Progress and Future of Biodiesel Synthesis - Advancements in Oil Extraction and Conversion Technologies

Energy Conversion and Management 182 (2019) 307–339
Contents lists available at ScienceDirect
Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman
Review
Progress and future of biodiesel synthesis: Advancements in oil extraction T

and conversion technologies
⁎
Bisheswar Karmakar, Gopinath Halder
Department of Chemical Engg, National Institute of Technology Durgapur, Durgapur-713209, India
A R T I C LE I N FO A B S T R A C T
Keywords: Biodiesel has gained the forefront of our focus on renewable transportation fuels. This article provides a com-
Biodiesel synthesis prehensive review on the sources used as feedstock and their classification based on generation or type (edible,
Feedstock classification non-edible, waste resources and animal fats) along with a variety of classical and modern oil extraction tech-
Glycerol-free niques. The technical aspects of the various biodiesel production methods currently implemented to the best of
Oil extraction
our knowledge are discussed here, which include in-situ biodiesel production, both catalysed (homogeneous and
Supercritical approach
heterogeneous systems) and uncatalysed classical production approaches, with emphasis on how each of these
Superheated technology
approaches are affected by their reaction parameters. The review also highlights the observed drawbacks of each
process with a view to assessing the implementation of supercritical and superheated technologies as an alter-
native, economically feasible advancement.
Supercritical process (SCP) has shown great prospect in the obtainment of high quality biodiesel from a wide
range of high to low grade feedstock with minimal impacts on the presence of water or FFAs (free fatty acids).
From available literature it is shown that these do not affect the process significantly, and various other su-
percritical fluids such as methyl acetate, tert-butyl methyl ether (MTBE) and dimethyl carbonate can also be used
to avoid glycerol formation. The process however, suffers from high initial implementation cost being the most
prominent drawback, among others like thermal degradation of the fuel. Another promising technique, the
superheated vapour technology (SHV) has emerged as an alternative, with limited literature proving the su-
periority of either of these processes to be inconclusive. In future works, researchers need to look into various
aspects such as developing a spiral reactor for heat recovery, using software based optimization for eliminating
redundant experiments analysing production cost for industrial scale-up and improving the fuel’s oxidative
stability by adding antioxidants for convenient long-term storage and use.
1. Introduction lowlands [3]. A pressing concern is the current energy crisis due to the
high energy demand in the industrial and domestic sector, which is
1.1. Background leading to the diminution of fossil fuels. The global depletion of fossi-
lized fuel resources is projected to face a surge approximated at about
Climate change, as evident from the alterations in weather patterns, 38% over existing demand, which will equate to 119 million barrels per
is at present the greatest environmental threat to every ecosystem on a diem by 2040. Transportation and industrial sectors attest for 92% of
global scale. We could be looking at the extinction of about 1 million the overall requirements [4]. A major part of the upsurge can be ex-
species, considering that the average global temperature rises above a pected from developing countries like India, China, and the Middle
nominal margin of 2 °C [1]. The usage of fossil fuels has been widely Eastern countries. The developed countries are expected to be rather
recognized as the ‘facteur premier’ resulting in global warming; conse- steady in their projected energy consumption per diem. Percentage in-
quently the dependence on fossil fuels for meeting energy requirements crease in real gross domestic product (GDP), more commonly known as
needs to be replaced with renewable, biodegradable energy sources in economic growth, goes hand in hand with proportionate surge in de-
an attempt at reducing CO2 and GHG (greenhouse gas) discharge [2]. velopment of the transportation sector [5].
Other unfavourable impacts of global warming comprise a probable rise A major percentage of the global energy needs are met through fi-
in the sea level which will probably result in the submergence of nite resources such as petrochemical sources, coal and natural gases;
⁎
Corresponding author.
E-mail address: [email protected] (G. Halder).
https://doi.org/10.1016/j.enconman.2018.12.066
Received 24 September 2018; Accepted 11 December 2018
0196-8904/ © 2018 Elsevier Ltd. All rights reserved.
B. Karmakar, G. Halder Energy Conversion and Management 182 (2019) 307–339
hydroelectricity, solar and wind energy, geothermal and nuclear energy Table 1
being a few exceptions [6]. The widespread usage of fossilized fuel Top biodiesel producing countries in 2016.
sources for energy has attracted wide recognition as an untenable im- Country Biodiesel production (in billion litres)
plementation since they are rapidly depleting while also contributing to
environmental pollution [7]. All in all, the myriad of factors we cur- USA 5.5
Brazil 3.8
rently face necessitates the development of renewable energy sources
Germany 3
with limitless usage capabilities combined with diminutive environ- Indonesia 3
mental impacts. The sustainable energy sources have low gaseous and Argentina 3
particulate emission profiles. Therefore, it has the prospective of at- France 1.5
tenuating climate change and environmental pollution [8]. Thailand 1.4
Spain 1.1
Belgium 0.5
1.2. Biodiesel Colombia 0.5
Canada 0.4
1.2.1. Emerging energy source China 0.3
India 0
The primary alternate to fossil fuels is biodiesel. The name
Singapore 0
‘Biodiesel’ was popularized in the US in 1992 by the National Soy diesel
Development Board which led the way to the commercialization of
biodiesel [9]. Biodiesel synthesis receives ample worldwide attention steady growth owing to increase in both public and private transport
with the public, being one of the first alternative fuels with diesel- vehicles [28]. Fig. 1a shows the global energy consumption (by sector)
equivalent properties [10]. According to ASTM, biodiesel is “a fuel between 2005 and 2035, based on consumption trends [27] while
comprised of mono-alkyl esters of long-chain fatty acids derived from Fig. 1b shows the overall global marketed energy from 1980 (data
vegetable oils or animal fats, designated B100” [11] with an added available) to speculated net energy production and its marketing up to
requisite of having GHG emissions that are at least half of baseline GHG 2030.
emissions [1]. The transport sector presently requires about 60% of world’s oil
Biodiesel is derived from a variety of chemical reactions involving demand and is becoming the fastest rising energy demand sector.
feedstock like vegetable oil or animal fats with alcohol in the presence Nearly all fossil fuel energy consumption in the transportation sector is
or absence of a catalyst [10,12–17]. Biodiesel is a lucrative alternate from oil (97.6%), with a small amount from natural gas [29]. There is
energy source for numerous reasons: (1) being renewable, it can sustain much speculation about the time span of peak oil production, with the
a continuous supply chain; (2) the molecular structure is highly bio- 2005 French Ministry report having suggested it to be in 2013, whereas
degradable with minimal combustion toxicity; (3) cultivation in rural other models predicted the peak year to have been either 2010 or 2005,
and wastelands can result in considerable improvement of a country’s while some studies contemplate the peak extraction to be in 2020. From
economic potential and reduce the dependency on crude oil imports the predictions it can be speculated that oil resources will probably be
[10,18–20]; (4) compared to diesel, it gives off negligible emissions of depleted in fewer than 45 years if consumed at an increasing rate of 3%
sulphates, aromatic hydrocarbons along with minute quantities of per annum [10,13,30,31].
smoke containing carbon dioxide (CO2), carbon monoxide (CO) and
particulates [7,21,22]; (5) it can be used as a substitute to diesel in
boilers or internal combustion engines without major modifications; (6) 1.3.2. Emission scenario
it contains more oxygen which aids the complete combustion of the In a span of just 13 years (from 2007 to 2020) a staggering 4.1
fuel, leading to decrease in emissions [23,24]; (7) it is suitable for use in billion metric tons of CO2 have been expected to be released into the
modern diesel engines (whether used as B100 or blended proportio- atmosphere. According to a 2016 report on global CO2 emissions by the
nately with diesel) with slight modifications (if any) with equally well PBL Netherlands Environmental Assessment Agency, around 4 billion
engine performance when compared to petro-diesel [25,26]; (8) it has metric tonnes of CO2 have already been emitted till 2015, the highest
better lubricity, therefore the fuel will lower the usual amount of contribution being from the public transportation sector. Furthermore,
wearing on the metal parts leading to egine longevity. projections indicate that additionally, 8.6 billion metric tons of CO2 can
be released into the atmosphere between 2020 and 2035. Fig. 2 depicts
1.2.2. Production and usage the expected global CO2 emission trends till 2035, which include
The overall biodiesel production around the world was an estimated countries both under the OECD (Organization for Economic Coopera-
15 thousand barrels per day in 2000 which increased to 289 thousand tion and Development) and outside the OECD (referred as non-OECD
barrels per day in 2008 [23,27]. Available statistics suggest that 85% of countries). It is worth noting that according to the 2016 PBL report, the
the global biodiesel production per year is sourced from the European actual values have far surpassed the predicted values.
Union [10]. Countries such as USA, Indonesia, Brazil, France and Worldwide, the transport sector contributed to around 23% and
Germany are the top consumers of biodiesel. Biodiesel markets have 22% of CO2 emissions in 2007 and 2008 correspondingly [32,33]. Road
recently started experiencing an enormous growth in the US and Asia, transport accounted for 10% of global GHG emissions [34]. As stated by
in particular India and China, where the government targets a 15% the United Nations’ Intergovernmental Panel on Climate Change’, the
substitution of petro-diesel by 2020. However, the potential for its transport sector contributed around 23% of GHG releases in 2004, with
production and application is much more. Table 1 shows the list of the passenger vehicles accounting for about 45% of this [35]. Transporta-
top biodiesel producing countries in 2016. tion emissions comprise of a number of gases, some of which are con-
sidered as GHG, while ozone, carbon monoxide and aerosols being non-
1.3. Global transportation sector GHG but having a secondary impact on global warming [36]. GHG
gases and their percentage emissions are summarized in Table 2.
1.3.1. Energy consumption scenario
After the industrial revolution, energy has emerged as a decisive 1.4. Biofuel policy considerations in India
factor for humanity’s economic growth and high standard of living. In
terms of worldwide energy consumption, the transportation sector now In 2009, a national biofuel scheme was established which re-
requires 30% of the global energy supply is the second largest after commended using renewable energy in transport, the purpose of which
industries. In the past few decades, the transportation sector has seen a was to replace 20% of petroleum-based fuel with biofuel by 2017. In
308
Fig. 1a. Global energy consumption scenario (sector-wise).
Fig. 1b. Global marketed energy (overall).
2014, diesel rates were relaxed in order to enable more conducive biodiesel [13,14,47]. Preferably, a good feedstock necessitates the ful-
conditions for biodiesel production. The government declared a filment of two requirements which are: a large scale production stem-
blending requisite of 10% ethanol in commercial gasoline, starting from ming from low cost of production.
the October 2015/2016 sugarcane season, together with prevailing
regulations that set the sugarcane price at a minimum. Consultations 2.1. Types and obtainance
are currently fixated on the amendment of the 2009 biofuels law, which
would include attention on a mandatory blend for biodiesel. India is The ease of obtainance of the feedstock for biodiesel production is
pushing on becoming a “Methanol Economy” quite recently and also dependent on the climate of the region, conditions of the local soil,
endeavouring to become a ‘net zero petroleum import country’. This geographical location and agricultural conventions followed by a
could be something to watch in the near future apropos to the impact country. From an overall point of view, feedstock for biodiesel synthesis
on biofuels and national policy associated with alternate fuels. can be allocated four main categories [9,10,13,23,25,48–55]:
2. Feedstock for biodiesel 1. Edible vegetable oils which include peanut, sunflower, soybean,
rapeseed, coconut and palm oil.
So far, estimates put more than 350 oil-bearing crops to have been 2. Non-edible vegetable oils including karanja, algae, halophytes, sea
identified worldwide as prospective sources for the production of bio- mango and jatropha.
diesel. A comprehensive list of most commonly used feedstock for 3. Waste oils which can be waste cooking/frying oils or yellow grease,
biodiesel production have been presented in Table 3. The extensive spent coffee grounds, organic municipal waste, olive stones.
variety of accessible feedstock is a significant factor in production of 4. Animal fats which include chicken fat, inedible or unusable by-
309
Fig. 2. Global carbon dioxide emissions from 2005 (recorded) to 2035 (expected).
Table 2 Table 4
Percentage contribution of transport vehicle exhausts. Biodiesel feedstock and their oil content.
Greenhouse gas (GHG) Percentage (%) Feedstock Oil content (%)
Carbon dioxide (CO2) 95 Coconut 63–65

Methane (CH4) and Nitrous oxide (N2O) 1 Corn 48
Hydroflurocarbons (HFCs) 3 Palm 30–60
Peanut 45–55
Rice bran 15–23
Soyabean 15–20
Table 3
Sunflower 25–35
Common feedstock for biodiesel production.
Castor 53
Edible oils Non-edible oils Animal fats Other sources Cottonseed 18–25
Jatropha Seed: 35–40
Barley Camelina sativa Beef tallow Algae (Cyanobacteria) Kernel: 50–60
Canola Castor (Ricinus communis) Chicken fat Fungi Jojoba 45–50
Coconut Cotton seed Fish oil Microalgae Karanja 27–39
Corn Croton megalocarpus Pork lard Miscanthus Linseed 40–44
Groundnut Jatropha curcas Poultry fat Poplar Neem 20–30
Palm Jojoba Switchgrass Rubber seed 40–50
Peanut Karanja (Pongamia pinnata) Calophyllum Sea mango 54
inophyllum Microalgae (low oil content) 30
Rapeseed Mahua (Madhuca indica) Olive stones Microalgae (medium oil content) 50
Rice bran Nagchampa Spent coffee grounds Microalgae (high oil content) 70
Safflower Neem
Sesame Rubber seed (Hevea
brasiliensis) for biodiesel production [14,17].
Soyabean Tobacco seed
Sunflower Krating oil
Wheat Kapok oil
Crude acorn Palm fatty acid distillate 2.2. Classification
(PFAD)
Manilkara zapota
2.2.1. FAO system of categorization
Waste Date pit oil
Bitter almond
According to the Food and Agricultural Organization (FAO) it is
Pumpkin seeds better to use a comprehensive, self-explanatory classification system
Avocado which depends on the nature of feedstock (based on the origin of the
Linseed biomass), instead of using the conversion technology. It categorized
biofuels into three primary groups, namely, woodfuels, agrofuels and
municipal by-products. Table 5 provides a comprehensive summary of
products from fish oil, lard and tallow.
the classification. Reports by Knothe [56] indicate that using the terms
first, second, third and fourth generation for biofuels may be a classi-
For the consideration of any feedstock as a source for obtaining
fying advantage but are misleading. They do not indicate that biodiesel
biodiesel, the oil content in percentage and the agricultural yield from
obtained from second or third generation feedstock possess better fuel
cultivated land are the main parameters. Table 4 summarizes the esti-
characteristics over fuel obtained from first generation feedstock, The
mated oil content of different biodiesel feedstock. Genetically en-
quality of fuel actually depends on the properties of the feedstock used
gineered plants like miscanthus, big bluestem, switchgrass and poplar
as well as the conversion procedure adopted.
are not associated with food crops and can be listed as new feedstock
310
Table 5
FAO system of classification of biofuel feedstock.
Woody biomass Herbaceous biomass Biomass from fruit and seeds Others (including mixtures)
WOODFUELS AGROFUELS
Energy crops Direct ● energy forest trees ● energy grass ● energy grain
● energy plantation trees ● energy whole cereal crops
By-products ● thinning by-products Crop production by-products ● animal by-products
● logging by-products ● straw ● stones, shells, husks ● horticulture by-products
● landscape management by-
products
Indirect ● wood processing industry by- ● fibre crop processing by- ● food processing industry by- ● bio-sludge
products products products ● slaughterhouse by-products
● black liquor
End use materials Recovered ● used wood ● used fibre products ● used products of fruits and MUNICIPAL BY-PRODUCTS
seeds ● kitchen waste
● sewage sludge
2.2.2. First generation feedstock to place in addition to being scattered in availability

The first generation biodiesel feedstock were the first oil crops to be [9,10,13,14,31,48,70,73,74,76,82,86–98]. Furthermore, biodiesel from
used for the production of biodiesel. They include sunflower [57–59], animal fats and vegetable oils performs poorly at low temperatures and
soybeans [60–62], rapeseed [57] and palm oil [63–67]. Using these has a greater amount of fatty acids. Due to this, the process of trans-
sources over the years lead to the generation of problems because this esterification encounters hindrance by saponification of the fatty acids,
practice impacts the food market on a global scale, destabilizing it and which retards the reaction [9]. An example would be beef tallow, with
leading to questions in food security [68,69], Although the con- nearly 50% saturated fatty acid content, which contributes to its high
sequences are somewhat exaggerated, the world may well face a critical viscosity and poor performance in cold weather [99].
issue of ‘food versus fuel’ in the near future if the practice continues.
Since these oils are also in high demands for consumption, their use for 2.2.4. Third generation feedstock
biodiesel production can result in the increase of costs of both biodiesel The first and second generation feedstock are lucrative for biodiesel
and edible oils [70]. production mostly when produced on a laboratory scale. Cost of the raw
The process has detrimental consequences on the environmental material is the major obstacle when the setup needs scale-up mod-
because of its requirement of vast areas of cultivable land for feedstock ifications for commercial scale production [57]. Another factor is that
generation. This leads to deforestation mostly in the tropical countries even if oil crop harvest is increased, for the sufficient synthesis of clean-
which supply more than 75% of palm oil globally. Continuation of this burning biodiesel as an alternative to petro-diesel, sustainable pro-
practice for the global production of biodiesel would damage the reduction in large quantities is not possible [71]. In contrast, microalgae
gional flora and fauna, with impacts culminating in climatic changes. as a third generation feedstock has the following benefits:
1. Since they are relatively low on biomass microalgae provide more

