Energy Conversion and Management 89 (2015) 349–367

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Review

Biogasoline: An out-of-the-box solution to the food-for-fuel

and land-use competitions
S.N. Hassan a,b, Y.M. Sani a,c, A.R. Abdul Aziz a,⇑, N.M.N. Sulaiman a, W.M.A.W. Daud a
a
Department of Chemical Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Faculty of Chemical & Natural Resources Engineering, University Malaysia, 26300 Pahang, Malaysia
c
Department of Chemical Engineering, Ahmadu Bello University, 870001 Zaria, Nigeria

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

Article history: Societal developments are hinged on the energy supplied by fossil fuels. However, the supply of these
Received 31 December 2013 fuels is finite in the foreseeable future. This is aside the associated environmental degradation and eco-
Accepted 17 September 2014 nomic sustainability of these fuels. These negative consequences and challenges spurred the search for
sustainable energy sources such as biofuels. However, affordable feedstocks and efficient synthesis for
renewable fuels remain indispensable and yet challenging line of research. Therefore, breakthroughs in
Keywords: plant biotechnology and mass production are essential prerequisites for ensuring the sustainability of
Biogasoline
biofuels as alternatives to petroleum-based energy. Conversely, public outcry concerning the food-
Bioethanol
Biodiesel
for-fuel conflicts and land-use change hinder the popularity of such biofuel energy sources. Therefore,
Food-for-fuel this paper reviewed the prospects of biogasoline production as sustainable alternative to ethanol and a
Microalgae compliment to biodiesel. Apart from reduction in greenhouse gas emissions, biogasoline promises to
Rubber seed oil be cheaper and more environmental friendly. Further, inedible feedstocks such as microalgae and rubber
seed oil would ensure higher net energy gain. Consequently, these will help resolve the food-for-fuel
conflicts and land-use competitions. However, achieving the biofuel central policy depends on advances
in processing the renewable energy sources.
Ó 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
2. Challenges associated with biofuel production and utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
2.1. Land-use change and associated implications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
2.1.1. Biogasoline land requirement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.2. Food-for-fuel conflicts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
2.3. Unavoidable utilization of fossil fuels & gasoline formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
2.4. GHG emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
3. Determinants that influence the demand and supply of biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
3.1. Prevailing market conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
3.2. Socio-economic factors, health effects and environmental concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
3.3. Governmental policies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
3.4. Irregular distribution of global oil reserves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
3.5. Need for long-term durability tests on vehicles powered by unblended biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
4. Is there a light at the end of the tunnel? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
4.1. Biodiesel and bioethanol are only part of, but not the panacea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
5. Biogasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
5.1. Catalytic cracking of triglyceride-based feedstocks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
5.2. Biogasoline via fluid catalytic cracking of microalgal oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
5.3. Properties, characterization and availability of RSO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359

⇑ Corresponding author. Tel.: +60 3 7967 5300; fax: +60 3 7967 5319.
E-mail address: azizraman@um.edu.my (A.R. Abdul Aziz).

http://dx.doi.org/10.1016/j.enconman.2014.09.050
0196-8904/Ó 2014 Elsevier Ltd. All rights reserved.
350 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367

5.4. Biogasoline via fluid catalytic cracking of RSO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360

5.5. Challenges in fluid catalytic cracking operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
5.6. Choice of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
5.7. Choice of reactor type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
5.8. Biogasoline technoeconomical challenges and advances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
5.9. Prospects for reduction in energy consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
6. Current scenario and future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365

1. Introduction to biofuels, tackling the implications of such transitions rests on

Apprehensions over diminishing oil reserves, increasing oil
prices, deteriorating health standards because of greenhouse gas
(GHG) emissions and associated environmental impacts have made
biodiesel emerge as the fastest growing industry worldwide [1]. It
is the second most abundant combustible renewable fuel. This is
because of the renewable and potentially inexhaustible sources
of vegetable oils [2,3]. Also, the energy content obtained therefrom
is comparable to that of diesel fuel (Fig. 1 and Tables 1 and 2).
However, to remain sustainable, some argue that nonfood crops
which require minimal cultivation should be the main sources
for biofuel production. Such cultivation should not compete with
other feedstocks over arable land or cause deforestation. These
include bioethanol from fermentation of sugarcane juice and
starch-based feedstocks and biodiesel from transesterification of
vegetable oil triglycerides (TGs). These issues raised the questions
of food availability and prices, land-use and land-use changes,
environmental degradation and socio-economic implications [4].
The proponents of this view claim the extensive utilization of seed
crops and vegetable oils may cause starvation especially in the
developing countries. Further, a general issue that affects the glo-
bal biofuel development is the high cost of feedstock which consti-
tutes more than 88% of the overall costs [1].
Bioethanol and biodiesel are the two globally acclaimed liquid
biofuels that have the potentials for replacing gasoline and diesel
fuels respectively. However, numerous challenges await the inge-
nuity of the research community and economic leeway from the
policymakers. Collaborative efforts from these communities are
vital in achieving the biofuel central policy especially in replacing
fossil fuels, protecting and creating jobs, and protecting the envi-
ronment [6]. While the research communities need to provide
solutions to the production technologies and transition from fossil
Fig. 1. Edible and inedible properties of plant oil compared to petrodiesel [5].
the policymakers. Interestingly, the need for concerted efforts
and cheaper feedstocks persists [6,7]. This is despite the numerous
developmental strides achieved such as utilization of abundant,
affordable, and sustainable sources since Rudolf Diesel’s vegetable
oil dream. These strides were facilitated by advances in rational
catalyst design and biotechnology. These techniques facilitate
strategies for designing optimal biocatalysts and engineering
native and de novo pathways for the sustainable production of bio-
fuels. Other strides include reduced GHG emissions by 78% [6]
while the Mcgyan ProcessÒ [8] produces biodiesel within 4 s by
utilizing inexpensive, non-food-grade and FFAs-containing
feedstocks.
The challenge in rapidly and efficiently switching from utilizing
the ‘ready-to-use’ energy sources (natural gas, coal and crude oil)
to the renewable energy sources is an arduous one. This challenge
is more pronounced especially when considering how to avoid
deforestation while promoting bioenergy. Furthermore, the energy
density of E85 (76,300–84,530 Btu/gal) is lower than that of gaso-
line (116,090–124,340 Btu/gal) based on location, time of year and
political climate (Table 2). Additionally, this value equates to 73–
83% the heat content of gasoline which gets lower in winter
months in cold climates. Besides, the cost of bioethanol ($3.41/
gal) is comparable to that of gasoline ($3.65/gal) [11,12]. Thus,
spreading the perceived risks over wide range of renewable energy
sources becomes appropriate. This will help provide a cocktail of
energy sources which might appeal to the different needs of the
consumers just like the fossil sources. Further, a diverse portfolio
of energy is more likely to meet the high levels of future energy
demands. Therefore, it is essential to understand and fully realize
the causes that determine technological development. This is
because process of developing a technology is not precise due to
availability of different routes for such developmental stages.
These include (a) minimal capital cost and investment, (b) utiliza-
tion of affordable feedstocks, (c) environmental performance and
(d) energy efficiency. Therefore, an out-of-the-box idea necessi-
tates employing least-resistance-path approach in developing bio-
gasoline expansion. This approach combines existing technologies
and experiences with cheap resources. Though it might be below
optimum initially, the approach ensures easy commercialization
with minimum risks. This does not negate recognizing and pro-
moting various ‘nonbio’ alternatives which are affordable, avail-
able, renewable and low-carbon alongside bioenergy [10]. Within
this broader approach, bioalcohol (fermentation of sugars), biodie-
sel (transesterification of TGs) and bio-oil (pyrolysis of biomass)
have received extensive experimentations. Similarly, the process
that is gaining the attention of the academic and research commu-
nities is catalytic cracking of inedible oil to biogasoline.
Currently, ethanol is the available commercial biofuel. How-
ever, as mentioned earlier, because of sustainability, food security
and economic competitiveness, it is imperative to find alternative
sources. The present-day primary feedstocks such as starch
 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367 351

Table 1
Comparison of common fuels used for propelling gasoline-powered vehicles [9,10].

Fuel Energy density, MJ/L Air–fuel ratio Specific energy, MJ/kg Heat of vaporization, MJ/kg RONa MONb
Gasoline 34.6 14.6 46.9 0.36 91–99 81–89
Butanol fuel 29.2 11.2 36.6 0.43 96 78
Ethanol fuel 24.0 9.0 30.0 0.92 129 102
Methanol fuel 19.7 6.5 15.6 1.2 136 104
a
Research octane number.
b
Motoring or Machinery octane number.

