Documenti di Didattica
Documenti di Professioni
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a r t i c l e
i n f o
Article history:
Received 31 December 2013
Accepted 17 September 2014
Keywords:
Biogasoline
Bioethanol
Biodiesel
Food-for-fuel
Microalgae
Rubber seed oil
a b s t r a c t
Societal developments are hinged on the energy supplied by fossil fuels. However, the supply of these
fuels is nite in the foreseeable future. This is aside the associated environmental degradation and economic sustainability of these fuels. These negative consequences and challenges spurred the search for
sustainable energy sources such as biofuels. However, affordable feedstocks and efcient synthesis for
renewable fuels remain indispensable and yet challenging line of research. Therefore, breakthroughs in
plant biotechnology and mass production are essential prerequisites for ensuring the sustainability of
biofuels as alternatives to petroleum-based energy. Conversely, public outcry concerning the foodfor-fuel conicts and land-use change hinder the popularity of such biofuel energy sources. Therefore,
this paper reviewed the prospects of biogasoline production as sustainable alternative to ethanol and a
compliment to biodiesel. Apart from reduction in greenhouse gas emissions, biogasoline promises to
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
conicts and land-use competitions. However, achieving the biofuel central policy depends on advances
in processing the renewable energy sources.
2014 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Challenges associated with biofuel production and utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Land-use change and associated implications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.1.
Biogasoline land requirement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Food-for-fuel conflicts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Unavoidable utilization of fossil fuels & gasoline formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
GHG emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Determinants that influence the demand and supply of biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Prevailing market conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Socio-economic factors, health effects and environmental concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Governmental policies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.
Irregular distribution of global oil reserves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5.
Need for long-term durability tests on vehicles powered by unblended biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Is there a light at the end of the tunnel? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Biodiesel and bioethanol are only part of, but not the panacea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biogasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Catalytic cracking of triglyceride-based feedstocks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Biogasoline via fluid catalytic cracking of microalgal oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
Properties, characterization and availability of RSO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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/ 2014 Elsevier Ltd. All rights reserved.
350
351
351
352
353
354
354
355
355
355
356
356
356
357
357
357
358
358
359
350
6.
7.
5.4.
Biogasoline via fluid catalytic cracking of RSO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5.
Challenges in fluid catalytic cracking operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.6.
Choice of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.7.
Choice of reactor type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.8.
Biogasoline technoeconomical challenges and advances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.9.
Prospects for reduction in energy consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Current scenario and future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
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 transesterication 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 global biofuel development is the high cost of feedstock which constitutes 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 ingenuity 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 environment [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].
360
360
361
362
363
363
364
364
365
365
351
a
b
Fuel
Airfuel ratio
RONa
MONb
Gasoline
Butanol fuel
Ethanol fuel
Methanol fuel
34.6
29.2
24.0
19.7
14.6
11.2
9.0
6.5
46.9
36.6
30.0
15.6
0.36
0.43
0.92
1.2
9199
96
129
136
8189
78
102
104
Table 2
Gasoline energy content compared to different biofuels [11,12].
Fuel
MJ/L
BTU/L
Liter gasoline
Petrogasoline
Biodiesel
Petrodiesel
Biobutanol
Bioethanol
32
33.3
40.3
29.2
19.6
30,336
31,568
38,204
27,682
18,581
1.00
1.04
1.25
0.91
0.61
Table 3
Some oil bearing plants and their oil productivity gures [5,6].
Common name
Latin name
Productivity, kg oil/ha
Palm
Corn
Rubber seed
Cotton
Deccan hemp
Soybean
Linseed
Mustard
Sesame
Safower
Sunower
Peanut
Opium poppy
Rapeseed
Olive
Jojoba
Babassum palm
Jatropha
Coconut
Pongamia
Erythea salvadorensis
Zea mays
Hevea brasiliensis
Gossypium hirsutum
Cannabis sativa
Glycine max
Linum usitatissimum
Brassica alba
Sesamum indicum
Carthamus tinctorius
Helianthus annuus
Arachis hypogaea
Papaver somniferum
Brassica napus
Olea europaea
Simmondsia chinensis
Orbignya martiana
Jatrpha curcas
Cocos nucifera
Pongamia pinnata
5652
145
217
273
305
375
402
481
585
655
800
890
978
1000
1019
1528
1541
1590
2260
2500
(cassava and potatoes), grains (corn, wheat and milo) and sugar
(sugarcane and beet) for bioethanol production are all food
sources. The feasibility of cracking the said alternatives catalytically is more than three decades old [14]. Further, the thermochemical technologies currently in use in most reneries are
suitable for converting seed-oil and biomass into biogasoline.
