (UBO) bio-oil over FCC catalyst at 500 ºC (%). Time on stream MAT
60 s, reaction time CREC Riser Simulator 15 s.

CBO UBO
MAT Riser Simulator MAT Riser Simulator
C1-C2 Hydrocarbons 59.6 29.7 55.4 28.6
C3-C4 Hydrocarbons 28.5 33.8 32.0 38.0
C5-C9 Hydrocarbons 4.6 15.7 5.7 15.3
Aromatics 4.6 20.8 5.7 18.1

The experiments performed in the MAT reactor showed much higher selectivities to
gaseous C1-C2 hydrocarbons, mostly to methane, and the selectivities to C4+ olefins,
mainly pentenes, were about one third of those observed in the CREC Riser Simulator
reactor. According to the operation mode of the MAT reactor, where at the beginning of
the experiments a small portion of reactants is contacted with the fresh, highly active
catalyst, overcracking of the liquid hydrocarbons, leading to gas products, is intense (Ng
et al., 2004).

The selectivity to hydrocarbons in the boiling range of gasoline was higher in the
experiments performed in the CREC Riser Simulator reactor (about 34 % for both
feedstocks) than in the MAT reactor (12.3 % for the upgraded bio-oil and 10 % for the
upgraded liquid). The content of aromatic hydrocarbons in this range was similar in all
the cases, about 54 %, but benzene and its alkylated homologous predominated in the
fluidized bed reactor, while aromatic hydrocarbons with two or more aromatic rings,
such as naphthalene and alkylated compounds, prevailed in the MAT reactor, a fact
which is consistent with the more extensive reaction in this reactor (Adjaye and
Bakhshi, 1995a).

Other authors like (Sharma and Bakhshi, 1993, Adjaye and Bakhshi, 1995a and
Williams and Horne, 1995), reported similar observations in the conversion of various
bio-oils from wood sawdusts over Y and ZSM-5 zeolites in fixed bed reactors. They
observed mainly methane and light C2-C4 olefins among the gaseous hydrocarbons,
with yields between 10 and 16 %wt. (Y zeolite) and up to 35 % wt. (HZSM-5 zeolite),
22
and reported selectivities to aromatics which were relatively low (less than 20 %) in the
case of the Y zeolite and very high (over 80 %) in the case of the HZSM-5 zeolite.
Aliphatic hydrocarbons occurred in the range of gasoline for both types of catalysts, the
most important ones being alkylated pentanes, hexene and decane, while the aromatics
covered a wide range of molecular weights, with toluene, xylenes and
trimethylbenzenes as the most important monoaromatics, and naphthalenes and
alkylated indenes, indacene and phenantrene, as the most important compounds with
two or more aromatic rings.

4. Co-processing bio-oils and FCC feedstocks

The laboratory studies about co-processing bio-oils together with conventional FCC
feedstocks play a key role in identifying the true potential of this approach, and it is
crucial that the information could be somehow extrapolated to actual circumstances and
commercial units. Some authors consider that high proportions up to 20 %wt. of bio-oil
(water-free basis) could be added to VGO, provided it is previously conditioned in order
to improve its properties by, e.g., hydrotreating (Samolada et al., 1998; Marker, 2005;
Lappas et al., 2009; Fogassy et al., 2010, de Miguel Mercarder et al., 2010). According
to their laboratory results, this would not modify significantly the product distribution or
the heat balance of the units. However, these high concentrations of oxygenated
compounds are probably unrealistic at the commercial level. These results are compared
in this section.

The fact that bio-oils are not soluble in VGO did not represent a problem in the co-
processing experiments in the CREC Riser Simulator reactor due to its operative mode,
where the feedstock, either a mixture or pure, is injected with the help of a syringe and
the vaporization is instantaneous, thus producing a homogeneous gas phase in the
reactor. Solutions to the problems associated to the achievement of a homogeneous feed
to other reactors were attempted by different researchers following various experimental
strategies. For example, Lappas et al. (2009) diluted a hydrotreated bio-oil, which is
more soluble in hydrocarbon mixtures than the bio-oil, in light cycle oil (LCO, in a
portion 15/75 by weight) before adding it to a VGO. de Miguel Mercader et al. (2010)
23
homogenized a mixture of heavy residue and hydrotreated bio-oil at 75 ºC, feeding it to
a MAT reactor. Agblevor et al. (2010) used zeolite HZSM-5 as a catalyst in the
pyrolysis of poplar sawdust to obtain a liquid product with characteristics similar to
those of a hydrotreated bio-oil, which was later homogenized with VGO by heating the
mixture before feeding the catalytic cracking reactor.