Table 2 options available for promoting sustainability are not mutually

Gasoline energy content compared to different biofuels [11,12]. exclusive. Therefore, considerations should be given to all feasible
Fuel MJ/L BTU/L Liter gasoline renewable energy sources which have the potential for long-term
Petrogasoline 32 30,336 1.00
economic viability and minimal environmental impacts. These
Biodiesel 33.3 31,568 1.04 concerted efforts should be implemented sooner than later while
Petrodiesel 40.3 38,204 1.25 ensuring continuity and consistency. Therefore, this article
Biobutanol 29.2 27,682 0.91 reviewed the economic potentials of a holistic approach to biogas-
Bioethanol 19.6 18,581 0.61
oline development especially from inedible feedstocks (Sections 4-
5). It specifically highlighted a general theme on the need for an
integrated set of solutions and the potentials of microalgal and
Table 3 rubber seed oil (RSO) in providing solutions to the food-verses-fuel
Some oil bearing plants and their oil productivity figures [5,6].
issues (Table 3). For brevity, we encourage the reader to consider
Common name Latin name Productivity, kg oil/ha all renewable sources of energy in the same respect for achieving
Palm Erythea salvadorensis 5652 a sustainable energy supply. Therefore, since the aim is to think
Corn Zea mays 145 out-of-the-box; the review also put into cognizance the important
Rubber seed Hevea brasiliensis 217 role that technological advancements, political influences and
Cotton Gossypium hirsutum 273 socio-economic situations will have to play (Sections 2–3). Conse-
Deccan hemp Cannabis sativa 305
Soybean Glycine max 375
quently, because of envisaged short-term fluctuations in market
Linseed Linum usitatissimum 402 conditions, the review advocates for a steady approach which tar-
Mustard Brassica alba 481 gets the long-term end returns.
Sesame Sesamum indicum 585
Safflower Carthamus tinctorius 655
Sunflower Helianthus annuus 800 2. Challenges associated with biofuel production and utilization
Peanut Arachis hypogaea 890
Opium poppy Papaver somniferum 978
Rapeseed Brassica napus 1000 Energy plays significant role in the economic growth of any
Olive Olea europaea 1019 country. Incidentally, the US manufacturers’ market share wit-
Jojoba Simmondsia chinensis 1528 nessed a major decline from 2002 to 2007. These and other con-
Babassum palm Orbignya martiana 1541 cerns regarding climatic changes, economic constraints and
Jatropha Jatrpha curcas 1590
Coconut Cocos nucifera 2260
efforts aimed at reducing oil imports have heightened the debates
Pongamia Pongamia pinnata 2500 by policymakers over decreasing gasoline utilization [16,17]. In
fact, according to most economists, the demand for gasoline has
limited short-term price elasticity. Veer [18] summarized these
shortcomings as the ‘‘three-hard-truths’’ the growing populace is
(cassava and potatoes), grains (corn, wheat and milo) and sugar
experiencing. These are: (a) growing energy demand, (b) depleting
(sugarcane and beet) for bioethanol production are all food
gas fields and oil reserves and (c) environmental impact accruing
sources. The feasibility of cracking the said alternatives catalyti-
from GHG emissions. Expectedly, the current global demand for
cally is more than three decades old [14]. Further, the thermo-
liquid fuels will reach 118 mmbls/d in 2030 with an average
chemical technologies currently in use in most refineries are
increase of 1.3–1.4% per annum. The potential benefits from the
suitable for converting seed-oil and biomass into biogasoline.
transition towards the biofuel economy are not peculiar to the
Moreover, the cost associated with engine modification is minimal
industrialized countries alone. In fact, the developing countries
because biogasoline has similar properties to conventional gaso-
stand to benefit as much if not much more. However, these coun-
line [15]. Other important characteristics of biogasoline include:
tries have to deal with the major dilemma that comes with this
(a) pure (100%) biogasoline or BG100 runs in any conventional gas-
transition. These include how to invest in the biofuel research
oline engine. (b) It substitutes petroleum-based gasoline because
and development and the challenges posed by the pace of this
of similar properties. (c) It is employed in high concentrations in
growth as well as its enormous scale. These countries have to
conventional gasoline engines unlike ethanol. (d) Biogasoline elim-
decide whether to invest in developing cutting edge technologies
inates the need to build new biofuel infrastructures for conversion,
or portable user-friendly devices. Even more worrying is the issue
storage and transportation systems. (e) Biogasoline has higher
of constant power supply especially in the rural areas [19,20].
energy content and is more fuel efficient than ethanol. Nonethe-
less, we are of the conviction that the panacea cannot come from
a single biofuel source. Consequently, the aforementioned issues 2.1. Land-use change and associated implications
require an ‘‘out-of-the-box-solution’’. These include incorporating
other sources aside biomass, sludge and wastes into one catalytic The potential to save fossil energy is one of the driving factors in
process. Thus, we advocate pertinence in developing and applying transiting to bioenergy economy. However, managing the potential
broader and more integrated sustainability criteria that encompass land use change associated with producing renewable resources is
not just biofuels, but other renewable sources. This is because the prerequisite to actualizing this potential. Otherwise, pressure on
352 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
the limited land resources might create unwarranted challenges
such as carbon debt and threats to biodiversity. The issue of land
use and land use change is gaining the attention of policymakers
as well as the academic and research communities. This is because
achieving fossil energy savings with reduced GHG emissions are
essential to attaining and maintaining environmental sustainabil-
ity from biofuels. Nguyen et al. [17] showed that increased energy
credits derivable from substituting fossil electricity with renew-
able electricity and gasoline with bioethanol have the potential
for fossil energy savings. They claimed the magnitude of the sav-
ings is dependent on two causes. The first relies on the efficiency
of an integrated system in producing energy from bagasse as well
as bioethanol from the sugar. The second depends on the efficient
recovery of the spent ethanol from the distillery and subsequent
conversion into biogas. However, the authors were quick to note
that minimizing or a total avoidance of land use change because
of transition to biofuel economy is essential in achieving such sav-
ings. In other words, the output volume per unit area of land (or
productivity) must be commercially feasible to meet the increasing
demands.
The exuberance displayed by the Brazilian sugarcane ethanol
production is encouraging. Brazil produced a GHG offset credit of
13–14 t CO2/ha/yr by 2005/2006. However, converting woodland
to sugarcane plantation created a carbon debt of 165 t CO2/ha.
Accordingly, it will take at least a 12-year period to repay this car-
bon-deficit. Only after such time-span is the environmental sus-
tainability of ethanol as an eco-friendly energy source
ascertained. Furthermore, threat to biodiversity is yet another con-
sequence of expanding biofuel production on land. Ultimately, the
question is whether it is possible for this transition with its con-
comitant expansion to create less, or possibly eliminate the pres-
sure on land. Is it possible for agriculture to fuel and feed the
world concomitantly? This is considering world energy demand
will exceed 705 exajoules (1 EJ = 1018 joules) by 2030. This
requires 37% more energy than in 2008 [13]. As if these are not
enough, the consequences of the continual carbon emission are
worrisome. Reports by FAO [21] suggests stable global warming
below 2 °C to avoid precarious effects of climate change. In fact,
to avoid undesirable risks, experts warn that 2020 must be the
threshold for GHG emissions. This is because there is no sector
more climate-sensitive that is both affected and affects climate
change like the agriculture sector. Hazardous climatic effects lead
to food shortages and consequently increase the demand on bioen-
ergy feedstocks which serve as food sources. Conversely, depend-
ing on type of feedstock and production technology, biofuel
expansion will reduce estimated 10–90% GHG emissions relative
fossil fuels [21]. However, despite the current stipulated policy of
CO2 at 450 ppm, the world would need 18% more energy in 2030
than it did in 2008 [13]. Though biofuel looks attractive, our opti-
mism should not becloud the apparent consequences. This is
Table 4
Net changes in land availability (Mha) [23].
Region Increased land Associated with
requirement co-products
USA 11.0 5.9
Brazil 4.9 1.8
EU 6.6 3.2
Indonesia and Malaysia 0.02 0.01
China 2.2 0.4
Mozambique 0.13 0.03
South Africa 0.12 0.04
Study area 24.9 11.4
Global total
MCI = multiple cropping index.
NHA = Net Harvested Area.
because the renewability and potential for lower carbon footprint
of biofuels also have opportunity costs.
Expectedly, food will be in higher demand in 2030 due to a pro-
jected world population of more than 8 billion. The consequence of
this population growth will create an unprecedented burden on
the natural resources. The availability and productivity of the avail-
able water and land will be competitive with attendant impact on
food prices [13]. Further, prospects of this transition has the poten-
tial to trigger demands on bioresources for producing new non-
energy products such as cosmetics, health care products, paints
and plastics. Evidently, a vicious circle of cause and effect is emi-
nent from excessive pressure on agricultural land. This is because
of converting areas serving as valuable carbon sinks such as peat-
land, savannah or rainforest. Searchinger et al. [22] argues that
emissions savings obtainable from extra bioenergy production
can hardly outweigh the impact from GHG emissions. Thus the
arduous task is in ensuring a smooth transition to renewable fuels
with minimal-carbon energy. It is necessary to achieve this with-
out exacerbating the world hunger or stifling economic growth.
2.1.1. Biogasoline land requirement
Though no official data is available on suitable and available
land devoted for biogasoline expansion, it is appropriate to make
analysis from the average annual increase in area harvested for
major biofuel feedstocks. Langeveld et al. [23] estimated the
amount of land dedicated to biofuel (including co-products) pro-
duction as 32 Mha. The report showed an increase of 25 Mha in
2010 compared to 2000 (Table 4). The authors argued that earlier
estimations presented ca. 40% overestimation of land requirements
by ignoring (11 million ha) co-product generation. Further, Table 5
depicts the scenario for substituting 10% of petroleum consump-
tion by biogasoline while Figs. 2–4 show suitable area not classi-
fied as forested or cultivated land for selected biofuel production,
average annual increase in area harvested for major biofuel feed-
stocks and percentage suitable land not classified as forest or cul-
tivated land required for substituting 10% of petroleum
consumption by ethanol. Interestingly, the United States consumed
150 billion gallons of gasoline in 2009 alone. This annual consump-
tion has increased since then In fact, America requires 240 billion
gallons of ethanol to substitute gasoline with corn ethanol. How-
ever, the US produced only 8.9 billion gallons of ethanol in 2008
[24]. This indicates the need for more acreage devoted to biogaso-
line expansion to meet the increasing energy needs. Hertel et al.
[25] showed how market-mediated global land use changes affects
biogasoline expansion in the US (Fig. 5). This scenario highlights
the importance of knowing the total global land suitable and avail-
able for biogasoline production. The foregoing further buttress the
general theme of this review in exploring out-of-the-box ideas for
ensuring sustainable biogasoline expansion.
Net biofuel area Changes in agricultural Extra harvested area Change in
increase area due to MCI NHA
5.1 3.5 10.9 2.3
3.1 12.0 4.9 13.8
3.4 11.5 3.6 11.2
0.01 8.9 2.0 10.9
1.8 13.4 20.3 5.1
0.1 1.3 0.9 2.0
0.1 2.7 1.2 4.0
13.5 9.0 41.5 19.0
47.8 91.5
 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367 353

Table 5
Scenario for substituting 10% gasoline with ethanol in the transportation sector for some selected countries [26].

Country Additional ethanol Proportion of harvest to meet Proportion of harvest to meet Proportion of harvest to meet Area required (ha) for
required (million ethanol target – cane juice ethanol target – A-molasses ethanol target – C-molasses dedicated
L) routeb (%) routeb (%) routeb (%) plantationsc
Argentina 731.6 36.6 105.5 304.8 164,317
Guatemala 159.6 9.4 27.1 78.3 35,834
Peru 151.6 24.6 70.8 204.7 30,315
Philippinesa 476.2 26.9 77.3 223.2 107,062
Thailanda 783.2 14.2 50.6 118.4 156,639
Vietnam 544.8 50.6 145.9 421.5 122,355
Mozambique 18.1 11.0 31.8 92.0 4058
Tanzania 41.4 26.1 75.4 217.8 9293
Zambia 30.7 18.4 53.1 153.3 6899

Note: Countries selected have a relatively well-developed domestic sugarcane sector and a low level of ethanol in their energy mix.
a
Food and Agriculture Organization of the United Nations (FAO) FAOSTAT: agricultural production data. http://faostat.fao.org/site/567/default.aspx#ancor [10 September
2010].
b
Based on sugarcane harvesting data from FAO (2010) and assuming that 75, 26 and 9 L can be produced per ton of sugarcane via cane juice, A-molasses and C-molasses
production routes respectively.
c
Area required assuming that 5000 L of ethanol can be produced per ha under sugarcane cultivation.