Moreover, the cost associated with engine modication is minimal
because biogasoline has similar properties to conventional gasoline [15]. Other important characteristics of biogasoline include:
(a) pure (100%) biogasoline or BG100 runs in any conventional gasoline engine. (b) It substitutes petroleum-based gasoline because
of similar properties. (c) It is employed in high concentrations in
conventional gasoline engines unlike ethanol. (d) Biogasoline eliminates the need to build new biofuel infrastructures for conversion,
storage and transportation systems. (e) Biogasoline has higher
energy content and is more fuel efcient than ethanol. Nonetheless, we are of the conviction that the panacea cannot come from
a single biofuel source. Consequently, the aforementioned issues
require an out-of-the-box-solution. These include incorporating
other sources aside biomass, sludge and wastes into one catalytic
process. Thus, we advocate pertinence in developing and applying
broader and more integrated sustainability criteria that encompass
not just biofuels, but other renewable sources. This is because the
352
Table 4
Net changes in land availability (Mha) [23].
Region
Increased land
requirement
Associated with
co-products
Changes in agricultural
area
Change in
NHA
USA
Brazil
EU
Indonesia and Malaysia
China
Mozambique
South Africa
Study area
11.0
4.9
6.6
0.02
2.2
0.13
0.12
24.9
5.9
1.8
3.2
0.01
0.4
0.03
0.04
11.4
5.1
3.1
3.4
0.01
1.8
0.1
0.1
13.5
3.5
12.0
11.5
8.9
13.4
1.3
2.7
9.0
10.9
4.9
3.6
2.0
20.3
0.9
1.2
41.5
2.3
13.8
11.2
10.9
5.1
2.0
4.0
19.0
47.8
91.5
Global total
MCI = multiple cropping index.
NHA = Net Harvested Area.
353
Additional ethanol
required (million
L)
Argentina
Guatemala
Peru
Philippinesa
Thailanda
Vietnam
Mozambique
Tanzania
Zambia
731.6
159.6
151.6
476.2
783.2
544.8
18.1
41.4
30.7
36.6
9.4
24.6
26.9
14.2
50.6
11.0
26.1
18.4
105.5
27.1
70.8
77.3
50.6
145.9
31.8
75.4
53.1
304.8
78.3
204.7
223.2
118.4
421.5
92.0
217.8
153.3
164,317
35,834
30,315
107,062
156,639
122,355
4058
9293
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 classied as forest or cultivated) for selected biofuel feedstocks [26].
Fig. 3. Average annual increase in area harvested for major biofuel feedstocks (20002008) [26]. Note: Jatropha is not included as no ofcial data on its cultivation are
maintained.
354
Fig. 4. Area of suitable land (not classied 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 gures 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 sustainability of biofuel production level achievable by 2050 [28]. The proponents 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 possible to source food and fuel from the same feedstock. This is
because most governments have the wherewithal to provide sufcient and affordable food to their populace while concomitantly
producing biofuel [28]. Notwithstanding these arguments, numerous 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 Agriculture 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-
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 determinants that need thorough consideration in biogasoline production.
This is because they have the potential to disrupt the biogasoline
production economics by inuencing 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 conicts. These include energy requirements, excessive demand for
oil, GHG emissions, environmental impacts, biofuel production,
food shortage, economic situations and land-use changes. Evidently, the ongoing search for sustainable and affordable biogasoline alternative is not only timely, but needs intensied global
concerted efforts.
3.2. Socio-economic factors, health effects and environmental concerns
The rural economies are facing sustainable development challenges 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 microalgae 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-nancing [47]. These factors affect the day-today activities of the individual directly. However, with proper
management, biogasoline economy can ensure socio-economic
developments in the said areas. Consequently, Rudolf Diesels foresight that development of national economies would rely on plantoil 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 several countries have beneted from the major boon of the existing
biofuels industries [5052]. 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 signicantly to the
environmental advantages. Neuwahl et al. [53] employed an
inputoutput 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 inefciency of the economic policy. The gains from the
food, agricultural and industrial sectors will undoubtedly compensate 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 implications of biofuels. The traditional heating and cooking fuels such
as charcoal, wood, crop residues and dung emit high levels of particles 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 [5658].
