Energy 35 (2010) 111–119

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

The current status and perspectives of biofuel production via catalytic

cracking of edible and non-edible oils
Yee Kang Ong, Subhash Bhatia*
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Biofuel development has gained the attention of researchers in recent years owing to the rate of
Received 24 December 2008 depletion of fossil fuels. Several processes are currently employed in the conventional production of
Received in revised form different biofuels: the production of biodiesel is catalytically performed either through the trans-
31 August 2009
esterification of triglycerides using alcohol or the deoxygenative ecofining of triglycerides in a non-
Accepted 1 September 2009
alcohol environment; bio-oil is produced by the pyrolysis of biomass; bio-ethanol is produced by the
Available online 24 September 2009
fermentation of sugars obtained from starch or cellulosic based biomass, while bio-gasoline is produced
from the catalytic cracking of triglycerides. Owing to the enormous dependency of transport vehicles
Keywords:
Biofuel running on gasoline engines, the development of bio-gasoline may well reduced the dependence of the
Catalytic cracking process fuel market on fossil fuels. The present article summarizes recent progresses and future prospects of
Palm oil biofuel production via catalytic cracking technology. This technology can be implemented in current
Transport riser reactor petroleum refineries with minor modifications. However, reactor design and catalyst choice are impor-
Zeolite based cracking catalysts tant issues and have to be addressed before successful implementation of this technology in commercial
ventures.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction routes for biofuels production. Biodiesel is produced by the trans-

esterification of edible and non-edible oils with methanol or
The world’s accessible oil reservoirs are gradually depleting due ethanol in the presence of catalysts [2–6]. Recently, an ecofining
to a burgeoning demand of fossil fuels. In addition, the production process developed by UOP reported the production of green bio-
and consumption of fossil fuels have caused severe environmental diesel from edible and non-edible oil in the presence of heteroge-
pollution by generating carbon dioxide leading to greenhouse neous catalyst and hydrogen gas [7]. Bio-alcohols that are widely
effects. Therefore, there is a pressing need for the development of used in Brazil and United States as blend in fuel are produced from
alternative energy sources as useful fossil fuel substitutes, and this fermentation of sugar obtained from biomass or corn [8–10]. Bio-oil
study investigates the use of biofuels as one of those alternative produced from pyrolysis of biomass can be further upgraded for
energy sources. Biofuels are generally referred to liquid or gaseous different applications by hydrogenation and catalytic cracking
fuels that are produced from renewable sources [1]. A variety of processes [11–15]. In addition, bio-oil rich in lipids can also be
liquid fuels can be produced from renewable resources and these obtained from algae and upgraded to biodiesel [16]. Catalytic
are ethanol, methanol, biodiesel, and Fischer–Tropsch gas oil using cracking process is used to produce biofuel rich in different frac-
synthesis gas obtained from biomass. Gaseous fuels such as tions (gasoline, diesel and kerosene) from edible and non-edible
hydrogen and methane can be produced from a number of oils [17,18]. Weisz [19] reported that gasoline could be obtained
renewable sources. Liquid biofuels are primarily used to fuel from plant extracts by using shape-selective catalysts via catalytic
transportation vehicles, but they are also applicable to fuel engines cracking process. This process is similar to the production of
or fuel cells for electricity generation [1]. gasoline from gas oil in the petroleum refinery.
Biofuels can be produced by several methods depending on the The catalytic cracking process shows several clear advantages in
types of feeds and final products required. Fig. 1(a) shows various comparison with the pyrolysis, fermentation or transesterification
processes. Firstly, the temperature of catalytic cracking process
(450  C) is lower than pyrolysis (500–850  C) [18]. Next, the
* Corresponding author. Tel.: þ60 4 5996409; fax: þ60 4 5941013.
product quality derived from pyrolysis is strongly dependent on the
E-mail address: [email protected] (S. Bhatia). type of feedstock used. The use of a highly cellulosic feedstock will

0360-5442/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2009.09.001
112 Y.K. Ong, S. Bhatia / Energy 35 (2010) 111–119

a
Biofuel Production
Processes

Catalytic Pyrolysis Fermentation Transesterification Ecofining of

Cracking of of biomass of sugar of edible and non- edible and non-
edible or obtained from edible oil edible oils
non-edible cellulosic
oils biomass

Gasoline,
Kerosene,
Bio-oil Bio-alcohol Biodiesel
Diesel,
Aromatics,
Olefins

b Biofuel Feedstock

Oil-based Biomass

Edible Oil from Waste Non-edible Waste Aquatic Energy Forest

Oil algae Oil Oil Materials Biomass Crops Products

Fig. 1. An overview of the biofuel: (a) production route (b) feedstock.