Fig. 2. Area of suitable land (not classified as forest or cultivated) for selected biofuel feedstocks [26].

Fig. 3. Average annual increase in area harvested for major biofuel feedstocks (2000–2008) [26]. Note: Jatropha is not included as no official data on its cultivation are
maintained.

2.2. Food-for-fuel conflicts
It is unfortunate to see this debate linger for so many years with
much disagreement even amongst same ranks of the same sector.
Sometimes, interests rather than prudent use of such resources play
major role in the perceptions of both proponents and opponents to
this issue. For instance, sales from biofuel feedstocks rather than
food are more profitable to the agro-business companies. Con-
versely, many groups and individuals opined of negative conse-
quences such as food shortages largely in developing countries.
However, countries like India, China, Brazil, Indonesia and Malaysia
are demonstrating the possibility for realizing the biofuel potentials
on economic growth, environmental impacts and energy security.
Ethanol (Brazil and US) is the dominant biofuel followed by biodie-
sel (Europe and Asia) [19,27,28]. These biofuels account for more
than 80% of total biofuel production. However, some quarters
argued that these expansions will lead to increase in deforestation
and deterioration of peatlands and wetlands, food prices and CO2
354 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
Fig. 4. Area of suitable land (not classified as forest or cultivated) for selected
ethanol and biodiesel feedstocks required for substituting 10% of petroleum
consumption in the transportation sector [26]. Note: Brazil was excluded from the
South America ethanol figures because it has higher blending mandates than used
in these scenarios.
Fig. 5. Global (regional) land conversion due to increased maize ethanol production
of 50.15 gigaliters per year at 2007 yields [26].
emissions. This is because of uncertainties surrounding the sustain-
ability of biofuel production level achievable by 2050 [28]. The pro-
ponents of this rationale are therefore calling for a global concept in
tackling the perceived concerns. However, a different reasoning
exists between these two extremes. This group opined that with
proper implementation of the right governmental policies, it is pos-
sible to source food and fuel from the same feedstock. This is
because most governments have the wherewithal to provide suffi-
cient and affordable food to their populace while concomitantly
producing biofuel [28]. Notwithstanding these arguments, numer-
ous proposals on how to alleviate the impending food shortages
are available [29]. These include experimenting inedible alternative
feedstocks such as microalgae oil [30], Jatropha, miscanthus, used
cooking oil and free fatty acid mixtures. Similarly, the Food and Agri-
culture Organization (FAO) of the United Nations considered the
prospects of microcredit system in biofuel economy especially by
the rural and subsistence farmers [31,32].
2.3. Unavoidable utilization of fossil fuels & gasoline formulations
The current estimated worldwide fuel consumption is 62% with
substantial projected increase [1]. To date, most production of bio-
energy still relies on energy produced from fossil fuels such as
(premium motor spirit, kerosene and diesel), natural gas and coal.
Therefore, any net energy savings derivable from the biofuel econ-
omy is dependent on the extent of the reliance on fossil fuel energy
usage [17]. These led to the search for immediate solutions as via-
ble source of energy and means of reducing GHG emissions. A com-
mon practice that is gaining the attention of automobile research is
the use of gasoline formulations with oxygenated compounds. This
improves the gasoline quality by increasing the octane rating and
reducing CO and unburned hydrocarbon emissions. Similarly,
increasing automobile engine thermal efficiency is another techni-
cally viable means of reducing CO2 [33]. However, these solutions
are only the beginning in the myriad of challenges as they neces-
sarily require the use of fossil fuels in larger percentages.
Historically, ethanol was the main fuel for propelling automo-
biles since the late 1800s. As at then, the prospects envisioned
for ethanol was much greater than transportation. However, devel-
opment of the petroleum industry marred such potential utiliza-
tion from becoming reality. The multifaceted concerns from
utilizing petroleum-based fuels have made the re-emergence of
bioethanol possible. According to U.S. Department of Energy [34],
it is possible to run all automobile engines produced after 1988
with E10 (mostly up to E20) ethanol–alcohol blends without prob-
lem. Notwithstanding its lower energy density, ethanol has 35–
40% higher octane rating, thermal efficiency and has the potential
for improving engine performance than pure gasoline. Encourag-
ingly, utilizing ethanol as blend in gasoline as well as a sand-alone
fuel is becoming the norm. In fact, thirteen out of the 134 billion
gallons (about 10% by volume) of gasoline consumed in 2012 by
the US was ethanol. Further, current US cornstarch production
capacity accounts for more than 95% ethanol used as E10. How-
ever, this is nowhere near the 38 billion liters p.a. and ca. 6% auto-
mobile consumption [35]. Incidentally, Solomon et al. [35,36]
showed that without subsidies, cost-competitive cellulosic ethanol
is possible from cheap feedstock and high biomass conversion
efficiencies.
Conversely, other analyses via different assumptions alluded to
opposing conclusion [37–40]. Nonetheless, a contingent valuation
reported by Solomon et al. [41] showed that most consumers from
north-central states of US are willing to pay extra to develop bio-
fuel in the short-term. Also, to attain competitive edge over con-
ventional gasoline as a blend or fuel, certain challenges need
resolving. These include the unavoidable anti-fuel properties such
as moisture, high flash point and lower heat of combustion inher-
ently present in ethanol. Lower energy density (24.0 MJ/L) which is
approximately 68–75% compared to 32–35 MJ/L of gasoline
[32,42]. Adding denaturant to the ethanol fuel usually minimize
these limitations. However, the energy derived from the conse-
quent ethanol fuel formulated has ca. 33% less energy than its
unblended gasoline counterpart depending on the amount added
(Table 1). For instance, the total mileage expected from an engine
run by 10% ethanol blended gasoline (E10) is up to 3.3% less [19].
Though modification of most engines not designed to run on etha-
nol requires only a few thousand dollars, corrosion, deterioration,
and breakdown of some rubber, plastic and metal components
remains major challenges. This is because during engine design,
specifications were for fossil fuels not on ethanol/gasoline blends
or pure ethanol [43]. This further highlights the potential advanta-
ges of biogasoline.
2.4. GHG emissions
A critical analysis of engine emission data reveals the need for
urgent solutions. This explains the clarion-call by UN Secretary-
General during COP19 climate conference. He warned that the
catastrophe in Philippines was enough for the world to
 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
comprehend the profound and dangerous consequences of a
warming planet [44]. Similarly, the Executive Director of the Uni-
ted Nations Framework Convention on Climate Change, Christiana
Figueres was more emphatic in her speech in Warsaw. She said:
‘‘The time is now . . . We have been talking and planning and analyz-
ing, and talking and planning and analyzing. But we need to act now
. . . We’re running out of time’’ [45]. These kinds of conferences and
mandates therefrom have significant potentials in altering future
oil demands [18]. Interestingly however, Hossain and Davies [5]
argue that CO2 emissions from engines running on blends or pure
plant oil are comparable to those obtainable from fossil diesel. The
report showed increase or decrease in CO and HC emissions
depending on feedstock homogeneity from engines propelled by
plant oil (Fig. 6). Other causes include engine choice (direct or indi-
rect-injection and brand), oil type, ambient conditions, instrumen-
tation accuracy, fuel inlet temperature, speed variation and high or
low load-operation. Similarly, at low-load operations, blends or
pure plant oil exhibited similar CO emission to fossil diesel. Con-
versely, engines at higher loads emit more CO due to the lower
oxygen content of plant oil. Also, NOx emission varies depending
on the nitrogen content of the oil [5]. However, there is a consen-
sus that NOx emission is a technical challenge facing the industrial
biodiesel production [1]. Hence, the need for biogasoline
expansion.
3. Determinants that influence the demand and supply of
biofuels
Reviewing the factors that affect demand and supply is essential
for sustainable biofuel production. This helps researchers and deci-
sion-makers take informed decisions regarding biogasoline pro-
duction. The following discusses such instances and their effects.
3.1. Prevailing market conditions
All future projections estimates a declining oil supply putting
into cognizance the prevailing market conditions and policies. Eco-
nomic situations and public perceptions play major role in the
demand for any particular product or service. Kjärstad and Johns-
son [19] argued that it is the numerous constraints to investment,
rather than limited resources that will ensure the peak of the glo-
bal oil production in the long-term. They also highlighted the
improbability of oil companies or nation besides Saudi Arabia to
maintain a surplus production capacity. Furthermore, only a few
feedstocks are available to the current biofuel production technol-
ogies. The obvious implication of this is the market potentials of
these processes are at the mercy of the commodity markets. Thus,
Fig. 6. Emission of CO, NOx and smoke by CI engines propelled by plant oil (or
blends with petrodiesel) compared to petrodiesel [5].
355
purchasing power and prevailing market conditions are determi-
nants that need thorough consideration in biogasoline production.
This is because they have the potential to disrupt the biogasoline
production economics by influencing the dynamics of feedstock
demand and supply [46]. From the above analysis, an intertwined
set of challenges abound in the food-for-fuel and land-use con-
flicts. These include energy requirements, excessive demand for
oil, GHG emissions, environmental impacts, biofuel production,
food shortage, economic situations and land-use changes. Evi-
dently, the ongoing search for sustainable and affordable biogaso-
line alternative is not only timely, but needs intensified global
concerted efforts.
3.2. Socio-economic factors, health effects and environmental concerns
The rural economies are facing sustainable development chal-
lenges with the biofuel sustainability issues, food security and food
prices due to the expanding biofuels sector. The rural area is the
stronghold for producing almost all the feedstocks except microal-
gae and municipal solid wastes. The three major socio-economic
issues associated with expanding biofuels development are health
and gender implications, job creation and economic development
and small-scale-financing [47]. These factors affect the day-to-
day activities of the individual directly. However, with proper
management, biogasoline economy can ensure socio-economic
developments in the said areas. Consequently, Rudolf Diesel’s fore-
sight that development of national economies would rely on plant-
oil from rural areas will become reality [48]. Further, the public
will embrace biogasoline production especially if it provides
household heat and electricity requirements and irrigation for
the farmers [48,49]. Already, farmers and rural economies in sev-
eral countries have benefited from the major boon of the existing
biofuels industries [50–52]. However, due to the large land-usage,
it is not possible to substitute fossil fuels in the short-term. This is
where the advantages of fuels such as biogasoline come in handy
because they have the potential to contribute significantly to the
environmental advantages. Neuwahl et al. [53] employed an
input–output framework to determine the job impacts of biofuel
production. The result they obtained from the Renewable Energy
Road map for the European Union market showed minor, but
mostly positive effects. These include net employment effects such
as losses from the services, transportation and energy sectors
caused by inefficiency of the economic policy. The gains from the
food, agricultural and industrial sectors will undoubtedly compen-
sate for these effects. Similarly, Sparovek et al. [54] discussed an
integrated native-farmers and livestock-ranchers system for