2.2.3. Second generation feedstock yield per hectare, thereby reducing costs on harvests and transport.
The search for alternative sources for the production of biodiesel These play no part in the human food supply chain, removing food
was aimed at reducing the reliance on edible oil. The second generation crisis.
feedstock include non-edible plant sources such as jojoba, sea mango, 2. They do not require areas of arable land, thereby having no impact
Jatropha curcas, tobacco seed, neem, Pongamia pinnata, rubber seed, rice on the production of crops used for fodder, food and other products
bran, desert date and nagchampa (Calophyllum inophyllum). Further, [100].
animal sources can also be considered such as fats like pork lard, 3. It is possible to cultivate microalgae in environments that are ha-
poultry fat and beef tallow. Recently, attention has also been shifted to zardous to other crops. These include brackish water bodies or non-
waste oils which include yellow grease and waste cooking oils, which arable wastelands [101]. Also, it is possible to cultivate them in
nullifies the disposal needs, since they can no longer be used for any bioreactors or even in farms [14].
other purposes [10,14,71–82]. A few advantages have been noted in the 4. Usually, microalgae contain 20–50% lipids on dry biomass weight,
use of these feedstock: but greater yields are possible with genetic modifications [79]. Since
they have a cell cycle of 24 h, genetic engineering can result in ex-
• Being unsuitable for consumption because of their toxicity, their use ponential growth rates with cell cycles lasting for about 3.5 h [77].
increases food availability [83]. 5. Microalgae are considered to be an efficient biological system for
• Yield and quality of biodiesel from non-edible oil is analogous to can harvest solar energy to produce carbon-based compounds [102]
that obtained from edible oils [84]. by fixing CO2 (a GHG) through a process termed ‘biofixation’
• Non-edible plants also grow well on wastelands, thereby leaving [77,103]. Because of their small size, they can also be easily che-
farming lands available for growing food crops [83]. mically treated.
• Methyl esters prepared from animal fats are advantageous over 6. The lipids contained in microalgae have high degree of saturation,
some feedstock in possessing noncorrosive properties and higher resulting in their neutral nature [104,105].
cetane number in addition to being renewable [85].
However, the commercial production of biodiesel from microalgae
The use of second generation feedstock for biodiesel production has faces the following hurdles, most of which require biotechnological
not been implemented widely for certain disadvantages. First of all, approaches for isolation or modification for obtaining the desired strain
they are not abundantly available to be enough to meet a significant as well as product separation:
amount of our net worldwide demand for transportation fuel. For waste
cooking oil, the groundwork for collection and the need for purification 1. The isolation of microalgal species from a local environment and
are hurdles since the composition of waste cooking oil varies from place
311
further screening of robust strains from the microalgae obtained is the apparatus, as shown in Fig. 3. This break opens the pores of the raw
difficult. material and releases the oil contained in it. The system yields a mixture
2. Genetic modification for improvement of light capture, carbon of a vapour and desired raw oil, which can be collected after elimina-
capture and photosynthetic efficiency is needed. tion of the vapour [38]. This procedure can also be performed under
3. The microalgal culture needs to be continuously monitored for CO2 variations of pressure depending upon the plant material and the dif-
solubility, proper aeration as well as removal of highly reactive ficulty of oil extraction under atmospheric conditions [39].
oxygenic by-products. The process has the benefits of low thermal degradation of oils since
4. The strains that are selected need to be genetically modified for the operatigng temperature rarely exceeds 100 °C. Also the amount and
improvements in biomass accumulation (rich in lipids) along with a qualtity of the steam can be contolled efficiently. However, this process
high rate of growth. suffers from quite a few disadvantages. The process requires that the
raw material needed for the extraction must be evenly dispersed for
2.2.5. Fourth generation feedstock and speculations high oil yields. The material should be homogeneous in size and
The concept of fourth generation biodiesel aims at the production of packing should be constricted since strong resistance to the passage of
sustainable energy along with a means to trap and store CO2. Materials steam results in the build-up of steam pressure to the point when it can
such as biomass which assimilate CO2 during their growth can be force its way through. A different predicament associated with this
converted into biofuels through the use of procedures similar to that of process is that initially the charge is cold. Until the temperature of the
second generation biofuels. The difference in this process of production entire load approaches the temperature of the steam being injected, the
lies in the fact that during every stage of the production process the CO2 process of wetting will continue. Capital investment required for this
is arrested with the use of techniques like oxy-fuel combustion [106]. pocess is large and when low-priced oils are the product, the investment
Geo-sequestration of the CO2 captured is then performed by storage in costs can take years for full recovery.
saline aquifers, gas fields or old oils. The ability to trap carbon in-
clusively, makes the entire process ‘carbon negative’ compared to 3.2. Mechanical extraction
merely being ‘carbon neutral’. Fourth generation feedstock includes
genetically modified algal species which are capable of high biomass This involves a manual ram press or an engine driven screw press,
accumulation, to be used in photo-biological solar cells that can directly the latter of which can extract 68–80% of the oil contained, while the
convert solar energy to usable biodiesel. former can only achieve around 60–65%. After mechanical pressing,
further treatment by means of filtration and degumming is needed for
3. Oil extraction techniques the extracted oil. A problem concomitant to mechanical presses is that
the design is suitable for particular seeds, making efficient yield low for
An important step in the production of biodiesel is the extraction of other seeds. However, pre-treatment techniques like cooking of the
oils. In this step, the plant materials that contain the oil are subjected to seeds increases the yield of oil for screw presses significantly, going as
physical, chemical or enzymatic treatments to extract the oil. The main high as 89% after single pass and 91% after double pass [43,44].
products are crude oil and cakes of used plant material which may or
may not be of further use. 3.3. Solvent extraction
3.1. Steam distillation 3.3.1. Chemical leaching

Chemical leaching relies on the removal of a component from a
Steam distillation is a kind of separation or extraction process which solid raw material by using a liquid solvent. In this technique, a mul-
is suitable for temperature-sensitive plants which contain aromatic titude of factors influence the rate of extraction, such as particle size,
compounds [37]. Without subjecting to maceration, the intact oil- type of the liquid to be used, temperature and rate of agitation that the
containing plant materials charged in the distillation apparatus are solvent is subjected to. A small particle size is desired to allow for a
exposed to steam. Injected steam will pass through the raw material in larger interfacial area between the raw material and the solvent. The
Fig. 3. Generalized setup for Steam distillation.
312
using fresh batches of the solvent. The system’s temperature being high
enough to approach the solvent’s boiling point, the heat improves the
kinetics of the extraction process. The extraction process is prone to
disadvantages such as the extended period of time needed for it to be
complete, requiring several hours or days. The distillation flask is he-
ated at high temperature for prolonged time periods, which results in
thermal degradation of the solvent. Most of the organic solvents used in
this process are flammable and/or hazardous, and these are neede to be
of analytical grade with high purity. The procedure is not considered
environment-friendly due to potential pollution problems arising out of
the use of such solvents. Also, the process is limited to the extraction of
products of small and finely divided solid samples.
3.4. Enzymatic oil extraction
The procedure of enzymatic oil extraction is proving to be pro-

mising for the extraction of oils. The method utilizes appropriate en-
zymes for the extraction of oil from the feedstock. The technique is
advantageous because of being environment friendly due to the non-
emission of volatile organic matter. Although the process has such high
potential, utilization of this technology as of yet still suffers hindrances
from the relatively high cost of enzyme production, lengthened periods
of incubation and the requirement of de-emulsification during down-
stream processing (DSP) [44,137,138]. The use of techniques such as
affinity chromatography and perfusion chromatography make DSP ea-
sier, while the approach of immobilization of enzymes lowers enzyme
Fig. 4. Diagrammatic representation of a Soxhlet apparatus.
losses and therefore the overall cost. However, immobilization of en-
zymes can reduce reaction rates due to steric hindrance. Also, the use of
solvent should be selective with low viscosity which helps in free cir- solvents such as n-hexane can result in generation of waste water and
culation. Temperature is also an important factor affecting the extrac- emissions of volatile organic matter, in addition to n-hexane being
tion rate as the solubility of the oil usually increases with a rise in flammable and hazardous to human health. This demands using alter-
temperature. Agitation of the solvent also affects the process, since it native extraction systems such as an aqueous enzymatic oil system in
increases the diffusion rate, consequently increasing the transferral of combination with ultrasonication pre-treatment [43,44].
material through and from the particle surface. Despite the sensitivity
of the process to changes in process conditions, application of solvent
extraction can be economical when applied on a large-scale production 3.5. Innovative oil extraction techniques
of biodiesel [43,44].
3.5.1. Supercritical fluid extraction (SFE)
3.3.2. Soxhlet extraction The use of supercritical fluids as solvents is prevalent for purposes
A Soxhlet extractor is a laboratory equipment [45] invented in 1879 like extraction of metal cations and essential oils. Mostly, SFE for
by Franz von Soxhlet [46] for extraction of a lipid from a solid (Fig. 4). analytical purposes is carried out using CO2, which has pretty low
The process effectively recycles a small quantity of solvent, using it to critical temperature and pressure. In addition to being non-flammable
dissolve a larger amount of the desired compound, allowing for un- and non-toxic, highly pure CO2 is obtainable at low costs and its
managed, unmonitored operation. It involves contact between the solid complete removal from the extract can be accomplished with ease
and liquid in order to extract the required compounds from the solid [107]. CO2 usage has a drawback since it is essentially non-polar, and
matrix by means of suspending the matrix into the refluxing solvent. hence polar analytes cannot be extracted [108]. SFE mostly uses CO2 as
The solid matrix is placed into a space which is steadily receiving the the supercritical fluid which can be adjusted according to the nature of
solvent by the condensation of its vapours travelling through the dis- the extractable analyte by the use of co-solvents like methanol or
tillation arm from the distillation flask. After reaching a certain level, ethanol. Fadel et. al. reported that extracts containing analytes using
the liquid is pulled from the cavity by a siphon returning it to the SFE showed higher antioxidant activity along with higher yield and
distillation flask. Therefore the extracted analytes are carried in the lower viscosity as compared to extracts prepared using other techniques
bulk liquid. The process can be continued till the extraction achieved is while Capuzzo et. al. noted the extracts to be of superior functional
complete or the solvent is saturated. Al-Hamamre et al. [315] used a quality [109,110].
Soxhlet apparatus for the extraction of coffee oil from spent coffee The process boasts selective extraction of the desired compound
grounds, collected from a pressurized bean-to-cup coffee machine. The because the properties of the supercritical fluid can be varied by
extraction involved the use of various solvents such as iso-propanol, changing the operating temperature and pressure. Polyphenols can be
ethanol, and acetone as polar solvents and toluene, chloroform, hexane removed by the use of pure supercritical CO2 at high pressure, after
and n-pentane as non-polar solvents for determination of the best6 which unsaturated fatty acids can be extracted by addition of ethanol to
solvent that can maximize the extraction of oil. Hexane showed max- the solvent. The process is reportedly fast since extraction is essen-
imum yield of 15.28% when the extraction was run for a duration of tiallyn a diffusion-based process, which means that high diffusivities
30 min. under supercritical conditions lead to faster extraction. On the other
Soxhlet extraction has advantages such as: the same solvent can be hand, the requirement of high pressures limits the cost-efficiency of this
recycled until it is saturated with the analyte, thus making the process process compared to conventional approaches of oil extraction. Also,
economical. Even if certain solvents are used which cannot be recycled since CO2 is non-polar and has limited dissolving power, and therefore
effectively, the sample can be recurrently subjected to extraction by polar solute extraction cannot be carried out using CO2.
313
path of the wave where the perpendicular lines are in proximity to one
another, with the resulting pressure being above regular. On the con-
trary, certain points have been calculated to exist and along them, the
lines seem to be stretched apart, and there the pressure drops to levels
lower compared to normal. The former points are termed as a ‘com-
pression region’ with the latter points being called as a ’rarefaction
region’. The wave travelling through the liquid medium is the energy
spread per unit time per unit area of the bulk liquid which can be linked
with PA in accordance with the Eq. (3):
I= P 2A (2ρc)−1 (3)
Fig. 5. Differences between conventional and microwave heating in terms of
Here, ρ refers to the density of the medium while c denotes the
heat transfer and mass transfer gradients.
velocity of sound travelling through the medium. For ultrasonic waves,
reduction of intensity is inversely proportional to the penetration
3.5.2. Microwave assisted extraction (MAE) through the medium. The sound waves travelling through the medium
Microwave-assisted extraction is a cutting-edge hydro-distillation induce molecular vibrations, which results in the wave losing its in-
procedure which makes use of a microwave oven in the extraction tensity, thereby transforming the lost acoustic energy into thermal en-
process. It has been successfully implemented in the extraction of ergy. Through the bulk of the liquid, heating takes place at the areas
components from plant materials and reported in recent studies, ac- where compression occurs, while cooling occurs at the areas where
cording to Golmakani et al. [111]. Heating using microwaves centres on rarefaction is observed. Heat is generated when the acoustic energy
their direct contact with the polar solvent and/or materials and is degrades by means of absorption, which is in accordance to the Eq. (4):
regulated by two phenomena: conduction through ion movement (also
termed as ‘ionic conduction) and dipole rotation, both ocurring si- I= Io e(−2αd) (4)
multaneously [112]. MAE is efficient, depending on the dielectric
properties of water and the sample [113]. A principle difference be- where the intensity I depends on the distance d from the source of the
tween conventional heating and microwave heating is the direction of ultrasound and α denotes the coefficient of absorption. Ultrasound
heat and mass transfers that occur during the process, with varying conducted through a bulk liquid medium is the root source for the
temperatures through the bulk of the liquid as depicted in Fig. 5. During formation of pressure waves. These result in vibration of the molecules
microwave heating, electrical energy is converted into thermal energy, from their mean position. On application of a huge negative pressure
in which the rate of conversion can be expressed as in Eq. (1): (Pc) on the medium, since Pc (the pressure under rarefaction) = Pa - Ph,
the inter-molecular distances exceed the critical distance (denoted by
P= K f ε E2 (tan δ) (1)
R), which results in the formation of cavitation bubbles, as the mole-
In this equation, tan δ refers to the dielectric loss tangent, E is the cular structure of the liquid is compromised. Even when the negative
strength of the electric field applied, ε denotes the substance’s absolute pressure is greatly reduced, the process of cavitation can still be wit-
dielectric constant, f refers to the applied frequency, K denotes a con- nessed since the gas nuclei (formed from heat fluctuations inside the
stant and P refers to the power dispersion of the microwave per unit bulk liquid) are present as gas bubbles, suspended gas and dissolved
volume of the bulk liquid. gas. The formation of transitory cavities (which last through only one
Conventional procedures requiring more time and resources, MAE acoustic cycle) during the phenomenon of cavitation, is noticeable with
boasts both a high rate and yield of extraction with low solvent re- an increase in the size of the bubble during the acoustic cycle and their
quirement and highly controllable heating process [114]. This mini- collapse into smaller bubbles near the end of the cycle. A collapsing
mizes CO2 emissions [115–117] and consumes only a fraction of the bubble typically needs a shorter duration when compared to the
energy used in conventional extraction methods [118]. The process has acoustic wave period, consequently a constant value for Pm during the
a few shortcomings because the presence of solid residue during the bubble collapse. A notable variable is the liquid pressure during sudden,
extraction process hinders heat and mass transfer. Also, the extraction momentary cavitation bubble collapse, which is summarized in Eq. (5):
process is significantly affected if the solvent or target compounds are
non-polar or if they are volatile. Pm = Ph + Pa . (5)
The time may be depicted as in Eq. (6):