produce a liquid fraction that contains acids, alcohols, aldehydes, compositions, cellulosic biomass is more difficult to convert into
ketones and phenolic compounds [20]. On the other hand, the fuel (bio-ethanol) compared to starch-based biomass due to its
production of ethanol via fermentation requires a necessary crystalline recalcitrant structure. Aquatic biomass such as micro-
pretreatment of feedstock with processes such as saccharification algae (Haematococcus pluvialis) has become an interesting feed-
and hydrolysis. In addition, fermentation requires a much longer stock for biofuel production due to the potential for significantly
reaction time than the catalytic cracking process. Trans- higher average photosynthetic efficiency compared to typical land
esterification is only applied to the production of biodiesel whereas crops [22]. In addition, plant oil-based feedstock such as vegetable
catalytic cracking can be applied for the production of kerosene, oils and palm oil are common feedstock to produce biofuels owing
gasoline and diesel. The main drawback of transesterification using to the presence of triglycerides. Triglycerides are easy to convert
homogeneous catalysts is still the costs associated with the overall into liquid transportation fuels compared to biomass since they are
high energy consumption and separation [18]. Therefore, hetero- high-energy liquids that contain less oxygen [21]. However, this
geneous transesterification processes and non-catalytic trans- feedstock is also an edible oil for food preparations, which might
esterification under supercritical conditions are still under result in a conflict over the most prudent use of such a resource.
continuous research and improvement. The issue concerning biofuels and food has been widely dis-
Extensive research has been done and discussed in the past on cussed around the world. Many individuals and groups have called
biofuel production by transesterification and pyrolysis [4,5,13,14]. for a global rethinking of how best to precede with biofuel
Therefore, the objective of this article is to review the production of production in the light of its potential impact on the world food
biofuels using catalytic cracking technology. Feedstock suitable for supplies; there is disagreement even among the ranks within given
the process, reaction mechanism, types of cracking catalysts, cata- sectors [23]. Agro-business companies are in favor of crops used in
lytic reactors, past research as well as future prospects of this biofuels as they will be able to reap more economic benefits from
technology are presented and discussed. biofuel feedstock sales than from food sales, while on the other
hand some individuals argue that the development of biofuels will
2. Feedstock have a significant impact on the global food supply especially in
developing countries. However, there are many who believe that
The feedstock for biofuel production is of reasonable cost as well fuel and food crops can coexist without one being sacrificed or
as sustainable in terms of their supplies, and can be represented by favored over each other, but the success of this balance is depen-
Fig. 1(b). The biomass-derived feedstock for biofuel production can dent on governmental policy, which is the ultimate decision maker
be divided into four categories depending on the source. They are in optimizing a target biofuel production goal while providing
obtained from waste materials (agricultural, wood, and crop resi- a sufficient and affordable food supply for the common people [23].
dues), aquatic biomass (algae, water weed, water hyacinth), energy Many solutions have been proposed to minimize the impact of
crops (starch crops such as corn, wheat, and barley, sugar crops) biofuel production on the world food supply. Jacques Diouf, the
and forest products (wood, logging residues, trees, shrubs) [21]. director general of Food and Agriculture Organization of the United
Although starch and cellulose both possess similar elemental Nations (FAO), saw the microcredit system as a potential way to
 Y.K. Ong, S. Bhatia / Energy 35 (2010) 111–119 113

help rural and subsistence farmers in poor countries to enter the cracking as it can take place at much lower temperatures. In
biofuels market [24]. In addition, scientists and researchers are addition, the catalytic cracking process produces a high octane
exploring alternative feed stocks for biofuels other than food gasoline and lowers the yield of heavy fuel oils and light gases.
crops. Currently, plenty of non-edible sources have been identi- However, coke is generated during the reaction and deposited on
fied as potential feedstock for biofuel production, comprising the active sites of the catalysts [28], leading to catalyst deactivation.
waste cooking oil, free fatty acid mixtures, Jatropha oil, micro- Therefore, regeneration of the deactivated catalyst is carried out
algae (H. pluvialis), Cerbera odollam (Sea mango) and giant grass continuously in a regenerator by burning the coke deposited on the
Miscanthus [25]. However, there are still many challenges for the catalyst in air to maintain its activity [29]. In addition, the catalytic
production of biofuels from this feedstock such as the high cost cracking reaction is endothermic while regeneration process is
of harvesting/extracting and comparatively undeveloped tech- exothermic. Some cracking reactors are designed to use the heat
nology in comparison with food-based biofuels production. from regeneration process to preheat the feed to reaction temper-
Hence, food crop demand is expected to dominate the biofuels ature [29].
industry in the short term [23]. In order to increase gasoline yield and reduce the coking
The compositions of plant oil-based feedstock are listed in Table phenomenon, many researchers found that a short contact time
1. All the oil-based feedstock generally consists of three main fatty (SCT) between catalysts and oil vapors at moderate temperature
acids: palmitic acid, oleic acid and linoleic acid. The composition of was highly preferable. The fluid catalytic cracking (FCC) process has
palmitic acid in crude palm oil is higher than used palm oil and been identified to be a potential way to cope with the catalysts’
fatty acids mixture. The fatty acid mixture consists mainly of oleic deactivation problem. The same concept is applied in the produc-
acid. Conversely, soybean oil and rapeseed oil consists of oleic acid tion of biofuels especially bio-gasoline from vegetable oils.
and linoleic acid. Triglyceride based feedstock is vaporized and brought in contact
Since Malaysia is one of the largest producers of palm oil, there with catalysts in a riser reactor. The cracking reaction takes place on
has been a sustained interest in the utilization of palm oil and oil cracking catalysts with short residence time (w20 s) [30].
palm biomass for the production of environmentally friendly bio-
fuels [18]. There are a number of advantages in utilization of palm 4. Chemistry and mechanism
oil for the production of biofuels. Unlike fossil fuels, the combustion
of palm oil biofuels does not increase the level of carbon dioxide in A reaction pathway for catalytic cracking of palm oil over HZSM-
the atmosphere as the oil merely returns carbon dioxide obtained 5 catalyst is proposed and shown in Fig. 2. Palm oil first undergoes
earlier from the atmosphere through photosynthesis. Therefore, thermal and catalytic cracking on the external surface of catalysts to
biofuels are regarded as carbon neutral [26]. In fact, the palm trees produce heavy hydrocarbons and oxygenates. These products were
that produce oil simultaneously absorb a substantial amount of further cracked into light alkenes and alkanes, water, carbon
carbon dioxide during photosynthesis to form biomass for the dioxide and carbon monoxide. It was assumed that primary
plant. Hence, the usage of palm oil-based biofuels can be said to be cracking occurs within the internal pore structure of zeolite cata-
one of the major contributing factors in the reduction of global lysts. However, initial fragmentation could occur on the external
warming. surface of catalysts followed by diffusion into the pores [31]. Light
alkenes can also undergo oligomerization to produce a mixture of
3. Catalytic cracking heavier alkenes and alkanes which are categorically arranged under
gasoline, diesel and kerosene fractions. The aromatic hydrocarbons
Catalytic cracking process is applied in the conversion of high were produced by aromatization, alkylation and isomerization of
boiling point, high molecular weight gas oil into valuable gasoline heavier olefins and paraffins. Coke is produced by direct conden-
and olefins at petroleum refineries. The feedstock for the catalytic sation of palm oil and polymerization of aromatics.
cracking process at the petroleum refinery has traditionally been The kinetics and modeling of catalytic cracking on used palm oil
gas oil with an average molecular weight in the range of 200–600 and a palm oil-based fatty acid mixture was reported by Ooi et al.
or higher [27]. This process is favorable compared to thermal [32] and Bhatia et al. [33] using different lumped models. The