expanding the Brazilian sugarcane-based ethanol production.
However, the important role that women play as the primary
caretakers in homes exposes them to gender and health implica-
tions of biofuels. The traditional heating and cooking fuels such
as charcoal, wood, crop residues and dung emit high levels of par-
ticles and hydrocarbons. Inhaling these substances above certain
thresholds causes pneumonia respiratory diseases and even death
[55]. Substituting traditional fuels with modern biofuels especially
in the rural communities is vital in alleviating these issues [56–58].
Biofuels have the potential to reduce the particulate matter emis-
sions that produce harmful effects on the environment and
humans [59]. Also, a problem seldom discussed is the substantial
freshwater demands for both biofuel refineries process water
needs and cropping systems in large-scale biofuel production
[60–63]. These accentuate the need for a transition from sugarcane
and corn to feedstocks and cropping systems that are less water-
intensive [64] such as rubber plant for biogasoline. Flaspohler
et al. [65] reviewed and critiqued effects of bioenergy systems on
aquatic and terrestrial biodiversity. The study suggested the use
of native forest species or perennial plants in polycultures and
356 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
lower cultivation inputs to ensure greater ecosystem resiliency in
biofuels development [61,65]. Similarly, [62] highlighted ecologi-
cal studies of fitness responses to various environmental scenarios
as precautions to invasion of biofuel feedstocks by non-native
plant species.
3.3. Governmental policies
Current estimates suggest that without the utilization as feed,
food, or other industrial uses, bioethanol from feedstocks such as
plant oils, starch, fat and sugar has the potential to meet 55% gas-
oline demands. However, it is only wishful thinking to consider a
halt in consumption of corn and sugarcane. However, the sugges-
tion by [43] that producers must rely on conventional feedstocks
before the full establishment of a cellulosic industry for biofuels
does not necessary hold for the near future. This is because culti-
vating feedstock such as microalgae and RSO in colossal quantities
has the potentials to provide the required energy [66]. The U.S.
Energy Policy Act (EPAct) of 2005 supported producing cellulosic
over traditional ethanol with several incentives to facilitate its
commercialization. The passing into law of the Energy Indepen-
dence and Security Act in 2007 helped to widen the prospects for
producing cellulosic ethanol [67].
The Brazilian government demonstrated similar efforts when it
launched the National Alcohol Program (Proalcool) for producing
biofuels in 1975. It mandated all retail fuel stations in towns pop-
ulated with more than 1500 residents to mount ethanol pumps
while it offered large subsidies to sugarcane farmers. Despite phas-
ing out of most subsidies on ethanol in 1990, the economic viabil-
ity of the fuel lingered into 2003. In fact, the ethanol produced in
Brazil is cheaper than is obtainable from Europe or the US
[68,69]. The Brazilian experience has proved the economic sustain-
ability of biofuel. The cost of gasoline is not only higher than the
Brazilian ethanol; Brazil is also a major exporter of the fuel today.
These viable nonsubsidized programs became possible via initial
subsidies and incentives. However, theoretical results obtained
by [70] showed that it is unlikely for these policies to reduce gas-
oline consumption and GHG emissions. This is because despite the
sinusoidal production of AFVs, producing conventional vehicles is
on the increase. In fact, if not properly managed, programs such
as the AFV under AMFA could reduce AFV production with a con-
sequent increase in gasoline consumption [70,71]. Similarly, it is
difficult for fuel-economy standards alone to reduce gasoline con-
sumption because of political reasons like lower gasoline taxes. A
Table 6
Engine modifications and adjustments for alcohol and plant oil use [5,74].
Issue
Alcohol
Alcohol does not evaporate as easily as gasoline
Low ethanol stoichiometric air–fuel ratio and high heat of vaporization
General corrosion problems associated with gasoline blends caused by ionic
(chloride ions and acetic acid) impurities
Dry (polarity of ethanol molecule) wet (azeotropic water, which oxidizes most
metals) corrosion problems associated with gasoline blends
Restricted flow rates
To maximize the higher octane rating advantage of the alcohol
Lack of lubrication resulting from the absence of lead in the fuel
To reduce the alcohol engine emissions
Plant oil
Incomplete combustion and HC and CO emissions due to the extra time required
for the plant oil to mix with the air
Poor performance and durability and carbonization inside the engine cylinder
Poor atomization of fuel at the nozzle outlet
Storage problems due to the presence of unsaturated hydrocarbons
more realistic policy as suggested by [72,73] which this review
aims to highlight is to increase the CAFE standard and promote bio-
gasoline as alternative fuel.
3.4. Irregular distribution of global oil reserves
Other factors that influence the demand and supply for fossil
fuels and by extension, biofuels are geopolitical instabilities and
irregular distribution of the world’s oil reserves. Seemingly, in
the foreseeable future, the world would need to turn to biofuels
for its energy needs. This is discernable from the declining produc-
tion rates and limited-access to the large reserves in places such as
Venezuela, Russia and the Middle East. Besides, the current field
outages due to frequent political instabilities and the increasing
difficulties in exploring and producing oil from difficult terrains
add to the constrains in global production [19]. Additionally, only
few areas have large oil reserves with exceptional geological fea-
tures. Asia has about 3.4% concentrated while 3.4% is in the Pacific.
North America has 5%, Central and South America has 8.6%. Africa,
Europe and Eurasia and the Middle East have 9.5%, 11.7% and 65%
of the world’s reserves. Biogasoline production from microalgal oil
has the potential for sustained expansion without irregular outages
common to petroleum fuels.
3.5. Need for long-term durability tests on vehicles powered by
unblended biofuels
It is now common to run vehicles designed to operate on gaso-
line with ethanol-blended gasoline. However, due to differences
between alcohol and gasoline (Table 1), some engines require
modifications for alcohol fueling. Table 6 presents some modifica-
tions made to achieve efficient alcohol and plant oil engines [5,74].
Most vegetable oil fuels showed good potential drivability as
indicated in the short-term tests reported by Huzayyin et al. [75].
In fact, several authors [76–80] reported the technical feasibility
of running compression–ignition (CI) engines with minor modifica-
tions and maintenance schedule with raw plant oils as alternative
fuel. However, the problems are the indications from the long-term
endurance tests because of low volatility and high viscosity of neat
vegetable oil from mahua, palm, karanja, rice bran and neem. These
include unburned fuel introduced into the lubricating oil, thicken-
ing, gum formation, poor atomization, and deposits in the combus-
tion chamber, ring sticking and injector chocking. Others include
carbon deposition on piston head, piston ring grooves, injector tip,
Modification
Redesign engine to provide more heating for evaporation
Recalibrate carburetor to increase heating of the air–fuel mixture and improved
drivability
Change tin and lead coating of the fuel tank to pure tin
Change fuel lines (zinc steel alloy) to cadmium brass
Change and re-dimension fuel-filtering system
Increase the compression ratio was to about 12:1
Change cast-iron valve housings to iron-cobalt synthetic alloy.
Change the catalyst in the catalytic converter from palladium and rhodium to
palladium and molybdenum
Change the injection timing and pressure
Add a separate combustion chamber
Increase the injection pressure and exhaust gas recirculation (EGR)
Storage temperature and storage time limits are <10 °C and <6 months respectively.
Also, check and change lubricating oil at least every 250 h
 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
Fig. 7. An overview of the biofuel: (a) production route and (b) feedstock [31].
and valve faces [81]. Also, Pandey et al. [59] reported considerable
drop in thermal efficiency and ignition delay for pure oils. Except
for viscosity, Hossain and Davis reported the significant chemical
and physical properties for 17 raw plant oils which fell within 12%
of the corresponding petrodiesel standard values for CI engine. Aside
safe handling and transportation advantages because of the rela-
tively high flash point temperatures, high pour point (6–14 times
more viscous) affects spray characteristics at low temperature. Fur-
ther, reports have showed similar technical difficulties with pure
(100%; unblended) biodiesel while durability tests are yet to be pro-
ven conclusively for long-term operations. However, pure (100%)
biogasoline or BG100 has the potential to run in any conventional
gasoline engine without these issues.
4. Is there a light at the end of the tunnel?
The foregoing analysis depicts the varying degrees of the dire
need for sustainable and secured energy for the future, alarming
imminent consequences and encouraging feats. From a general
overview, the future does not look too bleak especially considering
the deluge of publications. In fact, the Brazilian and Malaysian sce-
narios are worth highlighting. Both countries have been producing
biofuels from edible feedstocks. Interestingly, though the debates
are ongoing, starvation is yet to be a major problem. In fact, the
economic performance and consumer confidence of both countries
have being improving [82]. Of course, biofuel is not the sole con-
tributor to these economies, but it has indeed contributed immen-
sely. Plausibly, the Brazilian and Malaysian scenarios give credence
to the feasibility of biofuel economy. These economies have the
potentials for improvements especially when biogasoline produc-
tion from inedible sources is incorporated.
4.1. Biodiesel and bioethanol are only part of, but not the panacea
The debates regarding environmental and socio-economic chal-
lenges of sugarcane-based ethanol and biodiesel from palm oil are
ongoing. Consequently, the next decade or two will serve as the
357
major turning point for the biofuel industry. By then, most
researches would have yielded the needed results which will
encourage investments and policy decisions. It is important to note
that at the same time, biofuel will only assume its central role via a
concerted biofuel program. This should include not only bioethanol
and biodiesel production, but biogasoline and other greener
sources like wind, solar and hydroelectricity in an integrated sys-
tem. For instance, utilizing existing infrastructure for catalytic
cracking and hydrotreating vegetable oils and biomass-derived
molecules will minimize capital costs. With advancements in cat-
alytic activities and reaction pathways, converting TGs into biogas-
oline and biodiesel via catalytic cracking and hydrotreating
respectively will be fast and easy [27]. These advances would prof-
fer solutions to the numerous challenges highlighted above. Conse-
quently, rather than dwelling on the ‘‘ifs’’ or the ‘‘if-nots’’ of this
grey area, the focus is in exploiting feedstocks with large resource
and land base such as microalgae.
5. Biogasoline
Factors that ensured the dominant role of petroleum as the
automobile transportation fuel are cost per kilometer of travel
and large investments in human skills, physical capital and tech-
nology. The major challenge therefore for the biofuel industry as
a cost-competitive industry is in replacing these determinants
[74]. Interestingly, producing biogasoline from catalytic cracking
of TGs is not new. This technology is amenable to biogasoline with
minor modifications in the existing petroleum refineries [31]. This
will ensure smooth transition in the short-term especially on three
aspects. (a) Providing alternative for the enormous transport vehi-
cles which run on gasoline engines. Incidentally, utilizing system
design approach minimizes cost and time-constraints associated
with minor design alterations in the existing engines. (b) Providing
competition that will force reduction on fossil fuel dependence and
subsequent reduction in environmental impacts. (c) Most
importantly, the debate on food-for-fuel issue will be non-existent.
Biogasoline is certain to provide the needed energy security and
358 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367

Table 7
Comparative catalytic performance from different cracking processes [97].