3.5.3. Ultrasound assisted extraction (UAE)
Raw material usually obtained from plants is submerged in a polar t= 0.915 Rm (ρ/Pm )1/2 (6)
solvent (such as water) or non-polar solvent (alcohol or other solvents)
and then made to withstand ultrasonic vibrations [119].Vibrations in- Here, at the instant when it collapses, Rm denotes the radius of the
troduced into a system from an ultrasound source comprise of sound formed cavity. Temperature and pressure inside a typical cavitation
waves within the range of 18 kHz to 100 MHz. When a bulk liquid is bubble approach nearly 4000 Kelvin and 900 bars respectively. The
irradiated using ultrasonic irradiation it leads to the formation of an high temperatures reached inside the cavitation bubbles enhance the
acoustic pressure (Pa), and this extra pressure adds up with the hy- formation of radicles, while the shockwaves resulting from the collapse
drostatic pressure (Ph), already present in the liquid. Acoustic pressure of the cavitation bubbles enhance the overall chemical reactivity [120].
is dependent on the duration of exposure to the ultrasonic waves which UAE increases the extraction of essential oils by facilitating their release
obeys the Eq. (2): from source materials (such as flowers, seeds, leaves, etc.) when used
with a solvent [121,122].
Pa = PA sin 2π ft (2)
The process has low initial investment costs and very fast extraction
Here, PA denotes the upper limit of pressure amplitude of the wave, rate combined with high efficiency. However, the exposure of the oil to
f refers to the frequency when the duration is t. The denotation of sound the ultrasound waves can have deleterious effects on the structure of
waves is usually through sequences of perpendicular lines, where the the compounds present in the oil. Also, the process requires a large
separation between those lines indicate the intensity of the wave, which solvent volume for efficient extraction which adds to the operating cost,
can be correlated with its amplitude. There are certain points along the with repeated extractions required for optimal yield.
314
4. Conventional approaches for biodiesel production 4.2. Micro-emulsions
4.1. Pyrolysis Micro-emulsions represent colloidal dispersions of optically iso-

tropic liquid which exist as microstructures under equilibrium. These
Being a type of destructive distillation [123], pyrolysis is usually are formed impromptu from two immiscible liquids in the presence of
performed in an inert atmosphere within the temperature range of (one or more) ionic amphiphiles. The formation of micro-emulsions
300–1300 °C [124]. Pyrolysis methods have three types of approach, with the use of various alcoholic solvents has been examined by several
which are: conventional pyrolysis occurring within the temperature researchers, with these colloidal microstructures meeting the viscosity
range of 550–900 K, fast pyrolysis occurring within the temperature requisites for commercially usable diesel. It has been demonstrated that
range of 850–1250 K, and flash pyrolysis occurring within the tem- short-term performances for ionic as well as non-ionic micro-emulsions
perature range of 1050–1300 K [125,126]. The technique encompasses of ethanol in soybean oil were experimentally tested. It was found that
a change in chemical structure of the compound, such as cleavage of their performances are comparable to that of No. 2 diesel
chemical bonds to yield small molecules which is essentially irrever- [9,44,71,91,93,99,127]. A few prominent properties tested were
sible. The thermal cracking can occur by the application of heat alone thermal decomposition, cetane number and viscosity, among others
or with the aid of a catalyst along with high temperatures (termed as which helped in establishing performance characterization.
catalytic pyrolysis) [40]. Pyrolysis is used for production of fuel from Arpornpong et al. [330] studied the life cycle of a microemulsion-
material such as animal fats, vegetable oils, triglycerides or natural based biofuel (designated ME50) as an alternative to catalysed or un-
fatty acids. The pyrolysis of organic feedstock for the manufacture of catalysed transesterification processes for biodiesel production, using
synthetic diesel is not viable on an economic scale yet [41]. Sharma palm oil and ethanol. The biofuel was used for an environmental impact
et al. [42] inferred that pyrolysis of vegetable oils is able to yield a assessment right from oil palm cultivation stage to the exhaust emis-
product with desirable properties such as low viscosity, high cetane sions in the usage stage. Comparison of palm oil-ethanol based micro-
number, low quantities of sulphur and water with standard corrosion emulsions (ME50) was done with neat biodiesel (B100) and biodiesel-
values. As discussed by Mohan et al. [329], the pyrolysis of biomass for diesel blends (B50). Evaluation was done regarding various potential
the generation of bio-oil can be done by both conventional and flash environmental impacts (acidification, eutrophication, aquatic and ter-
pyrolysis. Under conventional pyrolysis, the vapour residence time restrial ecotoxicity, human toxicity, GHG emissons etc.) that can be
usually varies between 5 and 30 min, and as such, this contributes to affected during different stages of the production process. According to
overall reaction rate since the components in the vapour phase can their estimations, 1.17 t of ME50 emits 3142 kg of CO2 equivalent
continue to react with each other. Depending on the residence time during its life cycle. The environmental impact analyses revealed that
chosen, the vapours can be removed continuously for periodically. the production of palm oil from the cultivation stage through the oil
Since in flash pyrolysis the rate of heating is very high and the pre- refinery showed highest environmental impacts by eutrophication and
requisite is that heat transfer rates be high, the material needs to be acidification of water. The use of surfactants which are a key element in
finely ground in addition to short vapour residence times (< 2 s) being the formation of microemulsions has significant controbutions to
used. There are a considerable number of pyrolysis reactors being aquatic and terrestrial ecotoxicity. When compared to B50 or B100,
currently used with yields varying from 50 to 70%. These are (1) ME50 also has higher GHG emissions.
Bubbling Fluidized bed, (2) Circulating Fluidized bed, (3) Ablative, (4)
Rorarting cone, and (5) Focussed solar reactor. 4.3. Acid catalysed esterification
Another experimental study conducted by French and Czernik [171]
aimed at the production of biofuels from biomass involving fast pyr- When the acid value is high and the corresponding FFA value is
olysis through the use of zeolite catalyst. In their study they made an more than 2%, base catalysed transesterification is ineffective as it leads
attempt to evaluate quite a large number of catalysts that were either to soap formation (also termed as saponification), hydrolysis and the
commercially available or had been synthesized in the laboratory, generation of waste by-products which further hinder the reaction.
based on their ability to produce hydrocarbons when used in pyrolysis. Thus, yield is lowered significantly, requiring higher amounts of che-
The reaction conditions maintained were a temperature maintained micals, processing for removal of waste and also a longer duration for
within the range of 400−600 °C, while the weight ratio of catalyst: the completion of the reaction. A number of alternate treatment options
biomass was kept at around 5–10. Out of the 40 variations of catalysts are available for feedstock with high FFAs, which are:
taken up for their performance based on the final hydrocarbon yield, Ni
- substituted zeolite catalyst ZSM-5 was observed to provide the best • Esterification with ion exchange resins
deoxygenation, leading to the highest hydrocarbon yield of 16 wt% • Distillation
(approx.) which included a 3.5 wt% toluene when wood was used as the • Acid esterification (coupled with acid transesterification) in the
feedstock. When they operated the process under a semi-continuous presence of alcohols with acids such as sulphuric acid, methane
mode of flow operation, a drop in the deoxygenation activity was noted sulfonic acid, ferric sulphate (which acts as an acid in solution), etc.
with the passage of time, which was due to the deposition of coke on • Neutralisation using alkali after which the soap is separated in a
the catalyst. Bartocci et al. [314] used olive stones for the production of decanter
energy as ‘pyrogas’ via a batch pyrolysis reactor, in which they ob- • Usage of polar liquids for extraction, along with acid esterification
served the following: The feedstock contained a large amount of vola-
tile matter, which was collected in the form ‘pyrogas’ as the final pro- Amongst all of these techniques, acid esterification is easily one of
duct of the pyrolysis process. The pyrogas collected was more than 40% the most effective approach in the reduction of FFA content, in com-
by weight of the biomass used, with significant amounts of methane, bination with the conversion of the triglycerides present in the feed-
carbon monoxide and hydrogen, the result of which was an energy stock. In this paper we refer to the simultaneous process of acid ester-
value of 16 MJ/kg. H2 present in the gas is 29.47% w/w, which can be ification and transesterification simply with esterification process, with
useful if the pyrogas is coupled to fuel cells. Fig. 6 provides a com- occasional additional explanations where the processes differ sig-
prehensive overview as to the different approaches to the production of nificantly. The acids that are widespread for this approach are H2SO4
biodiesel. and HCl. It is worth noting that when acids (homogeneous or hetero-
geneous) are used as the catalyst, there occurs a simultaneous ester-
ification of FFAs as well as the transesterification of triglycerides. This
confers significant advantages over alkali catalysed transesterification
315
Fig. 6. An overview of the different approaches to biodiesel production.
Fig. 7. Mechanism of acid catalysed transesterification for triglycerides and FFAs.
in the production of biodiesel from low cost feedstock since the acid mole of alcohol, resulting in the production of one mole of biodiesel and
catalyst can esterify the free fatty acids even if hydrolysis of the tri- one mole of water. A detailed step-wise mechanism of the acid cata-
glycerides takes place due to the presence of water. It takes place in a lysed processes of esterification of FFAs as well as the transesterification
rather straightforward process, where one mole of FFA reacts with one of triglycerides is depicted in Fig. 7. The esterification reaction can also
316
be summarized in Eq. (7): shortest reaction time. Another experimental study carried out by
Neeharika et al. [128] using methane sulfonic acid for the esterification
R1 – COOH + R2 – OH ↔ R1 – COOR2 + H2O (7)
of Jatropha curcas oil reported similar results with overlapping con-
where R1 can represent any moiety of carbon atoms which may contain clusions.
any number of unsaturations, while R2 is an alkyl group of the alcohol.
The mechanism of the transesterification reaction encompasses a few 4.3.2. Impact of reaction time
steps, starting with the carbonyl group getting protonated, which is Medina-Valtierra et al. [178] used waste rubber tyre cut into small
followed by a production of a tetrahedral intermediate due to the nu- pieces for the development of carbonaceous catalyst by the pyrolysis of
cleophilic attack by methanol. The final step involves the migration of the raw material. The char was then sulfonated with H2SO4, which was
protons along with the breakdown of the intermediate products. The used as a heterogeneous catalyst for the production of biodiesel by si-
sequence of these reactions undergoes 2 more repeats, with the gen- multaneous esterification and transesterification of the waste frying oil.
eration of glycerol and biodiesel. Also, acid esterification can be of two The reaction was observed to be rapid, with only 20 min required to
types: homogeneous acid esterification in which the entire system achieve the maximum yield of 96.5%. This is due to the fact that the
consisting of the reactants and the catalyst are in one phase, and het- rate of mass transfer in the system is high, with methanol reaching
erogeneous acid esterification in which usually the catalyst is itself solid critical levels thereby increasing the miscibility of the methanol in the
in nature or is impregnated into an inert support that acts as surface system. Results reported by them are in agreement with those reported
sites for the reaction to take place. This process also provides more by Bora et al. [132], while the homogeneous esterification process
surface area for reaction. Nevertheless, both homogeneous and het- conducted by Halder et al. [136], Dhawane et al. [133], Karmakar et al.
erogeneous acid catalysis approaches have their own advantages and [134] and Chuah et al. [130].
disadvantages. A lot of research articles are available suggesting that
acid esterification is indeed effective in biodiesel production from a
4.3.3. Impact of alcohol: oil ratio
wide variety of sources. Studies by Neeharika et al. [128], Sendzikiene
In the two step catalytic production of biodiesel using waste frying
et al. [129], Chuah et al. [130], Ridha et al. [131] and Bora et al. [132]
oil, the untreated waste oil had an acid value of 32.82 mg KOH/g. This
confirm the efficiency of acid esterification in the production of bio-
was reduced to a value below 2 mg KOH/g in the pre-treatment step
diesel. As evident from the comparative studies of Dhawane et al. and
involving acid (H2SO4) esterification, which corresponds to an FFA
Karmakar et al. performed on waste cooking oil and castor oil respec-
concentration of less than 1%. After the pre-treatment, base catalysed
tively [133,134]. The homogeneous system has significantly higher
transesterification of the triglycerides present in the oil could be suc-
yields for a single run while the heterogeneous system boasts reusability
cessfully carried out. A maximum FAME yield of 93.32% was obtained
and ease of separation of the products. Acid esterification can also be
when the temperature of the reaction was kept at 60 °C, the reaction
used (in combination with alkali-catalysed transesterification) as a pre-
having being carried out for a duration of 1 h with a methanol:oil molar
treatment step for feedstock with high FFAs containing high amounts of
ratio of 14.71:1 after the addition of 1% w/w H2SO4, while the rate of
triglycerides that need to be transesterified by bases for high yield of
stirring was kept at 800 rpm. The results obtained are in agreement
fuel-grade biodiesel. Studies by Wan Omar et al. [135] and Halder et al.
with the works of Wan Omar et al. [135], who used ferric sulphate as an
[136] confirm this application of the process.
acidic catalyst to esterify waste cooking oil, having obtained a yield of
The vast amount of available literature suggests that quite a number
81.3% under similar reaction conditions. Studies reported by Berrios
of parameters dictate the outcome of the process of esterification, af-
et al. [174], Neeharika et al. [128], Ramachandran et al. [175] and
fecting the yield of the biodiesel significantly. Therefore, it is im-
many others clearly demonstrate that a high alcohol:oil ratio must be
perative that these process parameters be optimized to attain the best
maintained for the reaction to proceed towards the formation of pro-
results. Table 6 lists the various relevant research works that have been
ducts.
reported on acid catalysed esterification so far.
4.3.4. Impact of catalyst concentration

4.3.1. Impact of reaction temperature Bora et al. [132] performed the esterification of Mesua ferrea linn
Halder et al. [136] studied the esterification of castor oil as a pre- (MFL) oil using finely ground shells of the MFL seeds as a carbon based,
treatment step for the removal of high amounts of FFAs contained in it, heterogeneous catalyst. Using a variety of concentrations of H2SO4 as
to make the oil suitable for a subsequent alkali-catalysed transester- the acid which had been impregnated onto the carbon catalyst using the
ification step. They utilized RSM 24-full factorial CCD approach in the process of sulfonation. They observed that concentration of the acid
designing of their experiments. Observations made by them were: catalyst was a prime factor in determining the efficacy of the process
Within their chosen temperature range of 40–70 °C, the maximum and the FAME yield. They obtained maximum yield of 95.57% when
conversion of the FFAs present in the oil was when the temperature of the catalyst was maintained at a concentration of 10% w/w. The results
the reaction was kept at 50 °C. Their observations led them to the reported by them are in agreement with those of Dhawane et al. [133]
conclusion that high temperature would favor a forward reaction under and Karmakar et al. [134], who used H2SO4 as a homogeneous catalyst
conditions exceeding 0.1 MPa of pressure, which was not the case in for the esterification process, as well as those obtained from the ex-
their study. The conclusions made from their results were found to be in periments conducted by Ramachandran et al. [175] who used solid
agreement with those of Leung and Guo having experimented with neat aluminium bisulphate [Al(HSO4)3], obtained from the sulfonation of
canola oil and waste frying oil [173]. The studies by Dhawane et al. AlCl3 as a heterogeneous catalyst to obtain methyl esters from mixed
[133] and Karmakar et al. [134] made on waste cooking oil and castor waste vegetable oil. Experiments conducted on Hevea brasiliensis
oil using L9 and L16 Taguchi approach respectively, also how that the (rubber seed) oil from Malaysia (designated RSOM) and Vietnam (de-
temperature of the reaction is a significant factor in the homogeneous signated RSOV) by Chuah et al. [130] also showed similar results, since
acid esterification of high FFA oils, with high temperatures impeding the maximum reduction of the FFAs contained in RSOM was at 0.5% w/
the reaction due to evaporative loss of the alcohol used (methanol). w of acid concentration, while in the case of RSOV it was at 12% w/w;
They obtained a FAME yield of 95.376% w/w and 90.83% w/w when with higher amounts of acid having negligible to detrimental effects on
the temperature of the reaction was maintained at 60 °C and 50 °C the conversion of FFAs and lower amounts being insufficient for the
correspondingly. Reports stated by Berrios et al. [174] who used sun- reaction. The conclusions drawn by them were congruent to those
flower oil for their kinetic studies on esterification using H2SO4 showed drawn by Ramadhas et al. [176] and Morshed et al. [177] whose ex-
that a temperature of 60 °C gave the required FFA value below 1 in the periments on RSO led to similar results.
317
B. Karmakar, G. Halder
Table 6
Acid esterification for biodiesel synthesis / FFA reduction (pre-treatment).
Feedstock Catalyst used Reaction conditions Yield/Conversion (%) References
Reaction temperature Reaction time (h) Catalyst concentration (% w/ Alcohol : oil Agitation speed
(°C) w) Ratio (rpm)
Castor oil Concentrated H2SO4 50 2.09 1 15:1 700 73.27 [136]