Table 1
Composition (wt %) of some plant oil-based feedstock (edible and non-edible) [28,39,46].

Fatty Acid Feedstock

Edible Oil Non-edible Oil

Soybean Oil Crude Palm Oil Used Palm Oil Fatty Acid Mixture Rapeseed Oil Jatropha Oil
(CPO)
Lauric acid (C12:0) – 0.1 1.03 3.23 – –
Myristic acid (C14:0) – 0.5–1.5 2.34 1.59 – 0–0.1
Palmitic acid (C16:0) 14 40–45 22.47 6.11 4.8 14.1–15.3
Palmitoleic acid (C16:1) – 0.3–0.4 7.56 – – 0–1.3
Heptadecanoic acid (C17:0) – – 0.48 – – –
Stearic acid (C18:0) 4 5–6 12.51 8.25 1.5 3.7–9.8
Oleic acid (C18:1) 24 36–40 27.64 68.64 60.7 34.3–45.8
Linoleic acid (C18:2) 52 9–11 14.58 7.00 21.2 29.0–44.2
Linolenic acid (C18:3) 6 0.2–0.3 1.55 – 11.8 0–0.3
Arachidic acid (C20:0) – 0.3–0.4 0.64 1.80 – 0–0.3
Eicosenoic acid (C20:1) – Trace – 1.05 – –
Eicosadienoic acid (C20:2) – – 0.29 – – –
Arachidonic acid (C20:4) – – 0.37 – – –
Behenic acid (C22:0) – – – 0.59 – 0–0.2
Lignoceric acid (C24:0) – – – 1.21 – –
Others – Trace 8.54 0.53 – –
114 Y.K. Ong, S. Bhatia / Energy 35 (2010) 111–119

Vegetable Oil

Condensation Deoxygenation and cracking

Coke Heavy hydrocarbons + Oxygenates

Deoxygenation and
secondary cracking

Polymerization Light olefins + Light paraffins (gasoline)

+ CO2 + alcohol + CO + H2O

Oligomerization
Alkylation, Isomerization,
Aromatization
Aromatic Hydrocarbons Olefins + Paraffins (gasoline, diesel & kerosene)

Gases (light olefins, paraffin, CO, CO2, H2O)

Fig. 2. Proposed reaction pathway for the conversion of palm oil over HZSM-5 catalyst
to hydrocarbon products [31].

formulation of a lumped kinetics scheme is a common method used

to model the kinetic behavior of multi-component mixtures in the
catalytic cracking process. Hydrocarbons with similar chemical
functions are grouped into lumps and the kinetic model derived is
based on these few lumps. Fig. 3 demonstrates the use of lumped
kinetic models ranging from three lumps to six lumps, with their
corresponding rate parameters of three to six based on the lumping
system used.
The three-lumped model shows that feedstock can be directly
converted to gaseous products, coke and organic liquid products
(OLP). Coke and gaseous products in the three-lumped model were
separated into two individual lumps in the four-lumped model. The
organic liquid products were further split into more pseudo-
components based on their boiling points in a six-lumped model.
They were separated into three lumps consisting of the gasoline
fraction, the kerosene fraction and the diesel fraction. These were
defined according to the boiling range of the petroleum products in
the three fractions: gasoline fraction (60–120  C), kerosene fraction
Fig. 3. Kinetic scheme for (a) three-lumped model, (b) four-lumped model, and (c) six-
(120–180  C) and diesel fraction (180–200  C) [29]. The six-lumped lumped model [32].
model fits well with experimental data in term of comparison of
products yield towards reactor length and residence time [33]. Due
to complexity, three-lumped model was expanded to the six-
lumped model by incorporating energy balance equation to cracking of the feedstock chains. Catalysts with ordered structures
nonstationary and nonisothermal kinetic model [33]. The simula- provide the selectivity through their pores accessibility. The early
tion was done by using Runge–Kutta–Fehlberg (RKF) algorithm generation of FCC catalysts in gas oil cracking was made from X
available in Polymath software [34]. zeolite. Nowadays, virtually all of the catalysts are made from ultra
The kinetic model is also used to predict cracking product yield stable Y (USY) zeolite due to a higher thermal and hydrothermal
in a transport riser reactor using palm oil as feedstock. This model stability of Y zeolite in comparison with to X zeolite. The reduction
did not consider the catalysts’ deactivation function because cata- of lead in motor gasoline in 1986 created the need for a high octane
lysts did not show significant deactivation during the experimen- FCC gasoline [35]. Thus, catalyst manufacturers developed an ultra
tation. The model agreed well with experimental data and it can be stable Y zeolite in which a number of aluminum atoms from the
concluded that deactivation of the catalyst was insignificant for zeolite framework were removed through dealumination process
crude palm oil (CPO) cracking in a transport riser reactor due to [28]. Most of the cracking catalyst currently contains zeolite Y in the
a shorter palm oil residence time in transport riser reactor matrix of silica–alumina. ZSM-5 is commonly used as a catalyst
compared to that in a micro reactor [33]. additive to boost the gasoline octane number and to increase the
yield of light olefins [35].
Various types of zeolite catalysts are reported in catalytic
5. Cracking catalyst cracking for the production of biofuels from vegetable oils [15],
palm oil [30,36], used palm oil (UPO) [37,38] and palm oil based-
The choice of catalyst plays an important role in catalytic fatty acid mixtures (FAM) [39,40]. Mesoporous materials such as
cracking. Its function is to provide acid sites which promote MCM-41 [41] and SBA-15 [38,40] are also used as catalysts for
 Y.K. Ong, S. Bhatia / Energy 35 (2010) 111–119 115