Process Catalytic Hydrocracking Hydrotreating catalytic cracking Hydrotreating catalytic cracking Hydrotreating
cracking (USY) (MFI) hydrocracking
Conversion (%) 100.0 94.9 93.3 76.6 89.2
Isopara. sel. (%) 15.2 34.3 52.8 3.1 89.7
Olefins sel. (%) 57.6 25.6 46.9 25.0 5.0
Aromatic sel. (%) 26.0 39.6 0.0 69.2 0
Ave. number of Carbon 10.1 9.6 8.2 6.3 10.8
cracked

maintain safer environment without sacrificing engine operating
performance at relatively cheaper cost. This will increase consumer
acceptability. However, for successful implementation of biogaso-
line into a commercial venture, the research community must
address the issues of catalyst choice and reactor design [31].
5.1. Catalytic cracking of triglyceride-based feedstocks
It is feasible to produce biofuels rich in different fractions such
as gasoline, kerosene and diesel via catalytic cracking technique
from edible and inedible oils and plant extracts (Fig. 7). This is
one advantage of catalytic cracking process over transesterifica-
tion, pyrolysis (thermal cracking) and fermentation processes. It
employs low temperature of 450 °C compared to 500–850 °C in
pyrolysis. Moreover, feedstock type determines the product quality
derivable via pyrolysis. This technology will facilitate obtaining
compounds containing acids, alcohols, phenolic ketones and alde-
hydes from cellulosic feedstocks. Whereas transesterification of
high FFA-containing feedstocks such as RSO requires refining, cat-
alytic cracking process eliminates this requirement. Moreover,
shape-selective catalysts are capable of producing gasoline, kero-
sene and diesel compared to only biodiesel from transesterifica-
tion. Similarly, feedstock pretreatments such as saccharification
and hydrolysis are necessary during ethanol fermentation in con-
trast to catalytic cracking. Furthermore, fermentation requires
longer reaction time than catalytic cracking process [31]. The ame-
nability of catalytic cracking process to much lower temperatures
makes it preferred over thermal cracking. This saves energy and
costs while producing high-octane gasoline with minimal yields
in heavy fuel oils and light gases.
5.2. Biogasoline via fluid catalytic cracking of microalgal oil
Microalgal biomass and oil have received considerable attention
in the last decade because of their potential as sustainable feed-
stocks for biofuels [15,66,84–86]. These biofuels serve as drop-in
replacements for diesel, gasoline and jet fuel in existing engines
and distribution networks with higher gas mileage than ethanol
[87]. As early as 1979, Weisz and Marshall [14] demonstrated
the feasibility of producing biofuels from biomass. However, the
level of research reported in this area to date remains modest
[88]. This is despite sharp increase in the global production of bio-
fuels in recent years. Technically, extracting and drying processes
prior to reaction remains the most significant bottlenecks during
microalgal production of biofuels [66]. Moreover, extracting lipids
in industrial scale is hazardous, time-consuming and expensive as
it requires large quantity of inflammable and volatile organic sol-
vents. Waste solvent streams also create further economic glitch
and environmental impact. Apparently, these processes require
more energy than is obtainable from combusting such biofuels.
This is where the argument that raison d’etre in atmospheric CO2
reduction from biofuel production prevails. Furthermore, the pro-
cessing costs add to the overall economic challenges in ensuring
biofuel programs. Similarly, the cost of producing ethanol from
woody biomass is twice that of fermenting cornstarch [89]. This
is despite recent advances such as consolidation of processing
steps, readily deconstructed plants and more efficient enzymes
[90]. Further, alcohol is a low-priced end-product compared to
other more valuable products such as agar and carrageenan [91].
Therefore, actualizing the potentials articulated by the scientific
community into industrial scale becomes imperative. Plausibly,
this is where fluid catalytic cracking befits the much-sorted pana-
cea for overcoming these problems. It is a more water-tolerant pro-
cess than chemical transformation to biodiesel.
Huntley [92] estimated the cost of a barrel of algae oil in some
specific regions as low as $84. However, with current technology, a
barrel of algae based fuel is as high as US$300–2600 [93–95] com-
pared with that of petroleum which is $103 (2014). In this respect,
results obtained by Tracy et al. [96] from catalytic cracking of squa-
lene obtained from genetically modified E. coli to biogasoline are

Table 8
Comparison of fuel fractions obtained from different cracking processes [97].

Process Catalytic Hydrocracking Hydrotreating catalytic cracking Hydrotreating catalytic cracking Hydrotreating
cracking (USY) (MFI) hydrocracking
Conversion (%) 100.0 94.9 93.3 76.6 89.2
LPG sel. (%) 5.3 2.2 8.1 21.1 2.3
Gasoline sel. (%) 35.4 32.8 51.2 64.5 25.4
Kerosene sel. (%) 54.1 60.0 39.1 9.7 62.4
Diesel sel. 2.0 4.7 1.7 0.0 9.9
Hydrogen consumption 53.1 130.1 253.9 19.1 530.0
(NL/L)

Table 9
Summary of some crude microalgal oil compositions, fuel oil yields and composition obtained via catalytic cracking route [101].

Microalgae Crude oil (maximized yield, wt%) Upgrading method (catalyst) Oil property (maximized yield, wt%)
Botryococcus braunii Terpenoid hydrocarbons (75%) Liquefaction (Na2CO3) Botryococcene (78%) high-octane gasoline
Hydrocracking (Ni–Mo, Co–Mo) Diesel (15%), jet fuel (15%), gasoline (67%)
Chaetoceros muelleri Lipid consisting of FFA (36%), triacylglycerols (14%) Cracking (zeolite H-ZSM5) High-octane, aromatic gasoline (total organics 36%)
 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367 359

encouraging. The authors reported equivalent (not similar) gaso-
line properties from their study. This highlights the advantage of
microalgae over other renewable sources especially considering
its implementation in existing infrastructure. Similarly, Kimura
et al. [97] obtained 100% conversion with 57.6% olefinic selectivity
from catalytic cracking of isoprenoid compounds of microalgae oil
over nanoporous hybrid catalysts. Low hydrogen consumption
(53.1%) facilitated higher kerosene (54.1%) and gasoline (34.4%)
fractions. Further, mild cracking ability of nsAl2O3/USY zeolite
and low temperature of hydrotreating catalytic cracking hindered
the production of aromatics. However, due to dehydrogenating
and aromatizing abilities of onnsAl2O3/H-GaAlMFI zeolite, the
same hydrotreating catalytic cracking process produced high aro-
matics. The authors compared different cracking processes and
product selectivities (Tables 7 and 8) and showed catalytic crack-
ing has the highest conversion and olefin selectivity. Similarly, Kit-
azato et al. [98] obtained 43.5 wt% biogasoline from catalytic
cracking of diatomic microalgae. Similar product streams obtained
from cracking of VGO (46.4 wt%) and 20% rapeseed oil and 80%
VGO (45.0 wt%) proved the efficacy of the cracking process. The
same conditions in a fluidized catalytic cracking reactor at constant
conversion rate of 67 wt% ensured the comparison. Interestingly
[99,100], patented inventions for cracking renewable feedstocks
such as algal oil at lower catalyst-to-oil ratio. Table 9 summarizes
some crude microalgal oil compositions and yields obtained via
catalytic cracking route.
Despite challenges reported in the art, Schaverien et al.
[102,103] explored the prospects of obtaining fuels from cracking
microalgae. The authors obtained a low yield of 5.1 wt% from
cracking partially dried and milled chlorella microalgae with com-
mercial ultra-stable zeolite Y (USY) in an amorphous alumina
matrix. Interestingly, under the same conditions, the authors
obtained 67 wt% conversion of different fractions including gaso-
line yield of 43.5 wt% from a feedstock containing 80 wt% VGO
and 20% lipid from microalgae. This is despite the high heterogene-
ity of atoms such as metals and phosphorus. This proved the
method of co-feeding hydrocarbon (HC) with lipids from microal-
gae as advantageous and amenable to product adjustments. For
instance, at 500 °C, and a pressure of 1.1 bar (0.11 MPa), the pro-
cess produces gasoline which has boiling point below 221 °C with
improved RON octane number. Further, the hydrogen from the HC
feedstock facilitates the elimination of O2 from the microalgal oil.
5.3. Properties, characterization and availability of RSO
Presently, there is gross underutilization of rubber seeds
obtained from rubber plantations. This is because rubber seed does
not have major applications before the transition to biofuel. Except
for scanty reports on its possible uses in alkyd resin, soap and
lubricating oil industries, the oil has found little or no economic
importance. Some recent reports have explored its potentials for
biodiesel production. However, unrefined RSO contains ca. 17% free

Table 10
Properties of rubber seed oil in comparison with other edible and inedible oils [104,108,109].