Waste cooking oil Concentrated H2SO4 60 3 5 12:1 800 95.376 [133]
Sunflower oil Oleic acid 60 2 5 60:1 600 > 90 [174]
Waste vegetable oil Aluminium bisulphate [Al(HSO4)3] 220 0.83 0.5 16:1 – 81 [175]
Jatropha oil Methanesulfonic acid 60 4.5 1 20:1 400 97.9 [128]
Rubber seed oil (Malaysia) Concentrated H2SO4 50 2 1.38 15.98:1 400 99.3 [130]
Rubber seed oil (Vietnam) 65 1 10.74 10:1 98.6
Waste vegetable oil Sulfonated char (from waste rubber tyres) 210 0.33 0.04 Large excess – 96.5 [178]
Waste frying oil Concentrated H2SO4 60 1 1 14.71:1 800 93.32 [131]
Waste cooking oil Ferric sulphate 60 3 0.009 7:1 –_ 81.3 [135]
Calophyllum inophyllum oil Sulfonated char (from C. inophyllum seed 180 4 7.5 30:1 – 99 [180]
cake)
Palm fatty acid distillate Sulfonated activated carbon (from coconut 60 2 10 12:1 500 91 [200]
318
(PFAD) shell)
Canola oil Sulfonated biochar (using fuming/ 60 3 5 18:1 – 92 [201]
concentrated H2SO4)
Rapeseed oil Cellulose derived sulfonated carbon catalyst 65 6 20 20:1 600 93.4 [202]
Waste cooking oil Xylose derived sulfonated carbon catalyst 110 4 10 10:1 500 89.6 [203]
Microalgal oil Sulfonated biochar (from Douglas fir wood) 100 1 5 10:1 300 98.2 [204]
Palm fatty acid distillate Sulfonated carbon (derived from starch 75 3 2 10:1 600 94.6 [205]
(PFAD) solids)
Waste cooking oil Mesoporous carbon supported FeSO4 80 6 3 30:1 – 98.4 [206]
Waste cooking oil Sulfonated biochar (from oat hull) 140 0.25 10 10:1 – 90 [207]
Waste cooking oil Sulfonated rice husk char 110 15 5 20:1 – 87.57 [208]
Palm oil Sulfonated graphene catalyst 100 14 10 20:1 – 98 [209]
Waste fish oil Sulfonated activated carbon 55 1 11.04 14.85:1 – 88 [210]
Canola oil Sulfonated carbon catalyst (from de-oiled 65 24 7.5 60:1 600 93.8 [211]
canola meal)
Castor oil Concentrated H2SO4 50 1 1 20:1 700 90.83 [134]
Sulfonated char (from Mesua ferrea linn seed 71.23
shells)
Mesua ferrea oil Sulfonated char (from Mesua ferrea linn seed 55 2 10 6:1 – 95.57 [132]
shells)
4.3.5. Impact of agitation speed every step of the process of transesterification is reversible in nature,
The process of acid esterification for the conversion of FFAs present the addition of an excess of alcohol in addition to a catalyst (an alkali)
in the sample oil into their respective methyl esters is hardly sponta- [169] leads to an acceleration of the forward reaction, shifting the
neous enough to take place without the reactants being subjected to equilibrium to the right, thereby increasing the rate of formation of
some agitation or mixing. Aldo et al. [179] utilized a RSM 23-full fac- products. Under such a condition, the forward reaction tends to follow
torial design in order to optimize the production of biodiesel from Ja- pseudo-first order rate law while the reverse reaction has been observed
tropha oil. They noted that agitation speed, temperature of the reaction to adhere to follow second order rate law.
and molar ratio of methanol to oil were the significant parameters af- Fig. 9c is the diagrammatic illustration of the mechanism of a
fecting the process. Under a reaction temperature of 54 °C, methanol of generalized transesterification reaction with an alkali as the catalyst. In
oil ratio of 6:1 and an agitation speed of 660 rpm, a maximum biodiesel the first step, the alkoxide ion attacks the carbonyl carbon of the tri-
yield of 95% was obtained. The results obtained by them are in ac- glyceride molecule, leading to the formation of an intermediate with
cordance with those with those obtained by Karmakar et al. [134], and tetrahedral structure. This intermediate compound can now react with
Halder et al. [136] who esterified castor oil under different conditions. an alcohol to yield another alkoxide ion. Finally the tetrahedral inter-
Ramachandran et al. [175] esterified waste vegetable oil using alumi- mediate undergoes a structural rearrangement, which finally leads to
nium bisulphate as a catalyst and noted that mass transfer limitations the formation of a diglyceride in addition to an ester [99]. The process
play a vital role in hindering the progress of the reaction, hence higher continues with the further breakdown of diglycerides and mono-
agitation speeds are needed to overcome these limitations and obtain glycerides to yield 3 mol of biodiesel and 1 mol of glycerol.
higher conversions of FFA into fuel-grade FAME. The process of base catalysed transesterification is significantly af-
fected by the FFA and moisture content. For effective progress of the
reaction the FFA value should be less than 2%, with FFA value being
4.4. Base catalysed transesterification inversely proportional to conversion efficacy [145]. Transesterification
studies of beef tallow catalysed by NaOH both in the presence and
The process of transesterification (also termed as ‘alcoholysis’) in- absence of FFA and water was done by Ma et al. [148]. They observed
volves exchanging the alkyl group in an ester by the alkyl group of the that in the absence of FFA and water, yield of beef tallow methyl esters
reacting alcohol with the formation of fatty acid alkyl esters and gly- (BTME) was maximum. With the addition of 0.6% FFA, BTME yield was
cerol [6]. The wide use of this process is for the reduction of the high at minimum of 5% or lower, irrespective of the water content. With the
viscosity of triglycerides. The process undertaken for feedstock selec- addition of only 0.9% water, the yield dipped to approximately 17%,
tion, analysis for its suitability to be transesterified and the final pro- even in the absence of FFAs.
duction collection is summarized in a procedural flowchart as in Fig. 8. Dhawane et al. used activated carbon derived from waste flam-
Triglyceride transesterification leads to the production of alkyl esters of boyant pods impregnated with KOH as heterogeneous catalyst for
fatty acids (FAAE) with the simultaneous production of glycerol. Since transesterification of Hevea brasiliensis (rubber seed) oil and obtained
the glycerol layer is heavy, it forms a layer at the bottom when kept 89.81% yield of biodiesel under optimum conditions [156]. Ramezani
standing for separation in a separating funnel. The reaction has 3 steps, et al. performed transesterification of castor oil using four basic cata-
with the first step producing diglycerides as intermediates, after which lysts which were NaOH, KOH, NaOCH3 and KOCH3 in order to identify
these diglycerides are utilized to produce FAAE with monoglycerides as the most effective catalyst with maximum biodiesel yield under op-
the intermediates in this process. The overall reaction taking place timum conditions. It was noted that KOCH3 emerged as the most effi-
during transesterification can be seen in Eq. (8) and Fig. 9a: cient catalyst among all of the bases used [157]. For every experimental
study, parameters such as reaction time, temperature, catalyst con-
RCOOR1 + R2OH ↔ RCOOR2 + R1OH (8)
centration, mixing intensity, molar ratio of oil to alcohol etc. were the
Which depicts methanolysis (since methanol is being used), with parameters that were taken into account for their effect on biodiesel
Fig. 9b depicting stepwise transesterification of the triglycerides. Since yield [313]. Al-Hamamre et al. [315] used the oil extracted from spent
coffee grounds for the production of fuel-grade FAME using both one-
step and two-step alkali catalysed transesterification. They observed
that in two-step alkali catalysed transesterification, the pre-treatment of
the oil with H2SO4 results in the reduction of FFAs present in the oil by
esterification into FAME. The esterified oil can then be subjected to
further conversion to biodiesel using KOH (1.5% w/w) in the presence
of methanol at 6:1 M ratio, for a duration of 6 h at 60 °C under an
agitation speed of 800 rpm. The various relevant research findings for a
wide variety of feedstock used for biodiesel production via base-cata-
lysed transesterification have been listed in Table 7.
4.4.1. Impact of reaction temperature and time

In some studies, temperature of the reaction was seen to have a
solitary effect with low regard to the variation of other reaction para-
meters. Dhawane et al. [183] undertook an experimental study on the
synthesis of Hevea brasiliensis methyl esters (HBME) from its raw oil.
They varied the temperature of the reaction at 50 °C, 55 °C and 60 °C.
The highest yield of 90.61% was noted at 60 °C, when the other factors
impacting the reaction were kept at their respective optimum levels.
Below 60 °C, the yield variation was very less, being only 1% from 50 to
55 °C, with a stark rise at 60 °C. This can be easily understood as the
reaction rate improves with an increase in temperature, with increases
beyond this point leading to a decline in the yield due to evaporative
methanol losses, the boiling point of methanol being 64.7 °C. In another
Fig. 8. Flowchart of the alkali catalysed transesterification process. of their studies [182], they obtained similar results with rubber seed oil
319
Fig. 9. (a) Overall reaction for transesterification with methanol (methanolysis) (b) Step-wise production of alkyl esters from triglycerides in transesterification (c)
Mechanism of a generalized transesterification (alkali catalyst).
320
B. Karmakar, G. Halder
Table 7
Base catalysed transesterification for biodiesel synthesis.
Feedstock Catalyst used Reaction conditions Yield/Conversion (%) References
Reaction temperature Reaction time (h) Catalyst concentration (% w/ Alcohol : oil Agitation speed
(°C) w) Ratio (rpm)
Rubber seed oil Iron (II) doped activated carbon 55 1 5 12:1 1000 96.1 [181]
Rubber seed oil Activated carbon impregnated with KOH 60 1 3.5 15:1 750 89.3 [156]
Rubber seed oil Activated carbon impregnated with KOH 55 1 3.5 15:1 750 89.81 [182]
Rubber seed oil Iron (II) doped activated carbon 60 1 4.5 9:1 1250 97.5 [183]
Castor oil CH3OK 65 0.17 1.5 7:1 600 99.81 [184]
Castor oil CH3OK 65 2 0.5 8:1 400 87.3 [157]
Castor oil Sodium methoxide 40 1.5 1 5:1 800 85 [185]
Waste vegetable oil CaO from calcined egg shells 65 5.5 3.5 22.5:1 600 90.98 [186]
Sunflower oil KOH 48 2 0.679 6.8:1 290 98.18 [187]
Manilkara zapota oil KOH 50 1.5 1 6:1 – 94.83 [188]
Crude acorn (Quercus frainetto L.) KOH 50 0.67 0.7 8:1 600 90 [189]
321
kernel oil
Camelina sativa oil KOH 38.7 0.67 1.5 7.7:1 300 97 [190]
Waste cooking oil KOH 50 1.5 0.75 8:1 – 90 [191]
Safflower oil Sodium methoxide 60 2 1 6:1 600 98 [192]
Waste cooking oil CaO (from calcined chicken manure) 65 6.5 7.5 15:1 1400 90.8 [193]
Oil from waste Date pits KOH impregnated Date pit biomass 65 1 6 9:1 – 91.6 [194]
Canola oil Alumina (Al2O3) impregnated with 60 8 3 15:1 600 99.6 [195]
potassium fluoride
Bitter almond oil Activated carbon loaded with potassium 65 2.5 2.5 9:1 600 93.21 [196]
acetate
Soybean oil Calcium methoxide 65 1.5 1 9:1 1000 > 90 [197]
Palm oil KOH 60 1 1 6:1 – 88 [198]
Soybean oil KNO3 loaded on alumina (Al2O3) 55 7 6.5 15:1 600 87 [199]
Palm oil KOH supported on palm shell activated 64.1 1 30.3 24:1 700 98.03 [212]
carbon
Canola oil Potassium glyceroxide 60 90 0.36 6:1 1000 95 [213]
Palm oil CaO obtained from waste venus clam 65 6 5 15:1 600 97 [214]
Pumpkin seed oil Nano CaO catalyst 60 1 1.5 9:1 – 97.5 [215]
being subjected to transesterification using KOH impregnated AC cat- final yield. They observed that the parameters (as ‘linear-model terms’)
alyst derived from waste flamboyant pods under a Taguchi L9 ortho- can be arranged according to their order of significance as: catalyst
gonal array approach. concentration > time > temperature > molar ratio of methanol to
Other research works show a combined or synergistic effect of the oil. It was also noted that for all the process parameters, the obtained p-
temperature and the duration of the reaction. It is notable that an in- value from the statistical ANOVA analysis was lower than 0.05, which
crease in the temperature of the reaction results in a rise in the rate of meant that each of them had contributed significantly to the enhance-
the reaction, thereby the reaction should, theoretically, require a ment of the biodiesel yield. The observations made it clear that the
shorter duration for its completion [99,221]. It is possible to obtain concentration of the catalyst was the key factor that determined the
maximum yield at a variety of temperatures, which is directly de- impact on both the biodiesel yield as well as the FAME content of the
pendant on the type of oil used for the transesterification process. The product. Also, the research carried out by Wu and Leung, who used
process can be carried out at ambient temperature (the reaction mixture orthogonal design of experiments for biodiesel production from Came-
not exceeding 50 °C) [222] or close to the boiling point of the alcohol lina oil [217], is in proper agreement to this study. From the reports of
[218,223]. According to the observations made by Freedman et al. Bautista et al. [216] who used KOH for the transesterification of used
[141], the yield of the biodiesel seemed to be dependent on the reaction cooking oil, the concentration of the catalyst (KOH) had the highest
temperature while the reaction is in its initial phase, such the first influence in both the biodiesel yield as well as the ester content.
30 min. In the experimental study conducted by Phan et al. [191] on According to experimental observations revealed by Felizardo et al.
waste cooking oil by transesterification using KOH, they observed that [218], for obtainance of highest amounts of FAME, the optimum
under the reaction temperatures of 32 °C, 45 °C and 60 °C, the yield of quantity of NaOH to be used was 0.6 wt%. The studies of Leung et al.
the product (methyl esters usable as biodiesel) were 64%, 87% and 94% [173] on neat canola oil as well as used frying oil revealed the effect of
correspondingly. Since an increase in the reaction temperature is the loading of NaOH. Results obtained by them demonstrated the op-
known to augment both the rates of transesterification and saponifi- timum catalyst concentrations to be 1.0 wt% and 1.1 wt%, corre-
cation, further increase beyond 60 °C in case of this study (using me- spondingly. With the data from above-mentioned literature at disposal,
thanol) was not performed. Phan et al. [191] transesterified waste cooking oils with KOH, ranging
Rashid et al. [192] used different types of basic catalysts for the between concentrations of 0.5–1.5 wt% of the oil. When the reaction
transesterification of safflower oil and noted that under different re- was carried out for 2 h, they saw a yield of 82% and 90% under a KOH
action temperatures used in the experiments, all of them showed a si- load of 0.5 wt% and 0.75 wt% respectively. As expected, the conversion
milar progression of the transesterification up to 80% in the first 10 min observed a decline to 75% under 1.5 wt% load of KOH. Similar to
of the reaction, regardless of the temperature of the mixture. However, above-mentioned works, this is due to the formation of soap during the
after a total runtime of 2 h, the rate of conversion to esters were dif- progress of the reaction.
ferent for each temperature, with the highest yield obtained at 60 °C.
This further provided proof that the duration and temperature of the
4.4.3. Impact of alcohol: oil ratio
reaction have a synergistic effect on the outcome of the reaction. The
Centikaya and Karaosmanoglu [219] observed that the transester-
results obtained and the conclusions drawn by them are in agreement
ification reaction proceeds at an insufficient rate even when the oil to
with the works of Boz and Kara [195] as well as Mannerung et al. [193]
alcohol ratio is kept at 1:5, with higher ratios showing a significant
who observed that even at 45 °C, the transesterification proceeded to
improvement in the ester yield. Nevertheless, in order to shift the
completion if the reaction was continued for 8 h, while obtaining the
equilibrium of this reversible reaction towards product formation, a
highest yield at 65 °C under high reflux conditions. However thee stu-
great excess of alcohol is required to drive the equilibrium towards the
dies by Xie et al. [199] showed that within a duration of 1 to 20 h, the
formation of products. In the experiments carried out by Dhawane et al.
reaction attains an equilibrium after 7 h, the yield thereafter remaining
[181] who carried out the transesterification of rubber seed oil using
constant at 87%.
KOH impregnated AC catalyst derived from waste flamboyant pods, the
ratio was varied at 3 different levels of 7:1, 11:1 and 15:1 while the
4.4.2. Impact of catalyst concentration other parameters for the reaction were maintained at constant opti-
From the work undertaken by Dhawane et al. [182] on the synthesis mized conditions. Till the molar ratio of 11:1, the yield of esters im-
of Hevea brasiliensis methyl esters (HBME) from its raw oil (used as the proved from 76.6% to 80.44% with increasing ratio. On carrying out
feedstock), the concentration of the catalyst seemed to play the most the reaction in a 15:1, the yield drastically reduces to only 1.76% of
influential role on the yield percentages of HBME. They studied catalyst HBME. This may be attributed to the problems encountered in se-
load at values of 1.5 wt%, 3.5 wt% and 5 wt% while other parameters paration of the glycerol [181,220]. In another work by Dhawane et al.
affecting the reaction were kept constant. From their observations, the [181] employing Fe(II)-doped AC catalyst from waste flamboyant pods
yield of HBME reportedly improved from a value of 76.6% at 1.5 wt% to produce biodiesel from rubber seed oil, they observed similar results
to 82.68% at 3.5 wt%, which showed a marginal decline of only 0.3% as in their previous work, since the ratio in moles of oil to methanol
(of yield) as the concentration was changed to 5 wt%. Catalytic leaching impacted the RSME yield to the greatest extent. The results obtained by
causes this decrease, the catalyst having been provided in excess to the them strongly resembled to the pattern of those obtained from their
reaction requirements leading to saponification, thereby hampering the above-mentioned experiment, with inevitably similar conclusions.
progress of the reaction. Fig. 10 depicts the saponification of FFAs by According to the results reported by Phan et al. [191] who used
alkali radicals in water, leading to the formation of soap. waste cooking oils as the feedstock for their transesterification into
Yang et al. [190] conducted experiments on Camelina sativa oil biodiesel, a rise in the alcohol to oil ratio from 5:1 to 8:1 led to an
using a central composite design (CCD) approach to establish the in- improvement in the percentage of conversion. From a conversion of
dividual as well as interactive effects of the process parameters on the 50% for when the ratio was maintained at 5:1 to that of 64% when the
Fig. 10. Saponification of FFAs by radicals