Table 5 shows the results of laboratory experiments of co-processing bio-oils and VGO
in the CREC Riser Simulator reactor at 500 ºC, using the same equilibrium commercial
FCC catalyst which was used to study the conversion of model compounds and crude
and upgraded bio-oils. The VGO had paraffinic characteristics and the crude and
upgraded bio-oil was from pine sawdust.

The mixtures were produced by replacing 35 %wt. of the VGO with either crude or
upgraded bio-oil. Even though this concentration of oxygenated compounds is not
viable at the commercial level, it was used in order to observe more clearly the
contributions from the conversion of the oxygenated compounds in the co-processing.
However, an experiment with 10 %wt. of the upgraded bio-oil was performed following
a more realistic approach. It has to be considered that the content of water is different if
either the crude (49.6 %wt.) or the upgraded (62.2 %wt.) bio-oil is used. Then, on a
water-free basis, the resulting mixtures contained 21.3 %wt. crude bio-oil and 16.7 and
4.2 %wt. upgraded bio-oil, respectively. The hydrocarbon products were grouped
according to the usual refinery approach, that is, dry gas (C1-C2), liquefied petroleum
gas LPG (C3-C4), gasoline (C5-216 ºC), light cycle oil LCO (216-344 ºC) and heavy
cycle oil HCO (+344 ºC). Conversion in the case of the VGO was defined as the
addition of the yield of gas, gasoline and LCO hydrocarbons and coke. In the case of co-
processing it was not possible to assess the conversion of the oxygenated compounds in
the feedstocks due to the fact that some of them are also products in the conversion of
other components, an index of the magnitude of the conversion being given by the
yields of oxygenated compounds.

24
Table 5. Product distributions in the conversion of VGO and the co-processing of VGO
with the crude (CBO) and upgraded (UBO) bio-oil. Time on stream: 15 s

VGO VGO+CBO VGO+UBO VGO+UBO

Concentration of
oxygenated feedstock 21.3 16.7 4.2
(%wt.)
Hydrocarbons 94.6 91.8 93.4 94.5
Dry gas 0.8 2.4 3.8 0.8
LPG 8.4 11.7 13.4 7.9
Gasoline 45.8 34.2 33.8 45.9
LCO 18.6 14.7 14.3 17.4
HCO 21.0 28.8 28.2 22.5
Oxygenated compounds 3.0 1.7 0.1
Coke 5.4 5.3 5.0 5.4

When the VGO was fed alone, its conversion was high (79 %) due to its paraffinic
character and to the high content of zeolite and rare earths in the catalyst (18 and 1.2 %,
respectively). The main products were gasoline and LCO and the LPG was highly
olefinic (58 % selectivity). The observed yields corresponded to usual commercial
values, which widely change from 45 to 55 %wt. for gasoline (Nalbandian et al., 1994;
Mandal et al., 1994), from 10 to 37 %wt. for LCO (King et al., 1992)) and from 8 to 37
%wt. for LPG, depending on the operative mode of the unit (Mandal et al., 1994; King
et al., 1992).