cracking of crude palm oil and used palm oil. These findings show
that zeolites possess a great potential as solid acid cracking catalyst
due to its structure, acidity and high selectivity for the production
of biofuels from vegetable oils.
Twaiq et al. [41] reported that the selectivity of MCM-41 mes-
oporous materials towards particular liquid hydrocarbons such as
gasoline, kerosene or diesel in the cracking of palm oil was strongly
dependent on the pore size and the surface area of mesoporous
materials. In addition, mesoporous materials gave lower activity in
catalytic cracking of palm oil compared to HZSM-5 catalyst. The
selectivity of mesoporous catalyst was towards the diesel fraction
with a high content of linear hydrocarbons products [42]. Ooi et al.
[39] reported that HZSM-5 produced organic liquid products that
are rich in gasoline fraction from the catalytic cracking of palm oil
based fatty acids mixture (FAM). The cracking activity of meso-
porous materials such as MCM-41 and SBA-15 catalysts were lower
than ZSM-5 zeolite due to lower acidity and shape selectivity of
these mesoporous materials.
Different types of composite cracking catalysts were also tested
by introducing mesoporous materials to further moderate the
cracking activity as well as to enhance the thermal and hydro-
thermal stability of the zeolite catalyst. Ooi et al. [37] reported that
MCM-41/Beta zeolite composite catalyst has better activity than
physical mixture of zeolite beta and MCM-41. This composite
catalyst was more selective towards liquid fuel gasoline and
enriched with olefins. In addition, SBA-15 and MCM-41 containing
aluminum gave better performance for catalytic cracking of palm
oil based waste fatty acid mixture in the production of biofuels.
Furthermore, it was reported that aluminum-loaded SBA-15
possessed a higher hydrothermal stability than aluminum-loaded
MCM-41 with similar cracking activity [40]. Similar research using
a composite cracking catalyst was reported by Twaiq et al. [43]
using MCM-41/ZSM-5 as the composite catalyst. Composite cata-
lysts containing lower mesophase coating were preferred since the
thin coating of a mesophase layer allows reactants to access the
micropores, resulting in a higher palm oil conversion and yield of
gasoline fraction. Different types of catalysts have been reported in
the literature for the production of biofuels via catalytic cracking in Fig. 4. Schematic of the transport riser reactor set up [30].
fixed bed micro reactor units (MAT) and are presented in Table 2.
Twaiq et al. [40,43] studied the catalytic cracking of palm oil promising cracking catalyst among the different types of meso-
using HZSM-5, MCM-41 and composite material (MCM-41/ZSM-5). porous catalysts tested. The used catalyst contains coke and was
HZSM-5 gave the highest yield of bio-gasoline as the acidity of regenerated by using steam and air to burn up all the coke into CO,
HZSM-5 greatly influenced the product distribution of the cracking CO2 and H2O. Katikaneni et al. [44] reported that HZSM-5 gave the
reaction. Composite material of MCM-41/ZSM-5 gave similar highest amount of organic liquid products compared to H-mor-
gasoline yield as HZSM-5 catalyst. However, the selectivity for the denite, H-Y, silicalite, aluminum-pillared clay and silica–alumina
diesel fraction increased due to higher alumina content in the catalysts in the catalytic conversion of canola oil to biofuels.
coating. Ooi et al. [40] identified that aluminum containing SBA-15 However, aluminum-pillared clay gave the highest amount of
(AlSBA-15) had higher cracking activity as well as hydrothermal olefins in the gases products. Thanh-An Ngo et al. [45] reported
stability than SBA-15 and Al-MCM-41. AlSBA-15 was a more that the pyrolysis of soybean oil for production of bio-oil and

Table 2
Catalytic cracking of different feedstock for production of biofuel in the catalytic micro reactor unit (MAT).

Feedstock Catalyst Condition Product, Yield (Highest) Reference

Bio- Kerosene Diesel Gases Coke

gasoline (wt %) (wt %) (wt %) (wt %)
(wt %)
Palm Oil MCM-41 Pressure: 1 atm T ¼ 450  C WHSV ¼ 2.5 h1 43.3 11.0 9.6 21.8 12.2 [42]
Palm Kernel Oil 50.9 22.2 9.8 10.0 12.1
 1
Palm Oil HZSM-5 Pressure: 1 atm T ¼ 450 C WHSV ¼ 2.5 h 49.2 26.1 2.6 8.2 1.7 [41]
Composite material 48.4 8.8 7.0 11.4 5.4
1
Used Palm Oil MCM-41/zeolite beta Pressure: 1 atm T ¼ 450  C WHSV ¼ 2.5 h 28.9 15.9 12.3 13.4 10.7 [37]
(composite)
Palm oil based waste fatty acid SBA-15 Pressure: 1 atm T ¼ 450  C WHSV ¼ 2.5 h1 20.7 15.5 4.8 9.5 7.2 [40]
Al-SBA 36.0 17.2 4.6 16.2 6.3
Al-MCM-41 32.6 20.0 6.7 6.7 9.8
116 Y.K. Ong, S. Bhatia / Energy 35 (2010) 111–119