formed by alkali catalyst in water.
322
ratio was increased to 8:1 under a reaction time of 2 h, the improve-
References
ment in the percentage of conversion was around 24% for the first hour,
[224]
[225]
[226]
[227]
[228]
[229]
[230]
[231]
[232]
[233]
which dipped to around 13–16% for the final hour. Expectedly, in-
creasing the methanol:oil molar ratio from 8:1 to 9:1 showed a mar-
ginal improvement by less than 2% of the percentage conversion into
Yield/Conversion
methyl esters, while beyond the 9:1 ratio, the yield fell due to the same
problems as discussed above. An additional observation made by them
was that an increase in the molar ratio of methanol and oil also led to an
85.68
86.61
92.07
85.29
enhancement in the process of separation of the biodiesel and glycerol
96.8
100
100
(%)
94
92
94
phases. For the molar ratios below 7:1, the process of settlement took
hours to be completed appreciably, while the same process was com-
plete within 30 min for the ratios beyond 7:1. The ester layer also
Agitation speed
showed the presence of some unreacted (mono, di- or tri-) glycerides for
the reactions carried out at methanol:oil molar ratios below 7:1.
(rpm)
100
200
200
200
300
250
250
4.4.4. Impact of agitation speed
–
–
–
When the reactants are viscous, mass transfer becomes a limiting
factor in the progress of the reaction, since the reactants do not interact
Alcohol : oil
frequently enough for the formations of products. In case of feedstock
with high viscosity, the agitation speed therefore plays a pivotal role in
Ratio
20:1
10:1
12:1
6:1
4:1
4:1
6:1
4:1
6:1
6:1
overcoming the mass transfer resistances, thereby impacting the yield
of RSME. From the results reported by Dhawane et al. [183] who
transesterified Hevea brasiliensis oil using Fe(II)-doped AC catalyst de-
Catalyst concentration (%
rived from waste flamboyant pods, under an agitation of 1250 rpm, the
highest yield of RSME was noted to be 89.27%, while the concentration
of the catalyst was kept at a value of 4.5 wt%, the temperature of the
reaction was maintained at 50 °C and the molar ratio of oil to methanol
was 1:9. It was noted that the RSME yield improved with increasing
w/w)
agitation, which led to the inference that higher agitation speeds in-
3.6
1.5
10
20
5
6
3
1
creased the turbulence in the reaction mixture, which provided good
mixing and interactive collisions of the reactants, and as mentioned
Reaction time
above, helped overcome the mass transfer diffusional resistances en-

countered due to the viscosity of the reactants. This led to the en-
hancement of the reaction rate, thereby improving the conversion rate
0.33
0.33
(h)
10
36
40
32
60
until the agitation was continued beyond 1250 rpm, in which case
8
8
leaching of the catalyst occurs into the reaction mixture in addition to
the developed shear stress hindering the progress of the reaction. The
Reaction temperature
Reaction conditions
leaching directly resulted in the saponification of the oil which desta-

bilized the molar ratio and led to a decline in the yield observed [182].
Atmospheric
Atmospheric
4.5. Enzyme catalysed transesterification

(°C)
35
60
40
50
35
40
45
40
The problem with transesterification using chemical catalysts is that
Immobilized lipase on carbon nanotubes (CNT)
Immobilized lipase (from whole R. mucilaginosa
the effectiveness of the approaches are hampered due to the generation

Novozym 435 lipase [from Candida antarctica
Candida antarctica B lipase (immobilized on
of waste water, which needs to be treated before safe disposal. When

Lipase [from Candida antarctica Lipase B
Lipase [from Candida antarctica Lipase B
Lipase (from Chromobacterium viscosum)
compared to acids and alkali as catalysts, enzymes offer certain benefits

in that they do not saponify the oil and can convert both triacylgly-
Lipase supported on granular AC
cerols and free fatty acids into their esters in a single step with the
Enzyme catalysed transesterification for biodiesel synthesis.
process not needing a washing step later. This makes enzymes a lu-
Crude lipase from palm oil
crative choice for reducing production charges, which can be appre-

ciated when feedstock that contain high amounts of FFA such as mahua
mesoporous foam)
Lipase B (CALB)]
oil, rice bran oil, as well as spent oils and animal fats, which un-
Catalyst used
fortunately have questionable quality for use as raw material, as well as

yeast cells)
being complicated to transform using catalysts [141,142]. Nevertheless,

(CALB)]
(CALB)]
Lipase
they need to be utilized to avoid problems such as water and soil pol-
lution if discarded into the environment [139,140]. The use of waste
oils is a laudable choice since virgin oils cost more compared to waste
oils, while pressure on land used for crop cultivation is also reduced
Marine microalga Chlorella
[143–145]. The various relevant research works reported on enzyme

catalysed biodiesel synthesis from various feedstock have been listed in
Waste vegetable oil
Table 8. When paralleled to acids or alkali (both homogeneous and

Waste beef tallow
Waste cooking oil
heterogeneous), enzymes have been more successfully utilized as cat-

salina oil
Jatropha oil
Avocado oil
alysts, since they:

Waste lard
Feedstock
Castor oil
Palm oil
Palm oil
Table 8
• Require a low oil to alcohol molar ratio, with the ability of transe-
seterifying both triglycerides and FFAs
323
• Have increased versatility which can accommodate disparities in the cellulose. Reportedly, after a reaction duration of 12 h under an op-
raw material quality and are also reusable through de-emulsification timum temperature of 20 °C, they obtained a yield of 92% [152]. When
or other down-streaming processes the optimum temperature is lower, it greatly affects the energy con-
• Require a low reaction temperature with appreciably high alkyl straints for the process since it is lowered. Also, it causes a shift in the
ester yields, in addition to low product inhibition ecology, since many geographical locations are both excluded as well as
• Are capable of producing biodiesel through the use of lesser pro- included. Nelson et al. used tallow as a feedstock [284] which was
cessing stages, thereby consuming less energy transesterified using lipase extracted from Candida antarctica, which is
• Increase the ease of separation of products leading to the yield of commonly known as Novozyme 435. Findings by them show an yield of
high-quality glycerol [5,146–148] biodiesel around 96% when the temperature of the reaction was
• Are insensitive to the presence of water and FFAs in the feedstock, maintained at 45 °C, with a feedstock-to-alcohol molar ratio of 1:3, with
thereby reducing the chances of saponified product formation and the duration of the reaction approximating at around 16 h, using an
hydrolysis agitation speed of 200 rpm. It was further noticed that adding 6 mol%
of water resulted in the improvement in the production of esters. The
The use of enzymes has a few shortcomings: observation can be attributed to the fact that water essentially enhances
the activity of the enzyme. The marine lipase extracted from Bacillus
• A low rate of reaction, especially when immobilized for enhance- pumilus (strain B106) was shown to have high temperature, salinity as
ment of their reusability [142] well as pH tolerance, as was observed from another study which ex-
• Their cost, since acids or alkali are quite cheaper compared to en- plored its activity [153]. Other sources such as Aspergillus niger, Rhi-
zymes [5,99,146,149,150] zopus spp. and Penicillium spp. can be used for the economical pro-
• A problem concomitant with enzymes is their loss in activity, which duction of lipases using the technique of solid state fermentation [154].
may be gradual. This depends typically on the number of days of For a detailed, in-depth understanding, the reaction mechanism and
operation with the enzyme as well as their shelf life kinetics should be studied properly [155].
In addition to the extracellular enzymes produced by the different
In these type of reactions, lipase is the enzyme of preference. Being microbial strains, the use of immobilized whole cell enzymes (also
plentiful in nature, it can be obtained from microorganisms, plants and known as intracellular enzymes) is also popular for the obtainance of
animals [151]. For the production of biodiesel, lipases used must be biodiesel from both triglycerides and FFA. From the studies available, it
non-stereospecific, thus they can convert every mono-, di- and trigly- is clear that the intracellular enzyme approach is far more effective than
ceride to fatty acid alkyl esters (FAAE), in addition to catalysing the use of extracellular enzymes, since no separation and purification is
esterification of FFA present in the feedstock. Fig. 11 provides a sim- required before and after their use. The technique of enzyme im-
plified overview at the process of enzyme catalysed transesterification mobilization has a wide variety of approaches, which can be adsorption
for biodiesel production. [276], cross-linking [277], entrapment, and ion exchange [278]. All of
Fungal and bacterial lipases are mostly used as catalysts in enzyme the approaches make use of a solid support, which can be natural or
catalysed transesterification reactions. Since the formulation of the li- made up of a synthetic material such as glass or calcium alginate.
pase can vary to a great extent depending on its origin, the parametric Rhizopus oryzae has been extensively studied by quite a number of
optimization for its usage depends on these factors. Commonly, high- researchers who used immobilized whole cells for enzymatic transes-
grade enzymes can achieve conversions exceeding 90%, with reaction terification of the feedstock for the production of biodiesel. Matsumoto
temperatures between 30 and 50 °C. The duration of reaction can vary et al. [279] used immobilized R. oryzae cells, reportedly getting a
from as low as 8 h to around 90 h. Therefore it can be inferred that apart biodiesel yield of 71% under reaction conditions of 37 °C after 165 h of
from the lipase’s origin, other factors such as reaction temperature, reaction time. Another study reported by Ban et al. [280] showed that a
immobilization of the enzyme, and the type of alcohol selected have an high yield of up to 90% conversion to biodiesel is possible using R.
impact on the final yield of biodiesel, the duration required for the oryzae cells. A different approach of examining the effectiveness of
reaction to be complete and the longevity of the enzyme. From avail- cross-linking of the R. oryzae cells and addition of 0.1% glutaraldehyde
able literature, it is apparent that a vast number of sources and tech- for stabilization of the cells was undertaken by Ban et al. [281]. The
niques are at disposal to researchers worldwide in the approach of observations were: a conversion of only 50% in the absence of cross-
transesterification using enzymes for biodiesel production. Lipase pro- linking, while, cross-linking enhances the conversion up to 83%.
duced from a psychrophilic strain of Pseudomonas fluorescens (strain The use of higher ratios of alcohol in enzyme catalysed systems
B68) was isolated and screened by Luo et al. The lipase, designated as shows a sharper detrimental impact on the biodiesel yield because the
lipB68, was used for biodiesel production through the process of addition of excess alcohol (than is stoichiometrically required) leads to
transesterification while being immobilized on fabric made from an inhibitive effect of the enzymatic activity by the polar short chain of
alcohol, thereby hindering glycerol separation [282,283]. Therefore,
for enzyme catalysed transesterification reactions, the molar ratio of
alcohol to oil required is much lower than compared to acid/alkali
catalysed systems [285]. Also, among the various alcohols used such as
methanol, ethanol, propan-1-ol, propan-2-ol, n-butanol, isobutanol etc.,
methanol seems to be the preferred choice since it shows a high re-
activity as well as low cost. It was shown by Nelson et al. [284] that
short-chain alcohols inactivate enzymes more easily than longer ali-
phatic alcohols. For overcoming the hindrances of methanol inhibition,
a few steps can be ensured that include:
1. Addition of methanol over a few steps [284,286,287]

2. Using an appropriate solvent [288]
3. Using longer chain alcohols [289]
Using solvents like chloroform, benzene, n-heptane and hexane can