Biofuels have the potential to reduce the particulate matter emissions that produce harmful effects on the environment and
humans [59]. Also, a problem seldom discussed is the substantial
freshwater demands for both biofuel reneries process water
needs and cropping systems in large-scale biofuel production
[6063]. These accentuate the need for a transition from sugarcane
and corn to feedstocks and cropping systems that are less waterintensive [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
Other factors that inuence the demand and supply for fossil
fuels and by extension, biofuels are geopolitical instabilities and
irregular distribution of the worlds 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 production rates and limited-access to the large reserves in places such as
Venezuela, Russia and the Middle East. Besides, the current eld
outages due to frequent political instabilities and the increasing
difculties in exploring and producing oil from difcult terrains
add to the constrains in global production [19]. Additionally, only
few areas have large oil reserves with exceptional geological features. Asia has about 3.4% concentrated while 3.4% is in the Pacic.
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 worlds reserves. Biogasoline production from microalgal oil
has the potential for sustained expansion without irregular outages
common to petroleum fuels.
Table 6
Engine modications and adjustments for alcohol and plant oil use [5,74].
Issue
Alcohol
Alcohol does not evaporate as easily as gasoline
Low ethanol stoichiometric airfuel 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 ow 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
Modication
Redesign engine to provide more heating for evaporation
Recalibrate carburetor to increase heating of the airfuel 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-ltering 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
357
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 efciency and ignition delay for pure oils. Except
for viscosity, Hossain and Davis reported the signicant 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 relatively high ash point temperatures, high pour point (614 times
more viscous) affects spray characteristics at low temperature. Further, reports have showed similar technical difculties with pure
(100%; unblended) biodiesel while durability tests are yet to be proven 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 scenarios 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 condence of both countries
have being improving [82]. Of course, biofuel is not the sole contributor to these economies, but it has indeed contributed immensely. Plausibly, the Brazilian and Malaysian scenarios give credence
to the feasibility of biofuel economy. These economies have the
potentials for improvements especially when biogasoline production 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 challenges of sugarcane-based ethanol and biodiesel from palm oil are
ongoing. Consequently, the next decade or two will serve as the
358
Table 7
Comparative catalytic performance from different cracking processes [97].
Process
Catalytic
cracking
Hydrocracking
Hydrotreating
hydrocracking
Conversion (%)
Isopara. sel. (%)
Olens sel. (%)
Aromatic sel. (%)
Ave. number of Carbon
cracked
100.0
15.2
57.6
26.0
10.1
94.9
34.3
25.6
39.6
9.6
93.3
52.8
46.9
0.0
8.2
76.6
3.1
25.0
69.2
6.3
89.2
89.7
5.0
0
10.8
Table 8
Comparison of fuel fractions obtained from different cracking processes [97].
Process
Catalytic
cracking
Hydrocracking
Hydrotreating
hydrocracking
Conversion (%)
LPG sel. (%)
Gasoline sel. (%)
Kerosene sel. (%)
Diesel sel.
Hydrogen consumption
(NL/L)
100.0
5.3
35.4
54.1
2.0
53.1
94.9
2.2
32.8
60.0
4.7
130.1
93.3
8.1
51.2
39.1
1.7
253.9
76.6
21.1
64.5
9.7
0.0
19.1
89.2
2.3
25.4
62.4
9.9
530.0
Table 9
Summary of some crude microalgal oil compositions, fuel oil yields and composition obtained via catalytic cracking route [101].
Microalgae
Botryococcus braunii
Chaetoceros muelleri
Liquefaction (Na2CO3)
Hydrocracking (NiMo, CoMo)
Cracking (zeolite H-ZSM5)
359
encouraging. The authors reported equivalent (not similar) gasoline 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% olenic 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 aromatics. The authors compared different cracking processes and
product selectivities (Tables 7 and 8) and showed catalytic cracking has the highest conversion and olen selectivity. Similarly, Kitazato 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 efcacy of the cracking process. The
same conditions in a uidized 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.
Table 10
Properties of rubber seed oil in comparison with other edible and inedible oils [104,108,109].
Property
Oil content
Seed (wt%)
Kernel (wt%)
Non-edible
At 15 C.