By adding high proportions of oxygenated compounds to the feed (21.3 %wt. crude bio-
oil and 16.7 %wt. upgraded bio-oil) it was possible to observe significant changes in the
product distributions. The yield of HCO was higher, thus showing a lower conversion of
VGO, a fact which could be due at least in part to the dilution effect on hydrocarbons
produced by water and oxygenated compounds in the system. Cracking the mixtures
produced more gaseous hydrocarbons, particularly C2-C4 olefins, which represented 62
% of the LPG, and less liquid hydrocarbons in the C5-C20 range. Indeed, this implied
an important loss in gasoline yield, which was more significant in the case of adding
crude bio-oil. The mixture with the more realistic concentration of 4.2 %wt. upgraded
bio-oil showed a product distribution similar to that from the VGO alone, although a
slight decrease in LCO yield was also noted.
25
The scarce results which were published in the literature about the impact of adding bio-
oil to VGO aimed at co-processing, are ambiguous. Some authors, who co-processed
VGO with glycerol (Corma et al., 2007) and with hydrotreated bio-oil from pine
sawdust at concentrations between 5 and 20 %wt. over equilibrium FCC commercial
catalyst in both fixed and fluidized beds reactors (Marker, 2005; de Miguel Mercader et
al., 2010, Fogassy et al., 2011), reported that C2-C4 olefin yields increased from 10 to
20 %, that gasoline yield decreased between 5 and 10 % and that HCO yield increased
slightly. Other authors (Agblevor et al., 2010) reported that adding 20 %wt. of bio-oil
from the catalytic pyrolysis of poplar sawdust to a VGO did not affect significantly the
distribution of products and, particularly, that the yield of gasoline remained essentially
constant about 44 %wt. when co-processed over an FCC catalyst. In this last case
(Agblevor et al., 2010) the catalytic pyrolysis based on ZSM-5 as the catalyst yielded a
bio-oil with improved characteristics for co-processing (lower water (8.9 %wt.), oxygen
(27.9 %wt) and acid contents), though the yield is much lower if compared to a purely
thermal process. This type of catalytic pyrolysis process imposes the need to develop
technologies to regenerate the catalyst, which becomes rapidly deactivated.

The yield of oxygenated compounds (unconverted reactants are also included) was very
low in the co-processing of VGO with crude or upgraded bio-oil, even lower than 3
%wt., the main component being methanol and acetone, and furfural and phenol
showing much lower selectivities. It is to be noted that the mixture which contained
16.7 %wt. of the upgraded bio-oil produced about one half of the amount of oxygenated
compounds produced by the crude bio-oil (21.3 %wt.), thus confirming its higher
reactivity. Moreover, the amount of oxygenated compounds in the products of the
conversion of the mixture with 4.2 %wt. upgraded bio-oil was essentially nil (with
phenol as the only compound observed).

The selectivity of oxygenated compounds in FCC co-processing of bio-oil which were

reported in the literature is diverse. Some authors did not observe the occurrence of
oxygenated compounds among the products of co-processing VGO and 20 %wt.
hydrotreated bio-oil (de Miguel Mercader et al., 2010) or 15 %wt. bio-oil from catalytic
pyrolysis of pine sawdust (Agblevor et al., 2010), over commercial equilibrium FCC
catalysts at temperatures higher than 500 ºC. On the contrary, other authors (Fogassy et
26
al., 2010; Thegarid et al., 2013) reported alkylated phenols in the range of gasoline at
low proportions (< 0.2 %wt.), using similar feedstocks and the same type of catalyst at
500 ºC. Al-Sabawi et al. (2012) postulated that when the temperature is higher than 500
ºC dealkylation and dehydroxylation reactions in phenols are favored, yielding benzene
and alkylated aromatics.

4.1. Composition of the gasoline

The FCC process is the main contributor to gasoline in the refinery and, given the huge
volumes which are processed, small changes in yields or quality may represent large
differences in profit. Some of the most important issues in relation to gasoline are that
the content of aromatic hydrocarbons, particularly benzene, is becoming more restricted
as a consequence of regulations about environmental care, and that olefins are also
restricted due to their impact on the formation of smog and the stability of the fuel (de la
Puente and Sedran, 2004). Then, it is imperative to evaluate the impact on gasoline
composition that the addition of bio-oil to conventional VGOs and their co-processing
in FCC have.

The composition of the gasoline produced in the co-processing of VGO and crude and
upgraded bio-oil is shown in Table 6. The most important paraffins were branched,
particularly in the C6-C8 range, and the most important olefins were in the C5-C7
range. Hydrogen transfer reactions have a key role in the equilibrium between the
various hydrocarbon types in the gasoline range (Sedran, 1994; Cumming and
Wojciechowski, 1996), because they consume olefins and hydrogen donors such as
naphthenic compounds to produce paraffins and aromatics.