hydrocarbon gaseous products in the presence of HZSM-5 and Ga/ Tian et al. [47] reported the use of a two-stage riser fluid cata-
MCM-41 catalysts at a reaction temperature of 420  C produced lytic cracker (TSRFCC) for the cracking of palm oil and animal fats
2 different liquid product compositions: The liquid product from using Co-Rh catalyst containing ultra stable Y (USY) zeolite and LTB-
the HZSM-5 catalyst was rich in aromatics whereas the liquid 2 (ZSM-5 zeolite as active components). A schematic of the two-
product from the Ga/MCM-41 catalyst gave a mixture of alkanes, stage riser fluid catalytic cracking technology (TSRFCC) is presented
alkenes, aromatics and carboxylic acids. in Fig. 5. Fresh feedstock was injected into the first stage riser and
recycling oil (including gasoline and heavy oil) from the fraction-
ator was injected into the second stage. Both risers shared
a common disengage unit and regenerator. Thus, the fresh feed-
6. Catalytic cracking of vegetable oils
stock and the recycling oil (having different adsorption and reaction
properties) are contacted with regenerated catalyst and react
In the continuous production of bio-gasoline, Tamunaidu and
respectively under the most favorable conditions. Furthermore, the
Bhatia [28] reported the catalytic cracking of used palm oil (UPO)
lengths of the two risers differ markedly from each other and are
and crude palm oil (CPO) using rare earth Y (REY) catalyst in
much shorter than conventional FCC risers [42] and its advantage
a transport riser reactor. A schematic of the transport riser reactor is
lies in the catalyst relay and staged reaction. The result showed that
shown in Fig. 4. An organic liquid product rich in gasoline fraction
the cracking of palm oil gave a high yield of (liquid petroleum gas)
(33.5 wt %) was produced within a short residence time (10–30 s) at
liquid petroleum gas(LPG) (45 wt %) and the yield of gasoline
a 75.8 wt % conversion of CPO. The cracking of CPO and UPO in the
reached 21 wt % in a TSRFCC. The high olefin yield (47 wt %) was due
transport riser reactor was also studied over different catalyst
to the termination of the secondary cracking reaction by TSRFCC
additives comprising microporous, mesoporous and macroporous
technology. This research proved that a high aromatic concentra-
materials [28]. Microporous Zeolite Beta was found to be less active
tion was resultant from a large amount of hydrogen-transfer,
than HZSM-5 and less selective for gasoline fraction formation in
cyclization and aromatization reactions. A summary of the results
the cracking of CPO and UPO. In addition, there was found to be
reported in the literature on continuous production of biofuels via
a positive correlation linking the conversion of CPO as well as UPO
catalytic cracking is presented in Table 3.
with an increase in the acidity of the SBA-15 and AlSBA-15 meso-
porous materials. Alumina was also used as an additive along with
REY catalyst to study the effect of macroporous material. However, 7. Reactors
the activity and selectivity towards gasoline fraction increased only
by a small fraction with the addition of alumina in REY catalyst. The catalytic cracking process is characterized as a gas-solid
Dupain et al. [46] studied the catalytic cracking of rapeseed reaction and reactor choice is important when optimizing reaction
vegetable oil using a commercial equilibrium catalyst and a mixture rates and production schedules. Heterogeneous reactors such as
of the commercial equilibrium catalyst with ZSM-5. Their findings fluidized bed, entrained flow reactor, trickle bed, slurry phase,
showed that the presence of double bonds in the molecular bubbling bed and fixed bed reactors facilitate adequate contact
structure of feedstock enhanced the formation of aromatics in between fluid phase and catalyst [48]. Most of the continuous
gasoline and light cycle oil (LCO). A decline in lower olefin (C3 ¼ and production of biofuels via catalytic cracking uses the concept of
C4¼) yield was observed since large aromatic products were rarely fluidized-bed catalytic cracking, similar to the concept applied in
subjected to serial cracking reactions. conventional petroleum refineries. This continuous reactor

Rich Gas

Catalyst
Gasoline
Tank

Diesel
Disengager
Oil
1st Riser

2nd Riser
Flue gas

Slurry
Regenerated
Catalyst Crude Gasoline
Regenerator

Fresh
Feed

Regenerated
Catalyst

Spent
Catalyst

Fig. 5. Schematic of two-stage riser fluid catalytic cracker (TSRFCC) [47].