Conventional fuel
Rapeseed
oil
Soybean
oil
Gasoline
Diesel
Karanja
(Pongamia
pinnata)
Jatropha
(Jatropha
curcas)
Polanga
(Calophyllum
inophyllum)
4060
4050
2550
3050
2060
4060
65
22
11.65
16.0
12.01
6.8
3.49
11.67
11.75
7.50
6.5
12.95
3.26
0.85
0.89
3.15
51.59
43.5
34.09
16.93
64.4
13.27
23.26
16.46
34.4
38.26
73.73
22.3
57.51
55.53
2.65
0.80
0.3
8.23
6.31
0.913
0.920
0.896
0.918
0.914
0.912
0.92
27.8454
18.252.76
71.98
66.2
39.5
32.850
65
198263
174280
221
220
280
210243
230
45 min
3 to 6
3 to 5
15.0
31.7
10 to16
12.2
20 to 5
1315
810
34.038.8
38.20
42.15
39.25
39.5
37.62
39.540.1
39.6
5.06
3.8
44
0.15
1.14
0.11
0.2
4567
33.751
37.1
37.6
41.259.5
38.0
520
870928
901940
918
914
911921
914
6.06.5
0.20/0.44
0.23
0.30
0.42
0.27
Edible
Sunower
oil
1725
0.72
0.78*
0.37
0.44*
8.7 to 1.7
2.02.7
43.35
45
47 min
815
0.030.1
360
fatty acid (FFA). This means that its acid value is 34 which makes it
unsuitable for esterication and transesterication 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 esterication rate signicantly [105].
Furthermore, the storage life of such oils reduces with rening
[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 rst 10 days of storage. Obviously, it will be difcult
for farmers in the rural areas to observe these conditions. Hence,
there is the need to explore the potentials of this promising feedstock for biogasoline production. The use of RSO and other unexploited oil crops will alleviate pressure on the food. This is
because rubber tree plantation is not new and it is capable of producing fats and oils for the biogasoline industry. Further, it has
properties similar to vegetable oils employed for biogasoline production (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 3seeded capsule with each carpel containing one ellipsoidal seed.
The lustrous-mottled brown seeds vary in both size (2.53 cm
long) and weight (24 g). The seed kernel (5060% of seed) is
important as it contains about 4050% of brown color oil. Approximately, 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 uid catalytic cracking of RSO
As early as 1978, Chandra [110] patented a procedure for producing biogasoline from cracking of RSO with aluminasilica catalyst impregnated with metal oxides such as magnesium, nickel and
vanadium. The author obtained a conversion of 55 wt% in xed 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 ultrastable Y zeolite. The authors reported the method reduced the
problems associated with high carboxylic acid contents (acid value
116142 mg KOH/g). These undesired products have deleterious
361
Scheme 1. Proposed reaction pathway for the conversion of palm oil over HZSM-5 catalyst to hydrocarbon products [126].
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-pressure (70160 atm) hydrotreating. Hydrotreating also eliminates
typical catalyst poisons such as sulphur, nitrogen and oxygen compounds to prevent catalyst poisoning. Fundamental knowledge of
chemical composition of the FCC feedstock and how catalyst affects
it is crucial for efcient production. Research have showed that fast
thermal cracking step decomposes TGs into FAs and allylcarbenium 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 unsaturation of FAs [123]. Hydrogen consumption during water formation
leads to production of more olenic 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 different cracking gas from different vegetable oils. This is because of
degree of FA unsaturation in the TGs (in the order: soybean, rapeseed, 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 deactivation from coke formation [124]. It should be noted however that
aside increasing gasoline octane number, aromatics have undesired 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 providing fuel during the two world wars. In 1979, Weisz et al. [125]
362
Table 11
Biofuel production via catalytic cracking of different feedstocks.
Feedstock
Catalyst/reactor
Reaction conditions
Biogasoline
Kerosene
Diesel
Gases
Coke
57.9
NR
NR
27.5
NR
[122]
43.3
21.0
11.0
NR
9.6
11.5
21.8
7.2
12.2
2.7
[109]
[132]
49.2
28.9
36.0
26.1
15.9
17.2
2.6
12.3
4.6
8.2
13.4
16.2
1.7
10.7
6.3
[108]
[128]
[125]
Al-MCM-41
32.6
20.0
6.7
6.7
9.8
[125]
SBA-15
20.7
15.5
4.8
9.5
7.2
[125]
MCM-41
Ecat/Laboratory-scale
micro-riser reactor
Ultra-Y/ZSM-5 in a twostage riser FCCU
Ultra-Y/ZSM-5 in a twostage riser FCCU
50.9
43.0
22.2
NR
9.8
32.0
10.0
5.0
12.1
5.0
[109]
[107]
22.9
NR
15.0
6.2
5.2
[132]
32.8
NR
11.4
4.5
2.3
[132]
Palm oil
Palm oil
Palm oil
Used palm oil
Waste FA-based
palm oil
Waste FA-based
palm oil
Waste FA-based
palm oil
Palm kernel oil
Rapeseed oil
Soybean oil
Chicken fat
Ref.