The yield of gasoline was affected negatively when the addition of the bio-feedstocks to
the VGO was high (21.3 %wt. crude bio-oil and 16.7 %wt. upgraded bio-oil), in about
ten percentage points. Also some changes were observed in the composition of the cut,
the most significant ones being the increase in the amount of olefins, particularly C5,
and the decrease, about 10%, in the content of aromatics. The most important aromatics
in gasoline were benzene, toluene and xylenes, which showed higher selectivity in the
co-processing experiments; on the contrary, the selectivity to heavier aromatics such as
27
trimethylbenzenes and naphthalene decreased slightly. In co-processing, the selectivity
to total paraffins decreased slightly, but that to isoparaffins, mainly iC5, showed an
important increase of about five percentage points, which was compensated with a
similar decrease in the other branched paraffins in the C7-C8 range.

Table 6. Composition of gasoline in the co-processing of crude and upgraded bio-oil

with VGO over E-Cat in the CREC Riser Simulator reactor (%wt.).

VGO VGO+CBO VGO+UBO VGO+UBO

Proportion of oxygenated 21.3 16.7 4.2
feedstock (%wt.)
Gasoline yield (%wt.) 45.8 34.2 33.8 45.9
Composition
Paraffins 39.1 38.3 38.1 37.3
n-Paraffins 3.3 3.4 3.7 3.1
i-Paraffins C5-C9 8.5 12.8 14.8 7.9
Other branched paraffins 20.3 16.8 15.5 19.5
Cycloparaffins 7.0 5.3 4.1 6.8
Olefins 9.6 13.6 16.3 9.5
Naphthenes 1.6 1.6 1.3 1.9
Aromatics 44.7 40.9 40.9 44.8
Benzene 1.1 1.3 1.6 1.0
Toluene 4.2 5.1 5.3 3.7
C8 Aromatics 11.6 11.4 13.3 10.4
C9 Aromatics 13.7 11.6 10.4 14.6
C10-C11 Aromatics 14.1 11.5 10.3 15.1
Unidentified 5.0 5.6 3.4 6.4

Oppositely, when the VGO was co-processed with 4.2 %wt. upgraded bio-oil, the yield
and the composition of the gasoline were similar to that in the case of the VGO alone.

Some authors observed similar changes in the composition of the gasoline cut when co-
processing hydrotreated bio-oil and VGO over a FCC catalyst in fixed (Thegarid et al.,
2013) and fluidized (Agblevor et al., 2010) bed reactors. They reported that the addition
of bio-oil favored the production of branched paraffins against linear ones, as well as
monoaromatics against polyaromatics, and assigned this behavior to changes in the
availability of acidic sites due to the adsorption of oxygenated molecules and water, and
28
to the consumption of hydrogen by the bio-oil components, thus limiting hydrogen
transfer reactions.

It must be remarked that the amount of oxygenated compounds remaining in gasoline

after co-processing VGO with crude and upgraded bio-oil was lower than 0.2 %wt.,
similar to the concentration reported by Fogassy et al. (2010) and Thegarid et al. (2010).
This is a particularly interesting issue, because oxygenated compounds can play a role
similar to octane improving additives such as MTBE and alcohols (Sharma and
Bakhshi, 1993) and also help to ease combustion. Indeed, the formulation of older
octane boosters included phenolic compounds (mainly phenol, cresol and
dimethylphenol), ethers (such as methylmethoxypropane and methoxybenzene) (Shang
et al., 1974 and 1976), furans (dimethylfuran) and ketones (4-methyl-2-pentenone)
(Hoffman, 1974).

4.2. Coke in co-processing bio-oils and FCC feedstocks

The yield of coke is essential in FCC, since its burning off in the regenerator is the
source of energy to sustain the strongly endothermic cracking reactions in the riser
reactor. An excessive coke production would impose, besides the loss in selectivity to
products of interest, the need for disposing the additional heat, which should be used
somewhere else in the refinery. However, technologies exist which can operate with
residual feedstocks with high coke yields (Wilson, 1997; O´Connor, 2007).

The coke yields in all the cases of co-processing VGO with crude and upgraded bio-oils
in the CREC Riser Simulator reactor were close to commercial values (see Table 5),
which usually range from 3.5 %wt. to 8 %wt. (Mandal et al., 1994; Nalbandian et al.,
1994). However, the VGO produced slightly more coke when processed alone than in
co-processing with the oxygenated feedstocks at the highest proportions (21.3 %wt.
crude bio-oil and 16.7 %wt. upgraded bio-oil). This was an expected behaviour,
considering that about half of the crude or upgraded bio-oil was water. Water in the
reaction medium reduces considerably the formation of coke as the consequence of the
competition between water and hydrocarbon molecules for adsorption on the catalyst
active sites, thus decreasing the reactants’ conversion rate and, consequently, the
29
mechanisms leading to coke. This was also noticed by Corma et al. (2007) in the
conversion of glycerol-water mixtures with VGO and by Agblevor et al. (2010) in the
co-processing of VGO and poplar sawdust bio-oil, who reported that coke yields
decreased up to 42 % when the mixtures had between 15 and 30 %wt. oxygenated
feedstock with respectively 2 and 16 %wt. of water, over an equilibrium FCC catalyst.