Property Non-edible Edible Conventional fuel

Rubber seed oil Karanja Jatropha Polanga Sunflower Rapeseed Cotton seed oil Soybean Gasoline Diesel
(Ficus elastica) (Pongamia (Jatropha (Calophyllum oil oil (Gossypium oil
pinnata) curcas) inophyllum) herbaceum)
Oil content
Seed (wt%) 40–60 25–50 20–60 65 17–25
Kernel (wt%) 40–50 30–50 40–60 22
Fatty acid composition (%)
(i) Palmitic 10.2 11.65 16.0 12.01 6.8 3.49 11.67 11.75
acid C16:0
(ii) Stearic 8.7 7.50 6.5 12.95 3.26 0.85 0.89 3.15
acid C18:0
(iii) Oleic 24.6 51.59 43.5 34.09 16.93 64.4 13.27 23.26
acid C18:1
(iv) Linoleic 39.6 16.46 34.4 38.26 73.73 22.3 57.51 55.53
acid C18:2
(v) Linolenic 16.3 2.65 0.80 0.3 0 8.23 0 6.31
acid C18:3
Specific 0.91 0.913 0.920 0.896 0.918 0.914 0.912 0.92 0.72–
gravity 0.78*
Viscosity at 34.0–76.4 27.84–54 18.2–52.76 71.98 66.2 39.5 32.8–50 65 0.37– 2.0–2.7
40 °C 0.44*
(mm2/s)
Flash point 144–198 198–263 174–280 221 220 280 210–243 230 45 min
(°C)
Pour point 1 3 to 6 3 to 5 15.0 31.7 10 to16 12.2 20 to 5
(°C)
Cloud point 14 13–15 8–10 8.7 to 1.7 –
(°C)
Calorific 37.5 34.0–38.8 38.20– 39.25 39.5 37.62 39.5–40.1 39.6 43.35
value 42.15
(MJ/kg)
Acid value 25.6–34 5.06 3.8 44 0.15 1.14 0.11 0.2
(mg KOH/g)
Cetane 37–40 45–67 33.7–51 37.1 37.6 41.2–59.5 38.0 5–20 45–
number 47 min
Density (kg/ 910–930 870–928 901–940 918 914 911–921 914 6.0–6.5 815
m3, 40 °C)
Carbon 0.46 0.20/0.44 0.23 0.30 0.42 0.27 0.03–0.1
residue
concn (%)
*
At 15 °C.
360 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
fatty acid (FFA). This means that its acid value is 34 which makes it
unsuitable for esterification and transesterification processes
[1,104]. The saturated (palmitic and stearic acids) FAs (18.9%)
increase the cetane number, cloud point, and improve stability.
Conversely, polyunsaturates (oleic, linoleic and linolenic acids)
reduce the cetane number, cloud point and stability [104]. Again,
high unsaturation and conjugated bonds (80.5%) inhibit esterifica-
tion rate significantly [105].
Furthermore, the storage life of such oils reduces with refining
[106]. For instance, Zhu et al. [107] emphasized the negative effects
of storage on RSO for biodiesel production. They reported a critical
storage under relative humidity of 90% while RSO extraction must
be within the first 10 days of storage. Obviously, it will be difficult
for farmers in the rural areas to observe these conditions. Hence,
there is the need to explore the potentials of this promising feed-
stock for biogasoline production. The use of RSO and other unex-
ploited oil crops will alleviate pressure on the food. This is
because rubber tree plantation is not new and it is capable of pro-
ducing fats and oils for the biogasoline industry. Further, it has
properties similar to vegetable oils employed for biogasoline pro-
duction (Table 10). Proximate analysis of the seed kernel showed
the seed contains 45.63% oil, 24.21% carbohydrate, 22.17% protein,
3.71% moisture and 2.71% ash [106]. The tree bears ellipsoidal 3-
seeded capsule with each carpel containing one ellipsoidal seed.
The lustrous-mottled brown seeds vary in both size (2.5–3 cm
long) and weight (2–4 g). The seed kernel (50–60% of seed) is
important as it contains about 40–50% of brown color oil. Approx-
imately, 30,000 tons rubber seeds p.a. produces 5000 tons of RSO
[104]. This further highlights the techno-economic advantage of
producing biogasoline from RSO.
5.4. Biogasoline via fluid catalytic cracking of RSO
As early as 1978, Chandra [110] patented a procedure for pro-
ducing biogasoline from cracking of RSO with alumina–silica cata-
lyst impregnated with metal oxides such as magnesium, nickel and
vanadium. The author obtained a conversion of 55 wt% in fixed bed
reactor at 480 °C and liquid hourly space velocity of 0.3 L2/h.
Recently, Li et al. [111] obtained a high yield of 75.6% with ultra-
stable Y zeolite. The authors reported the method reduced the
problems associated with high carboxylic acid contents (acid value
116–142 mg KOH/g). These undesired products have deleterious
Fig. 8. Proposed concept for biofuel production in conventional refinery [31].
effects on freezing point, corrosion value and cold-filter plugging
point of the biogasoline. The process minimized RSO deep cracking
up to a ratio of ratio m(cat)/m(RSO) of 1:50. Any further increase
feedstock ratio resulted in formation of secondary products from
side reactions. The authors also showed the comparative yield
performance of zeolite over conventional base catalysts such as
Na2CO3 (73.3%) and K2CO3 (74.0%). These reports highlight the long
history and increasing interest in producing biogasoline from
catalytic cracking of RSO. Similarly, [112] patented an invention
for converting Natural rubber latex (Hevea Braziliensis) into
biogasoline with high content of isotopic carbon-14.
5.5. Challenges in fluid catalytic cracking operations
The number of secondary conversion units for producing vary-
ing products defines complexity of a refinery. A typical secondary
operation unit for additional production of gasoline is fluid cata-
lytic cracking (FCC). This chemical process differs from the physical
separation processes (vacuum and atmospheric distillations). It
employs catalyst in cracking larger molecules into smaller ones
such as high-octane gasoline as the main product. Other products
include distillate fuels and other higher-value products like olefinic
gas components (butane and propane) as well as residue cycle oil.
The flexibility of catalytic cracking makes it the process of choice
because it is amenable to changing product demands. Further,
other catalytic activities aside cracking include isomerization,
dehydrogenation and hydrogenation. Isomerization is responsible
for improving octane number of gasoline and cold flow properties
of middle distillate. Converting straight educts into branched com-
ponents becomes ease because of the activity of bifunctional cata-
lysts such as acid zeolites. On the other hand, hydrogenation has
potential for co-processing bio-oils with fossil oil. A combined fos-
sil and biofuels conversion process enhances middle distillate or
biodiesel production. During catalytic cracking, hot vapor and
liquid feed transforms catalyst into solid sand-like material much
as water makes sand into quicksand. This facilitates easy circula-
tion between reactor and regenerator vessels (Fig. 8). However,
another challenge that is facing biogasoline characteristics from
the refining perspective is high oxygen content. Depending on
the feedstock, the cracking process requires hydrogen source for
H-to-C ratio up-gradation and fuel quality improvement. Most bio-
mass-derived feedstocks requires oxygen removal for conversion
 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
Scheme 1. Proposed reaction pathway for the conversion of palm oil over HZSM-5 catalyst to hydrocarbon products [126].
into liquid fuels. Removal of oxygenated compounds enriches the
hydrogen content of the biogasoline [113]. High H/C and low O/C
ratios are indicative of high quality fuel [114]. Two major process-
ing routes currently adopted are hydrogen addition and carbon
rejection (visbreaking and delayed coking). The latter produces
upgraded high yield gasoline with commercial value greater than
that of the carbon rejection technology. However, due to larger
investment in producing hydrogen and steam, hydrogen addition
has limited acceptability. Despite this limitation, the approach
has recently started gaining momentum [115].
The chemical composition of algal oil is similar to vegetable oil.
It consists of TGs with high distribution fatty acids. This highlights
its potential for biogasoline production in a FCC or co-FCC opera-
tion. However, a few challenges require tackling for an efficient
and economic TG or microalgal biorefinery. Carbon or catalyst coke
deposited on the catalyst during cracking process reduces the abil-
ity of the catalyst to crack the oil [116]. Coking from condensation
reactions, leaching of active species and bulky molecules are some
of the apparent causes of deactivation during catalytic cracking
[117]. Coking usually occurs via two main routes. First is deposi-
tion of bulky molecules such as aromatics on the exterior and inte-
rior active sites of the catalyst because of pore constriction.
Secondly, reaction temperature over a time period pave way for
carbon depositions on the catalyst crystals [118–120]. Most deac-
tivation comes from the former (catalytic carbon) mainly because
it possesses lower hydrogen content than the latter (thermal car-
bon) [121]. Tamunaidu et al. [122] investigated the problems of
limited feed-to-catalyst contact and coking in continuous fixed-
bed reactors. They posit short contact times (SCT) and high tem-
peratures for industrial scale-up with high gasoline yield and
reduced coking. SCT of approximately 20 s increases gasoline yield
and minimizes coking. Also, the regenerator continuously reacti-
vates the catalysts while heat from exothermic catalytic cracking
process preheats the feedstock. This heat economy reduces the
overall production cost.
Vapour-solid reactions via dealuminating aluminosilicate mate-
rials also cause catalyst deactivation. This phenomenon affects the
morphology of the catalyst. Regeneration is a means of ameliorat-
361
ing this problem as it burns off the coke that adheres on the spent
catalyst. Thereby reactivating the catalyst and adding heat to the
FCC process. To ensure a prolonged catalyst lifetime, removing
water and sediments from the algae oil feedstock, hydrogenation
is essential in combination to mild cracking. This improves thermal
stability, oxidation and enables de-aromatization under high-pres-
sure (70–160 atm) hydrotreating. Hydrotreating also eliminates
typical catalyst poisons such as sulphur, nitrogen and oxygen com-
pounds to prevent catalyst poisoning. Fundamental knowledge of
chemical composition of the FCC feedstock and how catalyst affects
it is crucial for efficient production. Research have showed that fast
thermal cracking step decomposes TGs into FAs and allyl–carbe-
nium ions. The number of double bounds in fatty acids play a
key role in enhancing alkylation, cyclization and dehydrogenation
reactions. Experiments showed that obtaining higher aromatic LCO
are at the expense of cracking gas from TGs with higher unsatura-
tion of FAs [123]. Hydrogen consumption during water formation
leads to production of more olefinic compounds. Markedly, this
enhances aromatization without catalyst deactivation over more
than 100 h in a pilot plant operation. However, there was decrease
in conversion attributed to oxygen content of the vegetable oils.
Interestingly, the process produced similar gasoline yields with dif-
ferent cracking gas from different vegetable oils. This is because of
degree of FA unsaturation in the TGs (in the order: soybean, rape-
seed, palm oil). The yield of aromatic species in the gasoline
obtained from soybean and rapeseed was ca. 10 wt% more than
oil palm oil. These results are indicative of greater conversion
obtainable from cracking of RSO and microalgal oil. Interestingly,
degree of unsaturation had no marked effect on catalyst deactiva-
tion from coke formation [124]. It should be noted however that
aside increasing gasoline octane number, aromatics have unde-
sired effects to the environment.
5.6. Choice of catalyst
The use of catalyst in cracking vegetable oils is not new. In fact,
it was employed as early as 1921 and was instrumental for provid-
ing fuel during the two world wars. In 1979, Weisz et al. [125]
362 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367

Table 11
Biofuel production via catalytic cracking of different feedstocks.

Feedstock Catalyst/reactor Reaction conditions Product yield, wt% Ref.