Fig. 11. A simplified look at the enzyme catalysed transesterification process. also lead to a reduction in methanol inhibition because the lipase is
324
protected from denaturation since the solubility of the methanol is treatment steps [162]. This further cuts down on the production
improved. Also, the lipase catalysed reactions are not inhibited due to costs.
an increase in the solubility of the glycerol which leads to the formation 3. For both SCF and SHV, the rate of reaction is much higher than
of a single fluid phase [290,291]. The studies by Soumanou and catalysed approaches.
Bornscheuer on the impact of organic solvents [292] such as n-hexane
and petroleum ether or tert-butanol on the conversion of sunflower oil However, SCF requires a huge initial investment cost for the setup
using Pseudomonas fluorescens led to findings that a conversion of up to and requires high standard equipment that can withstand the high
80% biodiesel is possible through the addition of n-hexane and petro- temperatures and pressures involved in its operation. Here, SHV ap-
leum ether, while adding tert-butanol also enhances biodiesel yield. proach is the better alternative since the reactants do not need to attain
When the reaction was performed with a solvent-to-oil volumetric ratio supercritical state, nor are high pressures involved which would require
of 0.8:1 at 55 °C with the reaction taking 48 h to provide a maximum expensive, reinforced equipment to ensure safety and avoid losses due
yield of 94% [293]. In another study, adding 2-ethyl-1-hexanol led to to leakage.
an improvement in the production of biodiesel from rapeseed oil, with a
maximum conversion of 97% [294]. 6. Supercritical transesterification
5. Modern approaches for biodiesel production 6.1. A first look – Superiority over catalysed processes
Catalytic transesterification or esterification processes come with a The processes described earlier have their own disadvantages.
lot of disadvantages, each process with its specific set of drawbacks. In Uncatalyzed pyrolysis has the hindrances of low yield combined with
common all of these have one major disadvantage which is the se- formation of undesirable by-products. Also, the process is very low in its
paration of the catalyst after the reaction is complete, be it a homo- efficiency since a lot of energy is lost as heat during the process. The use
geneous acid or base, a heterogeneous catalyst or an enzyme. For the of microemulsions of oils combined with alcohols has the problem of
elimination of the difficulties faced by these processes, transesterifica- poor engine performance and injector choking on long-term usage due
tion in the absence of catalysts needed to be looked into. The results to the non-uniform nature of the components forming the microemul-
were the proposition of two methodologies, namely, supercritical fluid sion. Catalysed processes had the advantage of yielding alkyl esters
(SCF) technology and superheated vapour (SHV) technology. which had chemical and physical properties similar to that of conven-
Supercritical transesterification, which doesn’t need a catalyst for tional petro-diesel, with appreciable energy content. However, both
the reaction to take place, was first suggested by Saka et al. [158] as a acid and alkali catalysed processes share a few drawbacks, namely: the
means of the direct production of biodiesel from the transesterification difficulty in separation of the products and the catalyst (for both
of triglycerides. In this process, alcohols are heated to a temperature far homogeneous and heterogeneous approaches), effect of the presence of
above their critical points in order to attain a fluid phase because of contaminants in the sample, difficulties faced with the recovery of the
decreases in their viscosity with resulting increase in mass diffusivity. unreacted alcohol as well as the final downstream processes required in
This allows the reaction to occur without the presence of a catalyst to obtaining a product of acceptable purity. The challenges associated
facilitate the process, with almost as high as 95% conversion of the with the use of enzymes as catalysts in transesterification poses quite a
triglycerides into fuel-grade biodiesel. different set of challenges: The high cost of the product hinders the
The superheated vapour (SHV) technology, which is relatively new, usage of the catalyst in its homogeneous form to avoid losses with the
was originally suggested by Yamazaki et al. [159]. When an alcohol is by-products. This necessitates the entrapment or immobilization of the
heated far above its normal boiling point (within the range of enzyme, both of which are selective and time-consuming processes.
220–290 °C), it becomes superheated alcohol. The alcohol vapour in This further reduces the rate of reaction since the trapped enzymes
this state possesses large amounts of energy which enables it to react cannot come into contact with the reactants sufficiently to catalyse the
with the triglycerides present in the feedstock, leading to their ester- process effectively. Also, the leaching of the catalysts into the mixture
ification, which is actually usable as biodiesel. A distinctive advantage results in losses and further reduction in the catalytic rate. The enzy-
of this approach is its ability to produce high quality biodiesel with matic rate of reaction is also inherently slower than acid or alkali cat-
superior performance characteristics. The SMV technology requires that alysed processes, while the loss in catalytic activity owing to degrada-
the products formed during the reaction be converted by the super- tion of the enzymes over time also poses a significant disadvantage. A
heated vapour to form vapours. However, the operational temperature comparatively new substitute to these processes of transesterification
doesn’t surpass the autoignition temperature of the FAME or the boiling with the use of catalysts is the production of biodiesel under super-
point of the glycerol formed, therefore these can be safely retrieved. critical conditions. This approach was first put forward by Saka and
Nabetani et al. supervised an economic analysis on SHV approach Dadan [158], and it possesses a few distinctive benefits. The major
[160], which revealed that SHV can be operated at a lower production differences are the absence of a catalyst combined with the formation of
cost compared to alkaline catalysis. a single phase under high reaction temperature and pressure. These
The alcohol needs to be used in a large excess compared to the oil to reaction conditions result in the process boasting a very high rate of
be transesterified, which is applicable in both supercritical and super- reaction (within the range of a few minutes), while allowing for real-
heated technology. Nevertheless, the alcohol can be recovered easily time transesterification of triglycerides as well as the esterification of
since the boiling point of the alcohol used is low enough for it to form FFAs, a greater efficacy of production comprising of lesser number of
vapours and be recovered by distillation, while the biodiesel and gly- steps required for processing. Another advantage associated with this
cerol remain in the liquid phase. The resulting distillate is a pure al- process is its high tolerance of FFA and water, the presence of which no
cohol free of other unwanted by-products. longer affects the yield. Thus the process is applicable for a great
SCF and SHV technologies have advantages over catalysed process number of feedstock. The process is also pliable when under a con-
in the following ways: tinuous mode of operation as required.
Beyond the critical point of the alcohol, it shows an increase in its
1. The separation of products is relatively simple due to the absence of density while simultaneously, its dielectric constant decreases, which
a catalyst and undesirable by-products. result in the deviations in the mass transfer characteristics and the so-
2. The presence of water and/or FFAs doesn’t affect the progress of the lubility of the alcohol. Thus, both the alcohol and triglyceride form one
transesterification reaction in the supercritical state. Therefore, a phase. A decease in polarity of the alcohol is due to the increase in
variety of feedstock [160,161] can be used directly without any pre- viscosity, which is entirely due to the changes in the hydrogen bonding
325
of the molecules [158]. Thus the formation of a homogeneous phase optimum yield of the process as well as the kinetic and thermodynamic
including a non-polar triglyceride is due to its better dissolution even in feasibility of the process, to make it economic. Table 9 lists the various
methanol under supercritical conditions. As the temperature and pres- relevant research works that have been reported using supercritical
sure of the reaction mixture increases, the triglycerides show an in- reactants for biodiesel production with the reaction conditions for each
crease in their solubility in the supercritical methanol. This observation work resulting in an optimum yield.
was made by Glisic and Skala [234].
According to the reports by Glisic and Orlovic [235] on the phase 6.3.1. Effect of reaction temperature
behaviour of triglycerides (under subcritical or supercritical methano- Farobie et al. used a continuous mode of operation for a super-
lysis), the patterns of dispersion for glycerol, biodiesel, triglyceride and critical reactor system using canola oil as feedstock with supercritical
methanol were different because of their varying densities. These were methanol as the reactant [248]. They observed an improvement in
dependent on the pressure as well as the temperature of the reaction biodiesel yield as the reaction temperature was increased from 200 to
mixture. Under pressure and temperatures less than subcritical condi- 400 °C, with the optimum yield nearing 95% observed at 10 min of
tions, the mixture could easily be distinguished into two different reaction time. While the molar ratio of oil to feedstock was kept con-
phases. Around subcritical conditions, the phases become less distinct stant, temperature emerged as a more prominent factor compared to
as they interact more with each other to form products at a higher rate pressure, which was varied from 1 to 20 MPa. Madras et al. used refined
of reaction. Under supercritical conditions, the mixture of reactants, sunflower oil for the production of biodiesel in a supercritical reactor
products as well as the intermediates form a single phase, reacting operated under a batch mode. They used methanol and ethanol as the
vigorously to yield the products in a minimal amount of time. supercritical reactants, while also performing an enzymatic transester-
ification in the presence of supercritical CO2. Their observations were
6.2. Supercritical process under constant pressure of 20 MPa and a constant molar ratio of oil to
alcohol (40:1). Supercritical methanol could completely convert the oil
Saka and Kusdiana [236] studied the effect of water on the super- to biodiesel within 10 min. Supercritical ethanol showed lower reaction
critical treatment of triglycerides by methanol. They explained the re- times for the same yield, which is because the oil is more soluble in
action mechanism of triglyceride breakdown into FAME (biodiesel) and ethanol compared to methanol. Comparatively, enzymatic transester-
intermediate / end products as follows: The clusters of methanol mo- ification under supercritical CO2 required far longer time (in hours)
lecules separate into monomers under supercritical conditions, which with lower yields. Similar results were obtained by Saka and Kusdiana
allow them to attack the carbonyl carbon of a triglyceride through the using supercritical methanol for rapeseed oil transesterification in a
transfer of a methoxide moiety, which results in the formation of an batch type reaction system [158]. Also Bunyakiat et al. [251] used
intermediate compound. Next this compound breaks down into a di- coconut and palm kernel oil for supercritical methanolysis of with 95%
glyceride and one molecule of FAME. The diglyceride further undergoes and 96% conversion respectively achieved at reaction temperature of
the same kind of attack by yet another molecule of methanol, resulting 350 °C within 6 min of reaction. In another work by Madras et al., castor
in the formation of a monoglyceride and yet another molecule of FAME. oil and linseed oil were shown to require far greater reaction tem-
Lastly the reaction repeats on the monoglyceride following the same peratures (around 350 °C) with low rates of conversion as evident from
mechanism as described above to result in the yield of a molecule of the longer reaction duration required for both supercritical methanol
glycerol as well as another molecule of FAME. and ethanol [250]. Almost all research works presented in Table 9
The supercritical process has been applied for the conversion of a conform to the observation that an increase in temperature improves
large number of feedstock into high quality commercially usable bio- biodiesel yield with a large variety of feedstock and supercritical re-
diesel using a number of alcohols such as methanol, ethanol and actant, with the yield declining beyond 350–375 °C as the products
propan-1-ol. It is worth noting that the supercritical reactors used are become susceptible to thermal degradation.
commonly made from stainless steel and are typically small in size, An exception was observed in the study by Varma et al., who stu-
being of the order of a few metres in length while being a few milli- died the transesterification of sesame oil and mustard oil in super-
metres wide in diameter. The process can be simplified as follows: Both critical methanol and ethanol [255]. According to their findings, under
the alcohol and the oil feedstock are separately pumped through se- a pressure of 20 MPa, complete conversions could be achieved at 350 °C
parate lines where they are preheated, which are then mixed via a with ethanol in under 45 min and after 60 min at 325 °C. On the other
mixing tee near the inlet of the reactor, and fed into the supercritical hand, maximum conversion could not exceed 70% even after prolonged
reactor where the pressure is regulated with the help of both the pump treatment at 275 °C. Under similar conditions, the optimal conversions
pressure and a backpressure regulator. The mixture of reactants con- observed are poorer, with a temperature as high as 350 °C not being
tained in the bath is then dipped in a salt bath which is electrically sufficient for complete conversion after 1 h of reaction time, after which
heated. Therefore after attainment of the desired temperature and degradation occurs.
pressure, the reactants reach supercritical state due to which they react
vigorously and form biodiesel and glycerol or water, depending on the 6.3.2. Effect of alcohol to oil ratio
concentration of FFAs present with the triglycerides. The reaction Varma et al., performed the transesterification of sesame oil and
vessel is then cooled by dipping into a cold water bath and the products mustard oil with methanol and ethanol as the supercritical reactants
are collected through de-pressurization using a pressure regulator. After [255]. Under reactions carried out at a constant temperature of 300 °C
removal of the alcohol by distillation or evaporation as well as the and pressure of 20 MPa, they observed that the reaction rate did not
water or glycerol, the biodiesel product obtained can be analysed for improve beyond a molar ratio of 40:1 (alcohol to oil), within the range
residual TG, DG, MG content and alkyl ester content by the use of gas of 30:1 to 80:1. A variety of other oils such as castor oil, groundnut oil,
chromatography. J. curcas oil, P. pinnata oil, palm oil, linseed oil [250,274], rapeseed oil
[257] and soybean oil [262] have been used as feedstock for the su-
6.3. Impact of process parameters percritical production of biodiesel by various researchers. The results
reported by them as well as Demirbas (who used vegetable oils) [273]
A large number of feedstock have been used for the production of seem to be in accordance with that reported above. According to the
biodiesel, with the use of a wide variety of alcohols used in conjunction explanation by He et al. [262], this is mainly due to the formation of a
with co-solvents, catalysts as well as sub-critical pre-treatment strate- homogeneous phase. The formation of this phase and its maintenance
gies. However, in each of these works, the reactions have been greatly can be affected only in mixtures with low or moderate alcohol to oil
affected by one or more of the following parameters that determines the molar ratios. When the alcohol content in the reacting mixture becomes
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Table 9
Supercritical transesterification for biodiesel synthesis.
Feedstock Supercritical solvent Reaction conditions Yield (%) References
(+catalyst/co-solvent)
Reaction Reaction Alcohol : oil Residence time
temperature (°C) pressure (MPa) ratio (min)
Canola oil Propan-1-ol 400 20 40:1 10 94.4 [248]