Moreover, the yield of coke with the mixture containing 16.7 %wt. upgraded bio-oil
was 10 % lower than that with the crude bio-oil, in consistency with the lower CCR in
the upgraded bio-oil (60 % lower). When the VGO was co-processed with 4.2 %wt.
upgraded bio-oil, the yield of coke was similar to the yield obtained with the VGO
alone; this fact, in addition to the previous observations (similar hydrocarbon product
distribution, similar gasoline composition and essentially complete conversion of
oxygenated compounds, strongly suggests that it is possible to co-process upgraded bio-
oil in standard FCC units.

The opposite effect on the yield of coke (slight increase in coke yields when co-
processing hydrocarbon feedstocks together with hydrotreated bio-oil, which does not
contain water) was observed by Samolada et al. (1998), de Miguel Mercader et al.
(2010) and Thegarid et al. (2010). In those cases, where fixed and fluidized bed reactors
and equilibrium FCC catalysts were used, coke yields ranged from 4 to 8 %wt., which
represented slight increases in the case of fluidized beds up to very significant changes
(almost two fold) in the case of fixed beds. A similar situation corresponded to the co-
processing of hydrotreated bio-oil and LCO (Lappas et al., 2009; Fogassy et al., 2010),
where the coke yield increased from small changes about 1 % in fluidized bed reactors
to about two times in fixed bed reactors, in comparison to hydrocarbon feedstocks only.

5. Conclusions

Co-processing bio-oils from residual lignocellulosic biomass together with conventional

hydrocarbon fossil feedstocks in existing refining processes is an attractive alternative
to produce transportation fuels and raw materials for the chemical industry.
Hydrotreating and catalytic cracking are possible receptors for these highly oxygenated
30
mixtures. The various alternatives should be studied soundly, and the conversion of
actual bio-oils, as well as of model compounds representing the different chemical types
involved, over commercial catalysts under realistic process conditions, is necessary to
know about reaction mechanisms and contributions to the product slates in co-
processing. Finally, co-processing of bio-oils and fossil feedstocks is unavoidable to
define feasibilities.

Hydrotreating is effective to deoxygenate bio-oils, removing up to 90 % of the oxygen

in the mixture. However, reports so far do not show that it is completely possible to co-
process bio-oils and hydrocarbon feedstocks in the process. Moreover, at least two steps
are necessary to efficiently convert the oxygenated compounds into hydrocarbons: the
first one to stabilize them and the second one to truly deoxygenate them. This results in
high processing costs due to high hydrogen consumption; moreover, the lack of
solubility between feedstocks and the high coke yield leading to catalyst deactivation
and the need for plant shut off, might represent severe problems.

Studies about co-processing bio-oils and VGO in FCC show that this alternative is
possible. For example, if bio-oil from biomass pyrolysis is co-processed with a typical
VGO over a commercial equilibrium FCC catalyst in a CREC Riser Simulator reactor,
which closely mimics the conditions of an ideal riser reactor, it is shown that more
gaseous hydrocarbons, particularly C2-C4 olefins, and less liquid hydrocarbons in the
C5-C20 range are produced in comparison to the VGO alone. The loss in gasoline
yields was insignificant when upgraded bio-oil was added at 4.2 %wt. Moreover, coke
yields remained close to typical commercial values between 3.5 and 5.5 %wt. Co-
processing bio-oils in FCC is also attractive because most of the problems which are
foreseen in other processes do not interfere significantly here. For example, continuous
catalyst regeneration is used, new technologies allow processing heavy residual
feedstocks with high coke yields, and bio-oil could be fed separately at various injection
points in the units, without need for solubility between feedstocks. A previous thermal
upgrading of bio-oil would be convenient to decrease coke yields and improve
processability.

31
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