NR = not reported.
demonstrated novel mechanisms and capabilities of shape-selective zeolites in producing high-grade biogasoline from aromatics
of plant extracts such as corn oil, rubber latex and peanut oil. However, most conversion strategies have difculty in efciently
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 biomassderived feedstocks through the following reaction biogasoline
[113]:
the uid and catalyst [15,109]. The most popular amongst these
reactors for the continuous production of biofuels is the uidized-bed catalytic cracking system. It is similar to the uid catalytic
cracking unit (FCCU) of the conventional petroleum reneries. 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 uidized 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 facilitates easy access of reactants into the catalyst micropores. Alternatively, the catalyst is synthesized with coated mesoporous
ceramic material containing zeolite matrix or in situ overgrowth
technique. This ensures efcient chemical bonding between coating and catalysts with reduced attrition [133]. Reaction conditions
such as catalyst type, catalyst-to-oil ratio, reaction temperature,
and residence time and reactor design inuence the yield of the
desired product. These will facilitate the transition to biofuels with
minor modications to the existing reactors in the petroleum reneries. Fig. 8 presents the catalytic cracking of vegetable oils for producing biofuels in a riser reactor of a typical biorenery [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 reners 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 renery
gases. This led [134] to recommend signicant 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 production. These include: (1) efcient and economic pretreatment
and storage technologies. For instance, engineered enzyme systems for hydrolysis. (2) Genetically modied microorganisms
capable of metabolizing pentose and hexose sugars while withstanding stress imposed by the process inhibitors. (3) Maintaining
stable performance of the microorganisms during commercialscale fermentation. Improved means of lower energy consumption
with increase in fermentation concentration within shortest time.
(4) Harnessing the optimal conditions for ensuring economic system. (5) Availability of capital equipment for demonstrating scientic discoveries such steam explosion. (6) Recovery and waste
management techniques of pretreatment chemicals and wastewater treatment [135]. As search for solutions to these challenges
intensies, potentials of the most abundant feedstock lignocellulosic biomass for biogasoline production is gaining attention. However, integrating the production process into biorenery seems the
most feasible option for enhancing economic competitiveness
[135]. The foregoing led many universities, researchers [136,137]
private rms as well as governmental agencies to explore converting ethanol directly into hydrocarbons or H2 [138,139] or
biogasoline.
This alternative solves the problems associated with fermentation 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 scientic research discoveries transforming
363
364
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 renery 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 olen 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 olens.
This out-of-the-box idea has the potential to ameliorate most of
the challenges facing economic and sustainable biofuel production.
First, almost every renery 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, utilizing the products in conventional engines without modication.
Further, by-products such as ethene and propene will serve as
feedstock for the polymer industries. Again, this will ensure competitive selling price. Fifthly, the potential for co-processing of vegetable 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 reneries. The use of large-scale facilities has
the advantage of reducing investments with high conversion efciencies than other technologies. [131,166,167]. It is possible to
ne-tune physicochemical properties of the end-products as
desired due to high exibility 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 commercialization will require a detailed review on potential costs for the technology, yield and price as well as many other factors. This will help
to determine how algal-biorenery 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 advantages that facilitate both feedstock production and the catalytic
cracking technology. The public outcry on food security, environmental impacts and socio-economic situations will also further
the biogasoline transition. The wide acceptance accorded to conventional gasoline would normally be easily transferred to biogasoline. Further, no need for long-term capital investment in
establishing reneries because of similarities of uid catalytic
cracking processes. Nonetheless, it is essential to incorporate optimum process operating conditions from advances in research and
development of catalyst and reactor design into the existing reneries. 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 achieving this is through passionate cooperation of the vast stakeholders
who share common concerns as emphasized in this review. One
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