 Y.K. Ong, S. Bhatia / Energy 35 (2010) 111–119 117

Table 3 The yield of the desired product is greatly dependent on oper-

Summary of the study on continuous production of biofuel via catalytic cracking. ating variables such as reaction temperature, catalyst-to-oil ratio
Feedstock Reactor Condition Yield of Bio- Reference and residence time as well as reactor design. Therefore, it is
gasoline, possible to make minor modifications of the existing reactor
wt % schemes set up in petroleum refineries to support the production of
Crude Transport Riser Reactor T ¼ 400–500  C 57.9 [30] biofuels. Fig. 6 shows the concept of the production of biofuels by
Palm Residence
catalytic cracking in a riser reactor in a typical bio-refinery.
Oil time ¼ 10–30 s
Catalyst/feed Regenerated catalyst is mixed with feedstock vapors at the
ratio ¼ 5–10 bottom of the riser reactor. Catalytic cracking occurs along the riser,
Rapeseed Laboratory-scale once- T ¼ 480–585  C 43.0 [46] and the product and spent catalysts are separated by an internal
Oil through micro riser Residence cyclone located at the top of the riser reactor. Water is separated
reactor time ¼ 50 ms–
8s
from the organic liquid products before being fed into fractionators.
Catalyst/feed The organic liquid products are then separated in the fractionator
ratio ¼ 4 into different fractions of gasoline, kerosene and diesel based on
Palm Oil Two-stage riser fluid T ¼ 500–520  C 21.0 [47] their boiling point cuts. The bottom product of fractionator is
Chicken catalytic cracking unit Residence 32.8
recycled back to the riser reactor, while spent catalyst separated
Fat time ¼ 1.4–1.7 s
Soyabean Catalyst/feed 22.9 from the riser reactor is regenerated in a regenerator. Steam and air
Oil ratio ¼ 6–8 are used to regenerate the spent catalyst, which is then recycled
back to the riser reactor. The use of steam in the catalyst regener-
ation process necessitates the requirement that the catalyst used
must be hydrothermally stable.
generally provides uniform product quality as well as lower the
production cost for a large scale production [49]. 8. Future directions
Feedstock is preheated by a heat exchanger or a heater before
being fed into the riser reactor where it is then mixed with hot Several issues have to be taken into consideration for the
cracking catalyst. The cracking catalyst and feedstock vapor production of biofuels via catalytic cracking. The hydrodynamic
mixture then travel up along the riser into the reactor. The cracking flow behavior inside the riser reactor is a main issue as the
process starts once the feedstock vapors come into contact with the fluidization characteristic of catalysts possesses a large influence
hot cracking catalyst until the vapors are separated from the over feedstock conversion. On the other hand, the scale up and
cracking catalyst. The vapors are then sent to fractionators for design of a reaction-controlled bubbling fluidized bed reactor is
separation into liquid and gaseous products, while the spent fraught with uncertainty [50]. Ong and Bhatia [51] reported
cracking catalyst is sent to the regenerator for regeneration by a hydrodynamic study in a transport riser reactor, as it was
burning off the coke deposited on the catalyst. The hot regenerated suggested that cold (hydrodynamic) model is reported as the best
catalyst is continuously sent back to the riser reactor [35]. Air and option to study the hydrodynamic behavior [50]. In addition,
steam are used in the regeneration process where steam is catalyst characteristics, such as attrition resistance, have to be
primarily used to remove entrained hydrocarbon between catalyst accounted for in the overall reactor design. The attrition resis-
particles while air supplies oxygen for the combustion of coke [35]. tance is very important as the catalysts are in a constant fluidized

Transport
Riser
Reactor OLP+Water Fractionator
Regenerator
Olefins + Gas
Flue gas Heat
Cyclone Exchanger

Bio-gasoline

Spent
Catalyst
Kerosene
Water

Heat
Exchanger Diesel

Steam + Air

Reboiler
Regenerated
Fresh
Catalyst
Catalyst

Feedstock
(Palm Oil)
Recycle

Fig. 6. Proposed concept of biofuel production at conventional petroleum refinery.