Biogasoline Kerosene Diesel Gases Coke
Crude palm oil Zeolite REY in a transport 400–500 °C, 10–30 s residence time under 5–10 catalyst/ 57.9 NR NR 27.5 NR [122]
riser reactor feed ratio. Under continuous mode
Palm oil MCM-41 400 °C, 1 atm and 2.5 h1 WHSV. 43.3 11.0 9.6 21.8 12.2 [109]
Palm oil Ultra-Y/ZSM-5 in a two- 500–520 °C, 1.4–1.7 s residence time at 6–8 catalyst/feed 21.0 NR 11.5 7.2 2.7 [132]
stage riser FCCU ratio
Palm oil HZSM-5 400 °C, 1 atm and 2.5 h1 WHSV 49.2 26.1 2.6 8.2 1.7 [108]
Used palm oil MCM-41/zeolite b 400 °C, 1 atm and 2.5 h1 WHSV 28.9 15.9 12.3 13.4 10.7 [128]
Waste FA-based Al-SBA 400 °C, 1 atm and 2.5 h1 WHSV 36.0 17.2 4.6 16.2 6.3 [125]
palm oil
Waste FA-based Al-MCM-41 400 °C, 1 atm and 2.5 h1 WHSV 32.6 20.0 6.7 6.7 9.8 [125]
palm oil
Waste FA-based SBA-15 400 °C, 1 atm and 2.5 h1 WHSV 20.7 15.5 4.8 9.5 7.2 [125]
palm oil
Palm kernel oil MCM-41 400 °C, 1 atm and 2.5 h1 WHSV 50.9 22.2 9.8 10.0 12.1 [109]
Rapeseed oil Ecat/Laboratory-scale 480–585 °C, 50 ms–8 s residence time under 4 catalyst/feed 43.0 NR 32.0 5.0 5.0 [107]
micro-riser reactor ratio. Under continuous mode
Soybean oil Ultra-Y/ZSM-5 in a two- 500–520 °C, 1.4–1.7 s residence time at 6–8 catalyst/feed 22.9 NR 15.0 6.2 5.2 [132]
stage riser FCCU ratio. Under continuous mode
Chicken fat Ultra-Y/ZSM-5 in a two- 500–520 °C, 1.4–1.7 s residence time at 6–8 catalyst/feed 32.8 NR 11.4 4.5 2.3 [132]
stage riser FCCU ratio. Under continuous mode

NR = not reported.