Refined edible sunflower oil Methanol 400 20 40:1 40 96 [249]
Ethanol 98
Rapeseed oil Methanol 350 65 42:1 4 > 95 [158]
Castor oil Methanol 350 20 40:1 ∼40 > 99 [250]
Ethanol
Linseed oil Methanol 350 20 40:1 ∼40 > 99
Ethanol
Coconut oil Methanol 350 19 42:1 6.67 95 [251]
Palm kernel oil 96
Canola oil Methanol 350 20 40:1 10 100 [252]
Ethanol 30
tert-butyl methyl ether (MTBE) 30
Jatropha curcas oil Methanol 320 8.4 43:1 4 100 [253]
Jatropha curcas oil Methanol 300 9.5 16:1 30 99.67 [254]
Sesame oil and Mustard oil Methanol 350 20 40:1 60 99 [255]
Ethanol 350 ∼45 100
325 60 100
Rapeseed oil (treated subcritically Methanol 300 20 14:1 2 ∼96 [256]
by acetic acid) 270 17 15
Rapeseed oil Methanol 350 19 42:1 4 95 [257]
Canola oil Ethanol 350 20 40:1 30 93.7 [258]
Waste frying oil Methanol 300 20 40:1 Continuous 81.7 [259]
Ethanol 70.9
Rapeseed oil Methanol 250 6 24:1 10 > 97 [260]
Canola oil tert-butyl methyl ether (MTBE) 400 10 40:1 12 94 [261]
Soybean oil Methanol 320 32 40:1 25 96 [262]
Sunflower seed oil Methanol 252 24 41:1 6 ∼100 [242]
Soybean oil Methanol 400 10 3:1 2.12 ∼100 [263]
Ethanol 400 10 5:1 1.48
Sunflower oil Ethanol 375 10 5:1 1.56
Soybean oil Ethanol 325 20 40:1 30 76 [264]
Castor oil Methanol 266 6.8 50:1 5 96.34 [265]
Chlorella protothecoids Ethanol 275 20 20:1 180 89 [266]
Chicken fat Methanol 400 41.1 6:1 6 88 [267]
Waste vegetable oil Methanol 271 23.1 34:1 20.4 95.27 [268]
Waste lard Methanol 335 20 45:1 15 89.91 [269]
Waste cooking oil Methanol 300 10 25:1 13 90 [270]
Krating oil Methanol 260 16 40:1 10 90.4 [271]
Kapok oil Methanol 322 16.7 30:1 8 95.5 [272]
higher, the homogeneity of the solution is not affected further, thereby linseed oil in supercritical methanol and ethanol, with low conversions
maintaining a steady reaction rate. at up to 235 °C for 60 min, while complete conversion was achieved at
In another work by Saka and Kusdiana [257], the transesterification 350 °C in under 40 min.
of rapeseed oil at a reaction temperature of 350 °C and residence time of In another work by Farobie et al., methanol, ethanol and tert-butyl
4 min with methanol as the supercritical alcohol. HPLC analyses of the methyl ether were used for the supercritical transesterification of ca-
product samples have been used to identify the concentration of methyl nola oil into biodiesel. They observed that while the rates of conversion
esters as well as the concentration of intermediate products such as and thereby the yield were different for each supercritical reactant, they
monoglycerides and diglycerides. Their work revealed that the forma- were low for prolonged durations for every reactant in the order of
tion of methyl esters (within the range of 3.5:1 to 42:1) is best observed reaction rate: methanol > MTBE > ethanol at 270 °C and
at a molar ratio of 42:1 with 95% conversion. It can be inferred that methanol > ethanol > MTBE at 300 °C. However, in spite of pro-
increase in methyl ester formation is due to more methanol molecules longed reaction duration, near complete conversion could be obtained
which can react at an increased rate with the intermediate compounds, for supercritical methanol at both 300 °C and 350 °C, with very short
leading to a faster conversion to the final product. reaction time of 10 min at 350 °C. On the other hand, while ethanol and
MTBE showed complete conversion at 350 °C, they took 30 min for the
reactions to be complete. This shows that even the supercritical reactant
6.3.3. Effect of residence time used has an impact on the reaction rate, possibly due to the interactive
From the results reported by Farobie et al. [248], the residence time effects of the oil and the reactant and factors such as solubility affecting
seems to have an inverse relationship with the temperature of the su- the kinetics of the transesterification.
percritical reactant. This can be confirmed by the observation that the
yields obtained from canola oil at 270 °C were lower than that at 300 °C,
with complete conversion not possible even after providing 30 min of 6.3.4. Effect of pressure
residence time. At 350 °C, almost 93% conversion was achieved after During the progression of a reaction, a change in the reaction
20 min, with 400 °C providing near complete conversion in only 10 min. pressure may result in changes in the diffusion behaviour of the re-
An inverse relation between reaction time and temperature was also actants as well as the equilibrium of solubilization of the oil in the al-
observed by Madras et al. [250] from the conversion of castor oil and cohol. This has an impact in the reaction system that may be sufficient
327
to affect the biodiesel yield. Studies by Gonzalez et al. [259] on the formed by this process cannot be easily separated from the more useful
production of biodiesel in supercritical methanol and ethanol from biodiesel. Also, the glycerol formed during this process contains im-
soybean fried oil under a temperature of 300 °C and 350 °C was crucial purities and is thus far less useful than pure glycerol. Hence, the alco-
in estimating the impact of reaction pressure on the rate of conversion hols used for the conversion can suitably be replaced by equally re-
when the pressure was changed from 10 to 20 MPa. For both super- active compounds such as dimethyl carbonate or methyl acetate which
critical methanol and ethanol, the biodiesel yield improved when the can give FAME and more useful by-products such as glycerol carbonate
pressure was increased from 10 to 20 MPa at 300 °C, while at 350 °C the and triacetin, respectively [163,295].
increase in pressure led to a decrease on the biodiesel yield. The studies
by He et al. [262] on the impact of reaction pressure from 10 to 40 MPa 6.4.1. Carboxylate esters
resulted in the finding that 35 MPa is the optimum condition for FAME The use of carboxylate esters such as methyl acetate (MA) for the
yield at 310 °C with a 77% yield. Further increase in pressure did not conversion of biodiesel feedstock was first proposed by Saka and
improve the biodiesel yield. The study of Silva et al. [275] in the Isayama [296], the main reason being that the by-product resulting
continuous transesterification of soybean oil with ethanol as the su- from its use is triacetin, which is much more valuable when compared
percritical reactant led to the observation that the increase in reaction to glycerol. The main difference between the reaction of methyl acetate
pressure at 325 °C led to an improvement in conversion rate. They and methanol with the triglycerides present in the feedstock is that the
obtained an optimum yield of 70% under a reaction temperature of reaction with MA proceeds via an ‘inter-esterification’. The mechanism
325 °C, when the pressure reached 20 MPa, under an ethanol flow rate can be best described as an exchange of acyl group(s) between two
of 0.8 ml/min. different esters, which markedly differs to the mechanism of transes-
In a study conducted by Farobie et al. [261] on the production of terification in which an exchange of acyl group(s) takes place between
biodiesel from canola oil using tert-butyl methyl ether (MTBE), the fatty acid(s) and the alcohol. The conversion steps and the overall re-
impact of reaction pressure on the yield of FAME under a reaction action with supercritical methyl acetate closely resemble those of me-
temperature of 350 °C and a reaction duration of 5 min was in- thanol, when used as the supercritical reactant. The reaction includes
vestigated. It was observed that FAME yield improved with an increase three reaction stages, the first of which is a reaction between the tri-
in the reaction pressure from 6 to 8 MPa. Beyond that, the yield re- glyceride present in the oil and the methyl acetate, which gives way to
mained relatively constant. In a previous research work conducted by the formation of FAME and monoacetin diglyceride (MAG). The next
Kusdiana and Saka [236] on the transesterification of refined rapeseed step obviously is the further reaction of this MAG with yet another MA,
oil by supercritical methanol for biodiesel production, their reports giving rise to yet another molecule of FAME with another new by-
showed a linear dependence of the reaction rate on the pressure of the product, which is diacetin monoglyceride (DAG). In the final stage of
reaction up to 10 MPa, beyond which the reaction rate and resulting the reaction, this molecule of DAG reacts with another MA to finally
yield did not improve. Interestingly, in their studies on the transester- yield triacetin and another molecule of FAME. Largely, the reaction
ification of coconut oil with methanol as the supercritical reactant, involves the reaction of one triglyceride molecule with three molecules
Bunyakiat et al. [36] found that a variation in the reaction pressure had of supercritical methyl acetate, which results in the generation of three
no impact on the transesterification rate, with insignificant contribu- molecules of FAME (biodiesel) together with one molecule of a by-
tions to the optimum conversion of the feedstock. product, triacetin. The reaction has the properties of being reversible in
nature and therefore requires a large excess of methyl acetate in order
6.3.5. Effect of water and FFA in feedstock to shift the reaction equilibrium towards the formation of products,
In their study using fried soybean oil for the production of biodiesel resulting in the complete conversion of the triglycerides to biodiesel
with supercritical methanol and ethanol, Gonzalez et al. [259] obtained [297]. The reaction can be depicted as in Eq. (9):
optimum conversion using supercritical methanol. According to their
Triglyceride + 3 Methyl acetate ↔ 3FAME + Triacetin (9)
observations, the optimum conditions for maximum conversion were a
reaction temperature of 300 °C, reaction pressure of 20 MPa, with a According to the findings by Saka and Isayama [296] on the inter-
methanol flow rate of 1 ml/min and a molar ratio of 40:1. Under these esterification of rapeseed oil using supercritical methyl acetate, yield of
conditions, a maximum conversion of 81.7% in the presence of water biodiesel under a reaction temperature varied in range of 270–380 °C
was observed as compared to a yield of 72.7% in an anhydrous system for a duration of reaction ranging from 10 to 120 min under a fixed
under the same reaction conditions. Also, at a methanol to oil molar pressure of 20 MPa and a methyl acetate to oil molar ratio of 42:1 was
ratio of 20:1, the effect of presence of water could be noticed. At this observed at a maximum of 105% w/w (due to a drop in weight of the
molar ratio, the addition of 10% w/w of water improved the biodiesel reaction mixture during the progression of the reaction). The by-pro-
yield from 64.8% to 77.4%. Kusdiana and Saka [236] suggested that the duct triacetin was obtained instead of glycerol. Another added benefit
presence of water has a positive effect on the reaction mixture, since it to be noted is that the presence or formation of triacetin had negligible
aids the hydrolysis of the triglycerides present in the oil, which results effect on the stability of the biodiesel formed, since its oxidation
in the formation of FFAs. The formation of FFAs enhances the reaction characteristics were not affected.
rate since the FFAs can be esterified to form FAME, thus enhancing the Methyl acetate was also used in the inter-esterification of palm oil
biodiesel yield. by Tan et al. [298] under supercritical conditions in a batch reactor.
In case of supercritical ethanol, the results of the transesterification They observed that an optimum yield of 98% could be attained at
of soybean fried oil were similar. The addition of 10% w/w of water 399 °C molar ratio of methyl acetate to oil was kept at 30:1 for a
improved the yield to 69.1% and 70.9% under a reaction temperature duration of 59 min. In another of their studies [299], they reported a
of 300 °C, reaction pressure of 20 MPa, an ethanol flow rate of 1 ml/min 99% biodiesel yield at 400 °C and 22 MPa when the molar ratio of re-
while the molar ratio was maintained at 20:1 and 40:1, respectively, as actants was kept at 30:1 (MA:oil) for a duration of 60 min. An optimi-
compared to anhydrous systems. The improvement was largely due to zation experiment conducted by Goembira and Saka [300] on rapeseed
the same reasons as stated above. oil using methyl acetate as the supercritical reactant revealed that the
optimum reaction conditions were 350 °C, 20 MPa, 54 min and a molar
6.4. Glycerol free processes for supercritical transesterification ratio of 42:1 (MA:oil) which resulted in the conversion of triglycerides
into 97% w/w FAME and 8.8% w/w triacetin. Studies by Campanelli
The use of alcohols like methanol and ethanol for the supercritical et al. [301] on waste soybean oil, refined soybean oil, Jatropha curcas
conversion of the triglycerides and FFAs in the feedstock leads to the oil and sunflower oil also yielded similar results with an additional
production of biodiesel (FAAE) and glycerol. However, the glycerol observation that the use of methyl acetate makes the yield insensitive to
328
the composition of the feedstock. (biodiesel). According to their reports, the maximum conversion was
The impact of FFA content in the oil on the biodiesel yield was nearly 94% (w/w), obtained at 350 °C, 20 MPa, molar ratio of 42:1
studied by Dona et al. [302], who used macauba and soybean oils for (DMC-to-oil) after a duration of 12 min. An additional observation was
inter-esterification in supercritical MA. Their reports were indicative of made by them: any FFA present in the sample reacted with the super-
a superior conversion of macauba oil over soybean oil. For macauba oil, critical reactant to produce FAME and glyoxal. In another of their works
at 325 °C for 45 min with molar ratio of 5:1, the maximum conversion [307], they employed a two-step method in which the triglycerides in J.
was 83%, while for soybean oil it was a mere 44% at 350 °C for 45 min curcas oil were first hydrolysed in water at subcritical conditions of
with a molar ratio of 5:1. The better yield in macauba oil could be 270 °C and 20 MPa for over 25 min, after which the FFAs formed were
explained by its high FFA content which reacts with MA to yield FAME subjected to esterification with DMC at supercritical conditions at
in addition to acetic acid, which can act as an acid catalyst, thereby 300 °C and 9 MPa for 15 min. The optimum biodiesel yield obtained
enhancing the transesterification. A comparative study using Jatropha after using this technique was reported to be 97%.
curcas oil by Niza et al. [303] helped in understanding the difference in Tan et al. [308] reported an optimization study with reaction factors
the behaviour of the reactions as occurred with supercritical methanol such as temperature of the reaction, duration of the reaction, reaction
and methyl acetate. With methanol, an optimum yield of 89% was pressure and the molar ratio of DMC to oil for the production of bio-
obtained under more economical reaction conditions compared to diesel from palm oil. According to their findings that under optimum
methyl acetate, where the optimal yield was 72%. This difference can conditions, the biodiesel yield obtained was 91%. According to the
only be explained by the difference in the reactivity and mutual solu- reports by Kwon et al., coconut oil can also be converted into biodiesel
bility of the supercritical reactant and the feedstock. using DMC as the supercritical fluid [309]. Coconut oil can be con-
Goembira and Saka [304] also studied the addition of various verted into biodiesel with a 98% yield for only a reaction duration of
compounds on the biodiesel yield. An addition of acetic acid and water 1–2 min at 365–450 °C. It was also seen that the yield improved with an
resulted in an enhancement of the biodiesel yield, adding oleic acid and increase in the temperature of the reaction and residence time.
methanol had no impact on the yield of the biodiesel. The addition of
acetic acid enhances the production of biodiesel through the methyl 6.4.3. Tert-butyl methyl ether (MTBE)
acetate route. The addition of 12 specific carboxylate esters and their First proposed by Farobie et al. [261], the use of tert-butyl methyl
impact on the production of biodiesel production were also studied, ether is a very interesting alternative to supercritical methanol. The use
with methyl acetate resulting in the best yield of 98%, possibly because of MTBE in supercritical transesterification with a triglyceride in the
of the shorter chain in MA [297]. The reaction can be represented by feedstock results in the production of FAME along with a by-product,
the Eq. (10): which is glycerol tert-butyl ether (GTBE). According to reports from
research works on the biodiesel properties produced with MTBE, the
Triglycerides + 3 Carboxylate ester ↔ 3 FAAE + Triacin (10)
presence of GTBE has been shown to result in an improvement of the
Liu et al. [304], Lin et al. [171], and Nan et al. [305] carried out quality of the biodiesel produced since it increases the cetane number
detailed studies on the thermal degradation of biodiesel produced as well as reducing its cloud point (CP) [310,311].
under supercritical conditions. According to their findings, the thermal A look at the overall steps in the production of biodiesel using su-
degradation of biodiesel is mainly due to the following three mechan- percritical MTBE shows a close resemblance to that of the steps taking
isms: pyrolysis occurring at above 350 °C, through polymerization (also place with supercritical methanol. There appear to be three reversible
known as Diels-Alder reaction) taking place between a temperature steps, the first of which is a reaction between a triglyceride molecule
range of 300–425 °C and by means of isomerization occurring within with a molecule of MTBE to give diglyceride mono-tert-butyl ether
the range of 275–400 °C. (DGE), which can react with another molecule of MTBE, resulting in the
generation of monoglyceride di–tert-butyl ether (MGE). In the final
step, another molecule of MTBE is used to react with the MGE molecule
6.4.2. Dimethyl carbonate (DMC)
to finally produce FAME and GTBE.
The use of dimethyl carbonate (DMC) as the supercritical reactant
Farobie and Matsumura [312] reported the only work on their
leads to biodiesel production along with the production of glycerol
studies of the impact of temperature of the reaction as well as the re-
dicarbonate. Similar to the procedure of transesterification by the use of
sidence time on the yield of biodiesel using MTBE under supercritical
alcohols or the method of inter-esterification by methyl acetate, the
conditions. They noted that the yield improved with an increase in the
transesterification reaction with DMC involves three step -wise reac-
reaction temperature and a prolongation of the residence time. It has
tions, the first of which is the reaction of a triglyceride (TG) with a
also been observed that the conversion rate of triglycerides in super-
molecule of DMC leading to the production of a molecule of methyl
critical MTBE is lower when compared to that of methanol, although a
carbonate diglyceride (MCDG) along with a molecule of FAME. In the
higher temperature can be used and the yield being the same when the
next step, the MCDG reacts with yet another molecule of DMC, which
reaction is continued over a longer period. It is also interesting to note
results in the formation of dimethyl carbonate monoglyceride
that supercritical MTBE gives a higher yield compared to methyl
(DMCMG) and another molecule of FAME. The final step would now be
acetate. This is because MTBE has a lower polarity than methyl acetate,
the reaction of the DMCMG (formed in the previous step) with yet
which results in increased miscibility of MTBE in the oil, circumventing
another DMC molecule to finally give the products: the third FAME
problems encountered with mass transfer resistances.
molecule and citramalic acid as well as glycerol carbonate as the by-
products, as is represented by the Eq. (11):
6.5. Process intensification
Triglycerides + 3 DMC ↔ 3 FAME + Glycerol carbonate
6.5.1. Use of co-solvents
+ Citramalic acid (11)
Supercritical conditions require extensive careful maintenance and
There are a limited number of studies available that are relevant also cause huge losses in energy efficiency of the process. Therefore, it
with the use of supercritical DMC for the production of biodiesel. The has been suggested that co-solvents be used to reduce the stringency of
first reported study was that by Ilham and Saka [306] who reported the the supercritical conditions. Upon the addition of a co-solvent, the
production of biodiesel from rapeseed oil, having used a batch reactor hindrances observed in the solubility between methanol and triglycer-
which was built with an alloy, Inconel-625. Their observations were ides are greatly reduced. As a direct result of this facilitation, the pro-
that DMC reacted with the triglycerides to produce citramalic acid and duction of biodiesel is possible under benign conditions, which are
glycerol carbonate as by-products alongside the main product, FAME easier to maintain. Quite a few number of co-solvents are commonly
329
available such as: tetrahydrofuran (THF), n-heptane, n-hexane, n-bu- the duration of the reaction is 120 min.
tane, ethane, carbon dioxide and propane. From the reports by Cao For the transesterification of seed oils into biodiesel without the aid
et al. [237] it was observed that the addition of propane with a molar of catalysts, high temperatures, pressure and molar ratio of alcohol to
ratio to methanol of 0.1, the temperature of the reaction was reduced oil are needed. Therefore in an attempt to minimize these undesirable
considerably from 350 °C to 280 °C, with complete conversion to bio- outcomes, Kusdiana and Saka [247] proposed a non-catalytic proces-
diesel. Also, according to the findings by Imahara et al. [238], adding sing of the feedstock involving two steps. First a hydrolysis can be
CO2 as a co-solvent resulted in an improvement of the biodiesel yield by performed in subcritical steam in which the fatty acids are split from
enhancement of the methanolysis of canola oil which was used as the the glycerol backbone of the triacylglycerol resulting in the generation
feedstock. On the other hand, an increase of the co-solvent concentra- of FFA and glycerol. The next step involves the esterification of the
tion above 0.1 CO2/methanol resulted in a decrease in the yield. FFAs under supercritical conditions with an alcohol, with the reaction
Trentin et al. [239] observed that through the employment of a mi- now being able to proceed to completion with much lower alcohol to oil
crotube reactor, the impact of addition of CO2 on the yield of biodiesel molar ratios. This approach greatly reduces the consumption of energy
under supercritical conditions could be investigated. As the mass ratio because of the milder reaction conditions. Also, this is preferable to the
between CO2 and substrate was maintained around 0.2:1, the yield of catalysed supercritical processes, because of the lesser number of
biodiesel obtained was found to be optimum. Tan et al. [240] reported downstreaming steps required to obtain pure biodiesel, since there is no
that highest impact of supercritical n-heptane to oil molar ratio on need for removal of any catalyst.
biodiesel production from palm oil was when n-heptane: palm oil was
0.2:1 with methanol. For use as a co-solvent, the importance of n- 7. Superheated technology and its prospects
hexane has been studied by Muppaneni et al. They showed that an
optimum yield of biodiesel could be obtained when the ratio (in vo- 7.1. Overview – superiority over supercritical approach
lume) of n-hexane to oil was maintained at around 0.2:1 [241].
Saka and Dadan proposed the supercritical fluid technology, which
6.5.2. Use of catalysts is non-catalytic in its operating principle, having the ability to operate
Although the supercritical process is efficient in transesterification in the absence of a catalyst [158]. Nevertheless, this makes use of a
in the absence of catalysts, the process is highly energy-intensive and supercritical reactor which has the capability to be resilient to the high
costly, since high temperature and pressure-resistant reactors need to pressures and temperatures which fall in the limits of 10–30 MPa and
be developed. Therefore it has been proposed that the use of proper 300–400 °C correspondingly. This is very difficult to achieve even in a
catalysts under supercritical conditions might lead to an improvement lab scale reactor. For an industrial scale reactor, the price involved with
in the production of biodiesel. The investigations of Demirbas [242] its manufacture and maintenance for safe handling of huge volumes of
with sunflower oil (used as the feedstock) revealed that the addition of the reactants operating at such high pressures is almost impractical
CaO under supercritical conditions effectively led to an increase in the [163]. Later, as an alternative to the promising aspect of non-catalytic
biodiesel production. With only a 3% wt. of CaO added to the reaction transesterification, another innovative approach was proposed in the
mixture, the maximum yield of biodiesel could be recorded within a form of superheated alcohol technology for the production of com-