118 Y.K. Ong, S. Bhatia / Energy 35 (2010) 111–119

state during the reaction. Suitable coating methods for attrition and catalyst design as well as optimum process operation condition
reduction such as the in situ overgrowth technique are a prom- in order to further improve the bio-gasoline production.
ising solution since it ensures chemical bonding between cata-
lysts and coating [52]. The coating containing mesoporous Acknowledgement
ceramic material containing zeolite matrix could be one of the
solution to minimize attrition. The authors would like to acknowledge the financial support
The quality of bio-gasoline produced has to be verified for its provided by the Ministry of Science; Technology and Innovation of
suitability in existing gasoline engines. Since biofuels has become Malaysia (MOSTI) in the form of e-Science Fund Grant (Project
a popular substitute for fossil fuels, a standard testing method (such number: 03-01-05-SF0221) and Research University Grant
as ASTM D6751-01 for Biodiesel (B100)) for bio-gasoline must be provided by Universiti Sains Malaysia that resulted in this article.
developed. Due to global environmental legislation that limits the Special appreciation is also expressed to Mr. Joel Yong K.J for the
maximum aromatics concentration in gasoline to 35 vol % and help in this article.
15 wt % in diesel respectively, the hydrocarbon production spec-
trum has shifted from aromatics to napthenes and paraffins that
References
can burn cleaner [53]. Lowering the conversion of feedstock and the
cut point of the full gasoline distillation range are options to tackle [1] Demirbas A. Progress and recent trends in biofuels. Progress in Energy and
this problem, though these options are heavily unfavorable Combustion Science 2007;33(1):1–18.
economically [53]. The tuning of cracking catalyst is one of the [2] Kansedo J, Lee KT, Bhatia S. Biodiesel production from palm oil via heteroge-
neous transesterification. Biomass and Bioenergy 2009;33(2):271–6.
options to lower the aromatics concentration. Yet another potential [3] Kansedo J, Lee KT, Bhatia S. Cerbera odollam (sea mango) oil as a promising
alternative would be the mixing of vegetable oils and gas oils, as non-edible feedstock for biodiesel production. Fuel 2009;88(6):1148–50.
they can be catalytically cracked in the production of biofuels with [4] Jacobson K, Gopinath R, Meher LC, Dalai AK. Solid acid catalyzed biodiesel
production from waste cooking oil. Applied Catalysis B: Environmental
the desired properties. 2008;85(1–2):86–91.
Olefins such as ethylene and propylene are widely used as [5] Nakatani N, Takamori H, Takeda K, Sakugawa H. Transesterification of soybean
feedstock for manufacturing the basic polymers such as poly- oil using combusted oyster shell waste as a catalyst. Bioresource Technology
2009;100(3):1510–3.
ethylene and polypropylene that are needed for the plastics [6] Gui MM, Lee KT, Bhatia S. Feasibility of edible oil vs non-edible oil vs waste
industries. Thus, it is beneficial to explore the possibilities of edible oil as biodiesel feedstock. Energy 2008;33:1646–53.
processes suitable for the production of olefins along with bio- [7] Kalnes T, Marker T, Shonnard DR. Green diesel: a second generation biofuel.
International Journal of Chemical Reactor Engineering 2007;5:A48.
gasoline by using catalytic cracking technology. Catalytic cracking
[8] Hahn-Hägerdal B, Galbe M, Gorwa-Grauslund MF, Lidén G, Zacchi G. Bio-
processes using acidic zeolite catalyst such as ZSM-5 is a prom- ethanol – the fuel of tomorrow from the residues of today. Trends in
ising option to obtain olefins. There has been growing interest in Biotechnology 2006;24(12):549–56.
the application of nanoscale zeolites in catalytic cracking tech- [9] Linde M, Galbe M, Zacchi G. Bioethanol production from non-starch carbo-
hydrate residues in process streams from a dry-mill ethanol plant. Bioresource
nology. Zeolites with crystal sizes smaller than 100 nm are Technology 2008;99(14):6505–11.
potential replacements for existing zeolite catalysts and the [10] Keshwani DR, Cheng JJ. Switch grass for bioethanol and other value-added
crystal size of zeolites has a great effect on the catalytic activity applications: a review. Bioresource Technology 2009;100(4):1515–23.
[11] Ateş F, Pütün AE, Pütün E. Pyrolysis of two different biomass samples in
and selectivity [54]. It has been reported that when the crystal a fixed-bed reactor combined with two different catalysts. Fuel 2006;85(12–
size of HZSM-5 zeolite is reduced to the nanoscale, super catalytic 13):1851–9.
properties such as higher activity, lower coke content and better [12] Zhang H, Xiao R, Huang H, Xiao G. Comparison of non-catalytic and catalytic
fast pyrolysis of corncob in a fluidized bed reactor. Bioresource Technology
stability can be achieved [54]. This category of zeolite is 2009;100(3):1428–34.
a potential catalyst to be incorporated into the production of bio- [13] Özbay N, Apaydın-Varol E, Uzun BB, Pütün AE. Characterization of bio-oil
gasoline. There are still plenty of questions and issues that have obtained from fruit pulp pyrolysis. Energy 2008;33(8):1233–40.
[14] Boateng AA, Mullen CA, Goldberg N, Hicks KB, Jung HG, Lamb JFS. Production
to be overcome before large scale production of bio-gasoline can
of bio-oil from alfalfa stems by fluidized-bed fast pyrolysis. Industrial and
be implemented using this technology in bio-refinery. Szklo and Engineering Chemistry Research 2008;47(12):4115–22.
Schaeffer [55] presented and analyzed alternative energy systems [15] Suurs AAR, Hekkert MP. Competition between first and second generation
technologies: lessons from the formation of a biofuels innovation system in
utilizing alternative energy sources in an integrated refinery
the Netherlands. Energy 2009;34:669–79.
complex for the production of biofuels, electricity, hydrogen gas, [16] Posten C, Schaub G. Microalgae and terrestrial biomass as source for fuels-
liquid fuels and chemicals. a process view. Journal of Biotechnology 2009;142(1):64–9.
[17] Sharma RK, Bakhshi NN. Upgrading of tall oils to fuels and chemicals over
HZSM-5 using various diluents. The Canadian Journal of Chemical Engineering
1991;69(5):1082–6.
9. Conclusions [18] Chew TL, Bhatia S. Catalytic processes towards the production of biofuels in
a palm oil and oil palm biomass-based biorefinery. Bioresource Technology
2008;99(17):7911–22.
The production of biofuels (especially bio-gasoline) from palm [19] Weisz PB, Haag WO, Rodewald PG. Catalytic production of high-grade fuel
oil and waste vegetable oils by catalytic cracking is a promising (gasoline) from biomass compounds by shape-selective catalysis. Science
alternative. The yield of hydrocarbons produced is strongly 1979;206(4414):57–8.
[20] Klass DL. Biomass for renewable energy, fuels, and chemicals. San Diego, CA:
dependent on the choice of shape selective and acidity of the Academic Press; 1998.
catalyst. Zeolites (ZSM-5 and USY) and mesoporous materials [21] Hubber GW, Corma A. Synergies between bio- and oil refineries for the
MCM-41 and SBA-15 have shown great potential as cracking cata- production of fuels from biomass. Angewandte Chemie International Edition
2007;46(38):7184–210.
lysts. The cracking catalyst activity can be further enhanced by
[22] Vasudevan PT, Briggs M. Biodiesel production- current state of the art and
combining microporous zeolites and mesoporous materials to challenge. Journal of Industrial Microbiology and Biotechnology 2008;35:
increase its thermal and hydrothermal stability as well as selec- 421–30.
[23] Stein K. Food vs biofuel. Journal of the American Dietetic Association
tivity towards organic liquid products. Owing to the similarity of
2007;107(11):1870–8.
catalytic cracking process with the FCC process in petroleum [24] Forum Barcelona. Poverty, microcredits, and development: documents, 2004.
refineries, the continuous production of bio-gasoline via catalytic See also: http://www.barcelona2004.org/eng/banco_del_conocimiento/
cracking can be implemented in existing refineries with minor documentos/ficha.cfm?IdDoc_1523; 2004.
[25] Williams N. Biofuel debate deepens. Current Biology: CB 2008;18(19):
modifications, and this will greatly reduce the total capital invest- R891–892.
ment required. However, it is necessary to incorporate the reactor [26] MPOC, Malaysia Palm Oil Council. See also: http://www.mpoc.org.my; 2008.
 Y.K. Ong, S. Bhatia / Energy 35 (2010) 111–119 119