demonstrated novel mechanisms and capabilities of shape-selec-
tive zeolites in producing high-grade biogasoline from aromatics
of plant extracts such as corn oil, rubber latex and peanut oil. How-
ever, most conversion strategies have difficulty in efficiently
removing oxygen from hydrophilic biomass-derived feedstocks
into hydrophobic substances. Conversely, FCC catalysts effectively
remove oxygen in the form of CO, CO2 or H2O from biomass-
derived feedstocks through the following reaction biogasoline
[113]:
C6 O6 H12 ! aCx H2xþ2 Oy þ bCO2 þ cH2 O þ dCO þ eC
Contrary to the initial assumption that cracking occurs
primarily within the internal pore structures of the catalysts, initial
fragmentations occur on the catalyst external surface before
diffusing into the pores [31]. Hence, it important that the FCC
catalyst is robust and possess the required properties to facilitate
conversion on the external and internal surfaces. Oligomerization
of the light alkenes produces a mixture of heavier alkanes and
alkenes which are components under gasoline (60–120 °C), kerosene
(120–180 °C) and diesel (180–200 °C) fractions. On the other hand,
aromatization, alkylation and isomerization of heavier olefins and
paraffins produce aromatic hydrocarbons (Scheme 1).
Another factor that makes the choice of catalyst important is
because activity and selectivity of the catalyst determines the con-
version of a given feedstock and the derivable products [1]. The
right catalyst also lowers the reaction activation energy and pro-
motes cracking of the feedstock on its acidic sites. Initially,
ordered-structured catalysts such as X-zeolite were the main refin-
ing catalysts. However, the hydrothermal and thermal stability of
Y-zeolite such as ultra-stable Y (USY) ZSM-5 are preferred over
selectivity of X-zeolite. The need for motor gasoline with high-
octane and reduced lead as mandated in 1986 made catalyst man-
ufacturers to develop ultra-stable Y-zeolite. Dealumination process
during preparation reduces the number of aluminum atoms from
this robust catalyst. This explains the popularity of zeolite Y in
the matrix of silica–alumina as cracking catalyst. Similarly, utiliz-
ing ZSM-5 enhances increased light olefins yields and boosts gaso-
line octane number. This is because of the acidity, high selectivity
and structure of this solid acid cracking catalyst [31]. Other prom-
ising catalysts for cracking oil feedstocks include mesoporous
materials (MCM-41 and SBA-15) and b-zeolite.
According to Twaiq et al. [127], surface area and pore size of
MCM-41 determine the selectivity of any particular liquid hydro-
carbon. This explains the selectivity of these catalysts for high lin-
ear hydrocarbon-containing products [128]. Accordingly, HZSM-5
exhibited higher activity in catalytic cracking of palm oil than mes-
oporous materials [129]. Also, MCM-41/Beta composite cracking
catalysts exhibited higher activity than each parent catalyst. The
catalyst showed enhanced thermal and hydrothermal stability
and was more selective towards olefin-enriched biogasoline [83].
Similarly, MCM-41/ZSM-5 composite catalyst produced compara-
ð1Þ ble biogasoline yield obtained from HSZM-5. Studies by
[118,119] highlighted the activity for biogasoline production from
palm oil in the order: HZSM-5  MCM-41/ZSM-5 > MCM-41. Also,
HZSM-5 produced the highest yield from cracking of canola oil
than aluminum-pillared clay, silicate, silica–alumina H–Y, and H-
mordenite catalysts [130]. Evidently, acidity of HZSM-5 which
enhances product distribution during the cracking reaction influ-
enced the activity of HZSM-5 and MCM-41/ZSM-5. Equally, the
activity and selectivity of HZSM-5 towards biogasoline fraction for-
mation from crude and used palm oil were higher than micropo-
rous Zeolite Beta. It is therefore, plausible to assert the positive
correlation between acidity of the cracking catalyst to biogasoline
formation. Tamunaidu et al. [122,131] corroborated this when they
increased the acidity of the SBA-15 and AlSBA-15 mesoporous in
the catalytic cracking of crude and used palm oil. The feasibility
of cracking of palm oil, used palm oil, palm kernel oil
[15,31,89,122,127,129], rapeseed [123], soybean and chicken fat
[132] catalytically into biogasoline and other fractions was suc-
cessfully demonstrated (Table 11). Liu et al. [133] highlighted the
high stability, activity and selectivity with minimal deactivation
potentials of nanoscale zeolites. The authors envisaged efficient
biogasoline production from cracking oils with these super
catalysts.
5.7. Choice of reactor type
The SCT requirement and optimized reaction rates for the gas–
solid catalytic cracking reaction makes reactor choice important.
Heterogeneous reactors such as fixed-, trickle-, bubbling-,
entrained flow fluidized-bed and slurry phase reactors enhance
continuous production schedules via adequate contact between
 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
the fluid and catalyst [15,109]. The most popular amongst these
reactors for the continuous production of biofuels is the fluid-
ized-bed catalytic cracking system. It is similar to the fluid catalytic
cracking unit (FCCU) of the conventional petroleum refineries. It
facilitates large-scale continuous production of uniform product
quality at lower production cost [108]. However, this reactor type
requires coated catalysts to minimize attrition in a constant fluid-
ized state during the reaction. Accordingly, alumina containing
SBA-15 (AlSBA-15) exhibited higher hydrothermal stability and
cracking activity of diesel fraction than SBA-15 and Al-MCM-41
[83,129]. Composite catalyst with lower mesophase coatings facil-
itates easy access of reactants into the catalyst micropores. Alter-
natively, the catalyst is synthesized with coated mesoporous
ceramic material containing zeolite matrix or in situ overgrowth
technique. This ensures efficient chemical bonding between coat-
ing and catalysts with reduced attrition [133]. Reaction conditions
such as catalyst type, catalyst-to-oil ratio, reaction temperature,
and residence time and reactor design influence the yield of the
desired product. These will facilitate the transition to biofuels with
minor modifications to the existing reactors in the petroleum refin-
eries. Fig. 8 presents the catalytic cracking of vegetable oils for pro-
ducing biofuels in a riser reactor of a typical biorefinery [31].
5.8. Biogasoline technoeconomical challenges and advances
Currently, sugarcane and grains are the major feedstocks for
producing bioethanol. High-octane number of bioethanol ensures
suitability and value it adds to gasoline blend stock. However,
properties such as lower energy content, high solubility in water
and high vapor pressure impact on its cost and employability.
Some refiners utilize reformate in minimizing this problem. Yet,
this rises the total operating costs because increasing aromatics
in the reformate increases volumes of light lower-priced refinery
gases. This led [134] to recommend significant increase in ethanol
price to compensate cost-effective ethanol-blending reductions.
Further, the technology is not sustainable without subsidies and
requires more land and water for expansion. For energetic balance,
the technology is disadvantageous. Similarly, major advances are
needed to ensure large-scale competitive cellulosic ethanol pro-
duction. These include: (1) efficient and economic pretreatment
and storage technologies. For instance, engineered enzyme sys-
tems for hydrolysis. (2) Genetically modified microorganisms
capable of metabolizing pentose and hexose sugars while with-
standing stress imposed by the process inhibitors. (3) Maintaining
stable performance of the microorganisms during commercial-
scale fermentation. Improved means of lower energy consumption
with increase in fermentation concentration within shortest time.
(4) Harnessing the optimal conditions for ensuring economic sys-
tem. (5) Availability of capital equipment for demonstrating scien-
tific discoveries such steam explosion. (6) Recovery and waste
management techniques of pretreatment chemicals and wastewa-
ter treatment [135]. As search for solutions to these challenges
intensifies, potentials of the most abundant feedstock – lignocellu-
losic biomass for biogasoline production is gaining attention. How-
ever, integrating the production process into biorefinery seems the
most feasible option for enhancing economic competitiveness
[135]. The foregoing led many universities, researchers [136,137]
private firms as well as governmental agencies to explore convert-
ing ethanol directly into hydrocarbons or H2 [138,139] or
biogasoline.
This alternative solves the problems associated with fermenta-
tion as it converts dissolved sugars into hydrocarbons via routes
that resemble petroleum processing. Moreover, biomass-derived
fuels becomes prominent because of compatibility with existing
energy infrastructure and high-energy density [140]. The world is
witnessing an era of scientific research discoveries transforming
363
into industrial reality. This includes the development of several
routes for producing targeted range of hydrocarbons from biomass
and dissolved sugars (carbohydrates). Fuels and chemical feed-
stocks are produced from these processes while avoiding
unwanted by-products [141,142]. Similarly, Virent Energy Systems
developed ‘bioforming’ technique for transforming water-soluble
sugars into green gasoline, diesel, and jet fuel [143]. Interestingly,
a partnership between Virent and Royal Dutch Shell announced a
100 million gallons/year commercial production of hydrocarbon
fuels within 7 years from inception. Hopefully this will achieve
competitive price of $60/barrel compared with petroleum [144].
Likewise, ‘‘biomass catalytic cracking’’ process (BCC); an analogous
to fluidized catalytic cracking is soon to become operational by the
company – KiOr [145]. All these cannot become reality without
adequate supply of feedstock at affordable cost. To tackle this chal-
lenge, Sapphire Energy developed advanced algae farming technol-
ogy. The firm plans a production capacity of 100 million gallons of
gasoline/year by 2016. The system operates on nonarable land
with nonpotable water [146].
5.9. Prospects for reduction in energy consumption
It is difficult to estimate lignocellulosic biofuel production costs.
This is because of the indirect costs associated with different pro-
duction techniques involved. Nonetheless, the importance of high-
lighting reduction in energy consumption from biogasoline
production cannot be overemphasized. The viability of this alterna-
tive as having high net energy gain, economic competitiveness,
ecological benefits and industrial production would be established
[14]. For instance, the net energy value (NEV) of pyrolysis-derived
biogasoline (1.09 MJ km1) and pyrolysis-derived diesel
(0.92 MJ km1) is higher than the NEV obtained from conventional
gasoline (1.2 MJ km1) [147]. This energy gain obtainable from
biofuels highlights one of the major reasons for considering such
renewable sources. Utilization of a single microbial consortium
for cellulase production and hydrolysis and fermentation is
another approach. This technique; also referred to as direct micro-
bial conversion (DMC) or consolidated bioprocessing (CBP) inte-
grates reaction–reaction in producing bioethanol from biomass. It
reduces operating and capital expenditures necessary for enzyme
production [148]. The cost of enzymes for hydrolysis dropped
30-fold because of recent research efforts by Novozymes Biotech
and Genencor International. This solved the problem of hydrolyz-
ing recalcitrant biomass materials into sugars. This breakthrough
has the potential for reducing land use requirement by ca. 38%
(13–14 million hectares). [135,149]. To enhance economic effi-
ciency, Pfeffer et al. [150] proposed optimizing ethanol purification
(distillation – dewatering and concentration). Consequently, sev-
eral researchers are exploring sugar and ethanol process integra-
tion for improved energy recovery. Cogeneration and
polygeneration systems facilitate increased electricity generation
and overall energy and economic competitiveness. These processes
have the potential of generating more than 70% surplus electricity
from sugarcane plants by overcoming economic and technical bar-
riers of bagasse gasification process. This will reduce process steam
demand and CO2 emissions. The factories will benefit financially
from the surplus power generated while the rural communities
develop socioeconomically. As well, Brazil launched the world’s
first sugarcane-derived ethanol-fired power plant for generating
87 MW in 2010. The power generated is sufficient for a city with
150,000 inhabitants [151].
It is important to note that overriding deduction from energy
balance studies is the achievable net gain of replacing conventional
fuels with biogasoline or as additive. These studies compared all
energy delivered by biofuel such as agriculture, processing and
transportation against all fossil fuel energy inputs [152].
364 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
Consequently, biogasoline production and distribution requires
less energy than petroleum fuels [144]. These studies projected
favorable cost-effective biogasoline production with greater
energy output to input ratio than grain ethanol [36]. Bajpai [153]
also depicted a positive net energy balance for corn ethanol. The
process for producing ethanol from corn requires <35,000 BTUs
of energy, while energy obtainable is ca. 77,000 BTUs. Several stud-
ies have evaluated systems with integrated production of power,
heat, lignocellulosic ethanol, and synthetic natural gas [154–157].
For such systems, Daianova et al. [154] and Ilic et al. [155] both
reported better energy economy for the integrated system com-
pared to stand-alone systems. Bösch et al. [156] reports a potential
increase in both first law energy efficiency and exergy efficiency
when integrating the processes.
6. Current scenario and future outlook
The transportation sector has the potential to provide the
needed global energy-efficiency gains [150]. This is because more
than half of global liquids energy needs comes from this sector.
However, about a quarter of energy-related GHG emissions are
from the same sector. This calls for urgent alternatives [158–
162]. Although the sector comprises of rails, marine vessels and
airplanes, it is the personal-light-duty cars and commercial-
heavy-duty vehicles that accounts for more than 75% of the energy
consumption. Currently, internal-combustion engines (ICE) pro-
pelled by gasoline drive most of these vehicles. Accordingly, the
encouraging announcement by Shell and Virent in 2010 for com-
mencing a 38,000 L/yr of biogasoline in Wisconsin paves the way
forward [163]. The impact of this transition is possible within med-
ium term. This will likely occur in countries with sufficient land
resources or those with agricultural overproduction supply [27]
as well as those who can commit to additional measures especially
in the aspect of inedible oils. However, transforming these poten-
tials into large-scale production of biogasoline by catalytic cracking
of vegetable oils requires some advances. These include tackling
issues such as hydrodynamic flow behavior in a riser reactor
[31], verifying the quality and suitability of the biogasoline in
existing ICE. Also, there is need for developing similar standard
testing method such as the ASTM D6751-01 for Biodiesel (B100).
Another challenge facing biofuel production is the oxygen con-
tent of the end-product. High oxygen contents characterize bioeth-
anol and biodiesel compared to near-zero oxygen contents of
petroleum-derived fuels. Researches are underway for producing
renewable gasoline, jet fuel, and diesel with minimal oxygen and
maximal energy contents. In fact, until recently, cracking of TGs
in FCC unit to produce oxygen-free light cycle oil (LCO), gaseous
olefins and biogasoline is uncommon. However, this process is
gaining attention especially towards higher aromatics and olefinic
naphtenes with approximately MON and 86 RON 100. This indi-
cates the possibility of obtaining lower composition of naphtenes,
n-olefins and i-paraffines [124]. Additional challenge is the 35 vol%
maximum allowable concentration of aromatics in gasoline against
15 wt% for diesel. This is causing a shift to the cleaner-burning
napthenes and paraffins from aromatics [164]. Thus, some have
proposed lowering the feedstock conversion and the cut-point of
the gasoline distillation range. However, these options are eco-
nomically unfavorable [165]. A more suitable option is the rational
design and development of cracking catalysts. Fine-tuning these
catalysts will produce biogasoline with lower concentration of aro-
matics. Seemingly, no single technology can solve the world’s
energy challenges. The solution therefore relies on technological
breakthroughs on numerous fronts combined with political back-
ing. Given the political will and determination through further
research and development, biofuels in general and biogasoline in
particular will soon find its rightful place. The energy and automo-
bile industries have the potential to change how the world uses
energy by supplying more energy to more consumers at minimized
the cost. For example, [49] reported an integrated refinery complex
which utilizes alternative energy sources for producing biofuels,
liquid fuels and chemicals, hydrogen gas and electricity. Yet,
another example is the possibility of an integrated biogasoline
and olefin production via the same catalytic cracking technology.
This process will provide feedstocks for the plastics industries from
the rubber plantations as well as the ethylene (polyethylene) and
propylene (polypropylene) from olefins.
This out-of-the-box idea has the potential to ameliorate most of
the challenges facing economic and sustainable biofuel production.
First, almost every refinery has FCC unit because of its importance
in producing high-octane gasoline. Secondly, it eliminates the need
for R and D in establishing new biogasoline production plants.
Thirdly, it solves the problems associated with other procedures
such as fermentation and effect of water on catalysts. Fourthly, uti-
lizing the products in conventional engines without modification.
Further, by-products such as ethene and propene will serve as
feedstock for the polymer industries. Again, this will ensure com-
petitive selling price. Fifthly, the potential for co-processing of veg-
etable or bio-oil and vacuum gas oil (VGO) in plants will ensure
continuity in expertise and manpower [156]. This is evidently a
promising option for integrating numerous conversion processes
into the existing refineries. The use of large-scale facilities has
the advantage of reducing investments with high conversion effi-
ciencies than other technologies. [131,166,167]. It is possible to
fine-tune physicochemical properties of the end-products as
desired due to high flexibility in adjusting product characteristics.
Evidently, long-term and aggressive research efforts are essential
to establishing the economic feasibility of algae-to-fuels
researches. These developments and subsequent commercializa-
tion will require a detailed review on potential costs for the tech-
nology, yield and price as well as many other factors. This will help
to determine how algal-biorefinery will fare in the competitive
marketplace.
7. Conclusion
Seemingly, the best option for ameliorating the food-for-fuel
and land-use change issues is through biogasoline production from
inedible feedstocks. Accordingly, the future of biogasoline from
RSO looks bright and promising. This is evident from the advanta-
ges that facilitate both feedstock production and the catalytic
cracking technology. The public outcry on food security, environ-
mental impacts and socio-economic situations will also further
the biogasoline transition. The wide acceptance accorded to con-
ventional gasoline would normally be easily transferred to biogas-
oline. Further, no need for long-term capital investment in
establishing refineries because of similarities of fluid catalytic
cracking processes. Nonetheless, it is essential to incorporate opti-
mum process operating conditions from advances in research and
development of catalyst and reactor design into the existing refin-
eries. For instance, developing superior catalysts that possess high
catalytic activities of ZSM-5 and USY zeolites and MCM-41 and
SBA-15 mesoporous materials. However, it is pertinent to develop
and apply broader and more integrated sustainability criteria that
encompass not just biofuels, but other renewable sources. This is
because the options available for promoting sustainability are
not mutually exclusive. Therefore, all feasible renewable energy
sources which have the potential for long-term economic viability
and minimal environmental impacts should be considered. These
concerted efforts should be implementing sooner than later while
ensuring continuity and consistency. Yet, the only means of achiev-
ing this is through passionate cooperation of the vast stakeholders
who share common concerns as emphasized in this review. One
 S.N. Hassan et al. / Energy Conversion and Management 89 (2015) 349–367
such initiative concerned with ensuring sustainability which
involves international multi-stakeholders such as experts, farmers,
companies, governments, inter-governmental and non-govern-
mental agencies is the Roundtable on Sustainable Biofuels. Within
this all-embracing approach, the much sort-after panacea would be
achieved with biogasoline as a subset of the larger picture. Con-
comitantly, the agricultural sector will regain its prominence
where the potential role of biofuel, especially biogasoline will be
imminent.
Acknowledgments
The authors are grateful to University of Malaya High Impact
Research Grant (HIR-MOHE D000038-16001) and Fundamental
Research Grant Scheme (FP031-2013A) from the Ministry of Higher
Education, Malaysia which supported this study financially.
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