[27] Wikipedia. Fluid catalytic cracking. See also: http://en.wikipedia.org/wiki/ [43] Twaiq FA, Mohamed AR, Bhatia S. Liquid hydrocarbon fuels from palm oil
Fluid_catalytic_cracking; 2009. by catalytic cracking over aluminosilicate mesoporous catalysts with
[28] Tamunaidu P. Biofuel production from crude palm oil and used palm oil in various Si/Al ratios. Microporous and Mesoporous Materials 2003;
a transport riser catalytic reactor. Master thesis. Universiti Sains Malaysia; 2006. 64(1–3):95–107.
[29] Gary JH, Handwerk GE. Petroleum refining technology and economics. 4th ed. [44] Katikaneni SPR, Adjaye JD, Bakhshi NN. Catalytic conversion of canola oil to
New York: Marcel Dekker Inc; 2001. fuels and chemicals over various cracking catalysts. Canadian Journal of
[30] Tamunaidu P, Bhatia S. Catalytic cracking of palm oil for the production of Chemical Engineering 1995;73(4):484–97.
biofuels: optimizing studies. Bioresource Technology 2007;98(18):3593–601. [45] Thanh-An N, Kim J, Kim SK, Kim SS. Pyrolysis of soybean oil with H-ZSM-5
[31] Leng TY, Mohamed AR, Bhatia S. Catalytic conversion of palm oil to fuels (proton–exchange of zeolite socony mobil#5) and MCM-41 (mobile
and chemicals. The Canadian Journal of Chemical Engineering 1999;77(1): composition of matter No.41) catalysts in a fixed bed reactor. Energy. 1–6 [in
156–62. press, doi:10.1016/j.energy.2009.05.023].
[32] Ooi YS, Zakaria R, Mohamed AR, Bhatia S. Catalytic cracking of used palm oil [46] Dupain X, Costa DJ, Schaverien CJ, Makkee M, Moulijn JA. Cracking of a rape-
and palm oil fatty acids mixture for the production of liquid fuel: kinetic seed vegetable oil under realistic FCC conditions. Applied Catalyst B: Envi-
modeling. Energy & Fuels 2004;18(5):1555–61. ronmental 2007;72(1–2):44–61.
[33] Bhatia S, Chew TL, Tamunaidu P. Modeling and simulation of transport riser [47] Tian H, Li C, Yang C, Shan H. Alternative processing technology for converting
reactor for catalytic cracking of palm oil for the production of biofuels. Energy vegetable oils and animal fats to clean fuels and light olefins. Chinese Journal
& Fuels 2007;21(6):3076–83. of Chemical Engineering 2008;16(3):394–400.
[34] Fogler HS. Elements of chemical reaction engineering. 4th ed. Prentice-Hall; 2006. [48] Miller DJ, Jackson JE. Catalysis for bio-renewable conversion. In: National
[35] Sadeghbeigi R. Fluid catalytic cracking handbook. 2nd ed. Gulf Professional science foundation workshop report. (Virginia); 2004. See also: www.egr.msu.
Publishing; 2000. edu/apps/nsfworkshop
[36] Twaiq FA, Zabidi NAM, Bhatia S. Catalytic conversion of palm oil to hydro- [49] Leevijit T, Tongurai C, Prateepchaikul G, Wisutmethangoon W. Performance
carbons: performance of various zeolites catalysts. Industrial and Engineering test of a 6-stage continuous reactor for palm methyl ester production. Bio-
Chemistry Research 1999;38(9):3230–8. resource Technology 2008;99(1):214–21.
[37] Ooi YS, Zakaria R, Mohamed AR, Bhatia S. Synthesis of composite material [50] Levenspiel O. Difficulties in trying to model and scale-up the bubbling fluid-
MCM-41/beta and its catalytic performance in waste used palm oil cracking. ized bed (BFB) reactor. Industrial and Engineering Chemistry Research
Applied Catalyst A: General 2004;274(102):15–23. 2008;47(2):273–7.
[38] Ooi YS, Bhatia S. Aluminum-containing SBA-15 as cracking catalyst for the [51] Ong YK, Bhatia S. Hydrodynamic study of zeolite-based composite cracking
production of biofuel from waste used palm oil. Microporous and Mesoporous catalyst in a transport riser reactor. Chemical Engineering Research and Design
Materials 2007;102(1–3):310–7. 2009;87(6):771–9.
[39] Ooi YS, Zakaria R, Mohamed AR, Bhatia S. Catalytic conversion of palm [52] Liu H, Zhao H, Gao X, Ma J. A novel FCC catalyst synthesized via in situ
oil-based fatty acid mixture to liquid fuel. Biomass and Bioenergy 2004; overgrowth of NaY zeolite on kaolin microspheres for maximizing propylene
27(5):477–84. yield. Catalyst Today 2007;125(3–4):163–8.
[40] Ooi YS, Zakaria R, Mohamed AR, Bhatia S. Hydrothermal stability and catalytic [53] Dupain X, Gamas ED, Madon R, Kelkar CP, Makkee M, Moulijn JA. Aromatic gas
activity of mesoporous aluminum-containing SBA-15. Catalysis Communica- oil cracking under realistic FCC conditions in a micro riser reactor. Fuel
tions 2004;5(8):441–5. 2003;82(13):1559–69.
[41] Twaiq FA, Mohamed AR, Bhatia S. Performances of composite catalysts in palm [54] Zhang P, Guo X, Guo H, Wang X. Study of the performance of modified nano-
oil cracking for the production of liquid fuels and chemicals. Fuel Processing scale ZSM-5 zeolite on olefins reduction in FCC gasoline. Journal of Molecular
Technology 2004;85(11):1283–300. Catalyst A: Chemical 2007;261(2):139–46.
[42] Twaiq FA, Zabidi NAM, Mohamed AR, Bhatia S. Catalytic conversion of palm oil [55] Szklo A, Schaeffer R. Alternative energy sources or integrated alternative
over mesoporus aluminosilicate MCM-41 for the production of liquid hydro- energy systems? Oil as a modern lance of Peleus for the energy transition.
carbon fuels. Fuel Processing Technology 2003;84(1–3):105–20. Energy 2006;31:2513–22.