very short reaction span of 6 min under a reaction temperature of 525 K mercially usable biodiesel.
when the molar ratio of methanol to oil was maintained at 41:1. The Superheated liquids are those that have been heated to a tempera-
detailed study undertaken by Yoo et al. [243] aimed at examining the ture far exceeding their boiling point. When methanol is being con-
effect of adding various metal oxides like ZrO2, TiO2, ZnO, CaO and SrO sidered for use in the production of biodiesel, it has to be heated to
to the supercritical transesterification process of biodiesel production temperatures (nearing 250 °C) that well exceed its normal boiling point
with methanol. The results obtained by them showed that the yield was (64 °C) under a pressure of 0.1 MPa. Under these conditions, methanol
close to 95% within a very short reaction time of 10 min when ZrO2 was forms bubbles which then flow through a bubble column reactor that
added at 1% wt. concentration under a reaction temperature of 250 °C, already contains heated oil rich in free fatty acids and triglycerides in
while the molar ratio of methanol to oil was maintained at 40:1. It was order for the esterification and transesterification reactions to occur
observed that most of the heterogeneous metal oxide catalysts (with the simultaneously. The vapours of the alcohol used are also able to solu-
exception of zirconia supported metal oxide catalysts as well as zinc bilize the products of the reaction, namely methyl esters (ME) and
aluminate) used so far are unstable under the reaction conditions, glycerol (GL) which are formed within the vapour phase. However, the
which are supercritical [244,245]. Understandably, in an attempt to temperature of the vapour phase of the alcohol is still less compared to
avoid catalyst loss, homogeneous catalysts have also been used in trace the boiling point of glycerol and yet lower than the flash point or au-
amounts under subcritical conditions, with many researchers studying toignition point of the FAME formed. Therefore, it is easy to separate
their effects on the reaction [246]. The studies of Wang et al. [260] on the products from the reactants and the intermediate products that exist
the supercritical transesterification rapeseed oil with methanol using within the liquid phase [164]. The dual role of the alcohol as a reactant
NaOH as a catalyst showed that with the addition of a 0.2%-0.5% w/w and as a carrier ensures that the reaction witnesses a shift of the
of NaOH in the reaction mixture, the rate of reaction was drastically equilibrium towards product formation. The products formed are ra-
improved, with a 30-fold reduction in the duration of the reaction re- pidly carried away by the alcohol thereby reducing the probability of
quired for > 98% conversion into biodiesel under a reaction tempera- the reverse reaction taking place, which increases conversion rate. This
ture of 250 °C and pressure of 10.2 MPa. approach of transesterification has a benefit since the refinement of the
biodiesel obtained is simple owing to the absence of soap formation as
6.5.3. Two-step process using sub-critical conditions well as the system not utilizing any catalyst to work efficiently.
Advanced processes such as the Eisenlohr process, the Colgate-
Emery process and the Twitchell process have been developed from the 7.2. Observations from literature
hydrolysis of triglycerides. The Colgate- Emery approach of fatty acid
synthesis from the breakdown of fats and oils is the prevalent technique Over the last few years, quite a number of research works of sig-
till date in the industrial sector. Fig. 12 depicts the process of the hy- nificance have come to light, highlighting the potential of commercia-
drolysis of triglycerides to form water and FFA. The characteristic lization. Yamazaki et al. conducted an experiment on sunflower oil and
conditions of operation under this process tends to be around 250 °C was successful in converting 200 ml of sunflower oil to biodiesel. The
and 5 MPa. It has been observed that the aforementioned reaction experiment was operated in a semi-batch mode under conditions
conditions can be sufficient in the yield of fatty acids close to 97% when nearing a temperature of 290 °C and a pressure of 0.1 MPa, for 1.5 h
330
Fig. 12. Hydrolysis of triglycerides by water to form FFAs.
when methanol was used as the reactant and carrier at a flow rate of obtained under a feed flow rate of 4 ml/min, while the temperature of
10 ml/min. agitation was provided at 700 rpm to enhance the reaction the reaction was maintained at 290 °C with the optimum duration of the
and facilitate the transesterification [159]. Another experimental work reaction obtained at 210 min. Kinetic studies of the process revealed
undertaken by Joelianingsih et al. had also converted palm oil by non- that the process requires a high activation energy of 50 kJ/mol [167].
catalytic superheated transesterification to biodiesel in a bubble column
reactor, with a 95.17% FAME content achieved at atmospheric pres- 7.3. Impact of process parameters
sure. The reactions were subjected to similar variations of the reaction
parameters, with the final results reporting an optimized temperature of 7.3.1. Effect of initial oil mass
250 °C, the flow rate of methanol kept at 4 g/min for a time period of The transesterification under superheated conditions mainly occurs
5 h. They also went ahead in performing a kinetic study for the opti- where the two phases are at a state of convergence. Among all currently
mized superheated methanol transesterification reaction, with an en- available literature, only the research work reported by Ang et al. deals
ergy of activation at 31 kJ/mol and frequency factor of 4.2 min−1 with the aspect of variable initial oil mass to optimize the FAME pro-
[164]. duction by superheated methanol. Within the range of 40–70 g, the
When the triglycerides contained in palm oil are hydrolysed, a by- impact on the reaction based on primary oil mass were inspected under
product ‘palm fatty acid distillate’ (PFAD) is obtained, which contain a temperature of 290 °C keeping the rate of flow of methanol at 2 ml/
some unreacted fatty acids. In the uncatalysed esterification of PFAD min. The observed FAME yield was highest when the initial mass of oil
performed by Cho et al. [165] through the use of SHV technique, me- is 40 g since a major portion of the oil can fill the void by the formation
thanol used as the reacting alcohol was fed into the reactor containing of vapours, which can then react effectively in order to provide the
PFAD. Methanol will form bubbles and react with PFAD which results maximum yield, as observed. Higher initial loads lead to the increased
in the formation of FAME and water. An optimum condition was chances of more residual oil remaining in the reactor, which lowers the
formed at a methanol steady-flow rate of 2.4 g/min, when the tem- yield significantly as the vapour cannot react sufficiently with the
perature of the reactants was maintained at 290 °C as the pressure rose methanol.
to a value of 0.85 MPa. The convergence of all these conditions led to a However, since the mode of operation was a fed batch system, a
FAME yield of 102.8% which is comparable to the theoretical yield high primary load of oil results in the increase of the rate of production
placed at 104.5%. The yield astonishingly crosses 100% due to the and outflow leads to a minor increment. This is because the methanol
molecular weight increase during the reaction, because of the re- bubble gets a longer time to reside in the bulk liquid before reacting
placement of water by an equal quantity of methanol (in moles). Stu- with the oil vapours. Also the high primary load offsets the yield drop
dies aimed at an understanding of the kinetics of the reaction were also due to the formation of products. The findings made in this study are
carried out, with a kinetic model proposed to represent the reaction relatable to the reports by Yamazaki et al. [159].
mechanism [166]. According to their reports, a rise in the temperature
of the reaction leads to an accelerated methanol consumption from the
liquid phase. A rise in temperature would result in an increase in the 7.3.2. Effect of alcohol flow rate
kinetic energy of the methanol molecules which then would diffuse According to reports from the research work undertaken by Ang
faster when fed in the reactor. et al. [161] it is evident that an increase in the flow rate of methanol
Ang et al. conducted two separate research works on SMV tech- leads to a corresponding rise in FAME production. At a rate of flow of
nology. One involved the injection of superheated methanol vapour 2 ml/min, they obtained a maximum production of 5.22 g taken at
into crude Jatropha curcas oil in a ‘one-step SMV transesterification’, timely intervals of 30 min, when the reaction was conducted for
resulting in the successful production of FAME [161]. The crude oil is 180 min. When the rate of flow was stepped up to 3 ml/min, the rate of
non-edible containing large quantities of FFA (around 15%). Results biodiesel production dropped to a value approximating to 4.50 g, even
obtained indicate that the best yield of 71.54% was achieved when the when the duration of the reaction is varied between 120 and 210 min.
reaction was performed at a temperature of 290 °C, with the rate of flow As was seen by them, there was a drop in the production of biodiesel as
of the methanol (used both as a reactant and a carrier) kept at a con- the rate of methanol flow was increased. This is attributed to the re-
stant of 2 ml/min as the oil mass was kept at an initiatory value of 40 g. duction in available oil mass left in the reactor (to react with the in-
The second work also used the same principle of ‘one-step SMV trans- coming methanol vapour) with the progress of time. The observations
esterification’ on sea mango oil, but with the absence of any pre- made by the, are concordant with those made by Joelianingsih et al.
treatment steps. The crude Cerbera odollum oil therefore is a low cost [168]. Further results recorded for both the rate of conversion as well as
feedstock, having been obtained from sea mango trees which are grown the rate of outflow of the biodiesel demonstrated a significant im-
as ornamental plants. The injection of superheated methanol in its va- provement as the rate of flow was subjected to an initial increase to
pour form directly into the heated oil phase initiated a rapid reaction to 2 ml/min, starting from 1 ml/min. The rate of outflow of the biodiesel
form FAME from simultaneous transesterification of triglycerides and also showed an improvement to 0.12 g/min, from 0.03 g/min; just as
the esterification of fatty acids that the oil contains. Based on a fixed the overall rate of production showed a corresponding rise to 0.12 g/
initial oil volume of 100 ml, the maximum yield of 87.4% FAME was min, from 0.05 g/min. This can be attributed to the fact that the area of
convergence between the gas and the liquid improved when the rate of
331
flow of methanol was increased. Beyond that as the rate of flow was obtained, being significantly inferior to the yield procured at 290 °C.
increased to 3 ml/min, the rate of outflow as well as the total rate of Both the overall rate of production of FAME and its rate of outflow was
FAME production declined upon increment of the rate of flow to 3 ml/ observed to rise within the range 270–290 °C of operating temperature
min. As a result of this change, there was a decrease of the overall rate of the reaction, with the best value of 0.12 g/min (for both) obtained at
of production as well as the overall rate of outflow of the FAME, both of 290 °C. The rate of production is observed to rise because the increment
which now had a value of 0.11 g/min. This drop can be attributed to the in the temperature of the reaction leads to a corresponding improve-
lowering of the levels of oil in the reactor, since flow of methanol in- ment in the reaction rate [159]. Conversely, on further increment of the
creased, which led to an incomplete reaction, with the outgoing gas reaction temperature to 300 °C, both the rate of outflow of the FAME as
sample product now having inferior quality. This is because it contains well as the overall rate of production of the biodiesel were noted to
lesser amounts of FAME and more amounts of intermediate products decline to a value of 0.10 g/min. This can be attributed to the pro-
such as monoglycerides as well as diglycerides. duction of unwanted products in the biodiesel (which were identified
In another study conducted by Ang et al. [167] to understand the through the use of GC/MS), which can be reasoned as due to the pyr-
impact of the flow rate of methanol using sea mango (Cerbera odollum) olysis of the oil used as the feedstock. Obtained results and their cor-
oil, initially the volume of the oil obtained from sea mango as well as responding conclusions as evident were found to be in accordance with
the temperature of the reaction were maintained at 100 ml and 290 °C those reported by Yamazaki et al. [159] and also with Jansson, in which
respectively. Variation of the flow rate of the methanol was done within a variety of oils were subjected to pyrolysis and the components ob-
the range 1–4 ml/min with the collection of FAME at timely intervals of tained were the same as those that were identified in this work [170].
30 min, which is useful in obtaining the rate of FAME production (in g/ The complication arising out of this is that the highest yield of FAME
min). The rate of FAME produced using the superheated methanol can (91.22% w/w) was obtained when the temperature of the reaction was
be observed to rise to 0.23 g/min from 0.16 g/min as the rate of flow of 270 °C, while biodiesel yield was low, having achieved a maximum of
methanol is stepped up to 4 ml/min from an initial value of 1 ml/min. only 21.56% w/w as compared to 71.54% obtained at 290 °C. The drop
The results obtained are in perfect agreement with their previous work in the FAME content can be attributed to the fact that FAME is unstable
and with the conclusions obtained from the experiments conducted by at temperatures surpassing 275 °C, owing to possible thermal de-
Yamazaki et al. [159] due to similar reasons. Optimum value of the rate gradation of the components [171].
of flow of methanol is chiefly reliant on the primary mass of oil in the In another work by Ang et al. using sea mango oil as the feedstock
reactor. [167], the temperature was varied within a range of 260–290 °C while
A study conducted with the use of refined palm oil as the feedstock the rate of flow of methanol and the starting volume of the oil were
by Joelianingsih et al. [168] reported their results in terms of biodiesel maintained at constant levels of 4 ml/min and 100 ml, correspondingly.
productivity which is the biodiesel obtained from the reactor (in kg) For this work, they avoided raising the temperature to 300 °C since in
that has been produced per unit volume (measured in L) per unit time their previous work, pyrolysis of the oil was observed to hamper the
(h). Under reaction conditions maintained at 290 °C with a fixed vo- productivity of the process [161]. The product acquired in the form of a
lume of 200 ml of refined palm oil set as the standard, the product condensate at precise time intervals of 30 min was subjected to analysis
formed was withdrawn from the reactor at fixed durations set 30 min for the rate of production of FAME contained in it. The attained results
apart with the reaction still in progress. This was done under a different point to the conclusion that the rate of production of FAME improved as
methanol flow rates, with the reaction time extended to study the effect the temperature of the reaction was raised. Similar to their previous
of the drop in the leftover oil mass in the quality of the FAME obtained work, the highest rate of production of FAME was observed when the
as the methanol flow rate changed. From their observations, the FAME reaction was carried out under temperatures reaching 290 °C, with the
productivity rose with an increase in reaction duration, becoming reaction having continued for 210 min while the rate of flow of me-
steady after 5 h. The FAME productivity also rose with higher rates of thanol was kept at 0.272 g/min. Thereafter, a drop in the production
flow of methanol. At a reaction duration of 5 h, the obtained FAME was rate was observed, and this can be explained by the decline in the vo-
0.028 kg/L/h under a flow rate of 1.5 ml/ min, 0.128 kg/L/h under a lume of the sea mango oil that is available to sustain the reaction rate.
rate of flow 3 ml/min, and 0.180 kg/L/h when the flow rate was 6.0 ml/ Similar to the experimental approaches reported above,
min. The attainment of these results confirm the fact that a higher rate Joelianingsih et al. [168] attempted to understand the impact of the
of flow of the alcohol leads to an increment in the available methanol temperature of the reaction on biodiesel productivity. They varied the
that can react with the oil, leading to better productivity. On the con- reaction temperatures within a range of 250–290 °C at intervals of 20 °C
trary, the rate of flow of methanol has mixed effects on the methyl ester while keeping the rate of flow of methanol constant at 3 ml/min for a
content of the product attained. When the reaction was continued for total duration of 5 h of reaction. Productivity of biodiesel as obtained
5 h, an increase in the feed flow rate beyond a certain threshold resulted from the reaction conditions maintained were 0.010, 0.052 and
in the drop in methyl ester content of the biodiesel obtained. As ex- 0.128 kg/L/h at temperatures of 250 °C, 270°Cand 290 °C correspond-
plained before, this is due to a lowered residual time of the methanol in ingly. From the results it is clear that reaction temperature is propor-
the reactor, which results in an incomplete reaction and hence, the tional to the biodiesel production, with higher temperatures improving
biodiesel product obtained has greater amounts of monoglycerides and the productivity which is in accordance with the kinetic and thermo-
diglycerides than methyl esters. dynamic principles of a chemical reaction.
Methyl ester (ME) content of the biodiesel obtained from the su-
7.3.3. Effect of reaction temperature perheated transesterification reaction appears to decrease with the
According to the experiments conducted by Ang et al. on crude progression of time at higher temperatures. Results from the study
Jatropha curcas oil [161], temperature was found to be a facteur premier conducted showed that while the initial ME content in the biodiesel at
in the yield of biodiesel as well as the methyl ester content of the higher temperatures is greater, it soon declines after the duration of the
biodiesel obtained. While the rate of flow of the methanol fed into the reaction crosses 210 min. A lower temperature corresponded to a
reactor was maintained at a constant value of 2 ml/min, all experi- greater content of methyl esters. From a point of view based on che-
mental studies focused in the elucidation of the impact of temperature mical reaction kinetics, it makes sense that the reaction time required
on the reaction were started with an oil mass of 40 g. The FAME yield for optimum FAME yield decreases with an increase in the temperature
was observed to improve with progress in time when the reactions were of the reaction, with temperatures of 250 °C, 270 °C and 290 °C needing
carried out at temperatures of 270 °C to 290 °C at 10 °C intervals. 4 h, 3 h and 1.5 h for optimum yield, correspondingly. This is due to the
Conversely, beyond 290 °C at a reaction temperature of 300 °C, the fact that an increase in the rate of the reaction is usually the result of a
progress of the reaction showed a drop in the yield of the biodiesel rise in the reaction temperature. It was also noted that when the
332
reaction was continued for 5 h, the amount of methyl esters at tem- at room temperature, with molar ratio of 543:1:2.0 of methanol:a-
peratures of 250 °C, 270 °C and 290 °C contained in the product were cylglycerol:NaOH, under the same reaction duration of 8 h. The yield
97.7%, 96.5% and 94.9% correspondingly. This can be reasoned on the from the lipids extracted reached a maximum of 84%, therefore overall
basis of the thermodynamics of the reaction, since the reaction is an efficiency of transesterification from direct soy flakes is calculated to be
exothermal one [172]. By their characteristics, lowering of the tem- 80%.
perature of the reaction corresponds to a shift of the equilibrium to the Supercritical methanol was used as the reactant by Calixto et al.
formation of products. Therefore, ME content is more due to reduced [326], who used spent coffee grounds as the raw material for the pro-
amounts of monoglycerides and diglycerides in the final product. As the duction of fuel-grade FAME. The reaction conditions maintained for
reaction temperature is increased, these intermediate products also maximizing yield of methyl esters were: reaction temperature of 603 K
form greater amounts of vapours and pass off into the products, thereby and pressure of 30.0 MPa, with a yield of 84.9%.
reducing the yield as well as the ME content. However, triglycerides are
not found in the product since they are far more stable and exist in the 9. Future prospects
liquid phase. The results are in agreement with another of their works
involving a kinetic study for the production of biodiesel from palm oil A lot of the processes that have been discussed here have quite a few
in a bubble column reactor [164]. drawbacks. The process of acid catalysed esterification/transester-
ification has the problem of water present in the feedstock as well the
8. In-situ biodiesel production removal of acid and alcohol from the product. This also the case for
base catalysed transesterification, in which again base catalysed
In the process of biodiesel production from organic feedstock, there transesterification can be hampered by the presence of water, FFA and
are three steps: solvent extraction of the oil, esterification/transester- also glycerol. The process is also not energy and cost-efficient. The
ification (often coupled to ensure maximum yields and purification of process of enzyme catalysed transesterification requires prolonged time
the product. Additionally, this step-wise process is susceptible to durations for completion with low yields and is also not cost-efficient,
changes in the adjustment of reaction parameters depending on the with cost of the enzyme being the main hindrance. The process of su-
approach selected, with time and cost increasing as a direct result. The percritical transesterification uses a high temperature, pressure as well
approach of in-situ transesterification is therefore a promising alter- as a high reactant to oil ratio. Even with the modifications that have
native that has been successfully used combining all the steps in one been reported under Section 6 of this paper, some challenges remain
simple transesterification step. Several biodiesel feedstock have been which are:
experimented on using this technique, such as algae [317–319], soy-
bean [320], and Jatropha [321] etc. [322,323]. Both acid and alkali 1. The process remains energy-intensive and thus is not energy effi-
catalysts can be suitable for this approach. Acid catalysts are suitable cient.
for feedstock with FFA concentration higher than 2 mg KOH/g oil. The 2. Even after the development of processes which result in the for-
studies by Liu et al. [316] were on spent coffee grounds with sulfuric mation of useful by-products (which are easier to separate) with a
acid as catalyst to obtain 98.61 wt% esters under a reaction tempera- commercial value higher than glycerol, the process is still wasteful
ture of 70 °C, 20% w/w H2SO4, and 12 h reaction time. as a large amount of the supercritical reactant is used which has to
According to Siler-Marinkovic et al. [324], transesterification of be recovered subsequently.
vegetable oils for the production of biodiesel can be done by the simple 3. The reactors capable of handling such high temperatures and pres-
use of the raw feedstock without the extraction of oil. This serves as an sures are costly, which accounts for high start-up costs, resulting in
alternative for the commonly used esterification and transesterification the process being unattractive, since scale-up will be difficult.
of the oils extracted from various sources. They observed that the usage 4. A lot of research works reported in this field have used manual
of whole sunflower seed oil in situ in the presence of acidified methanol optimization strategies, which is our view is cumbersome and in-
results in the production of FAME. The yield is considerably higher efficient as it wastes both time and resources.
when compared to conventional transesterification with pre-extracted
seed oil. This can be due to the additional lipid content of the hull of the The energy recovery remains a challenge for which a spiral reactor
seed, which would result in the contribution of the overall ester yield. design as reviewed previously by Farobie et al. [295], however, ac-
Also, the loss of lipids resulting from the separation of hull and kernel cording to our view, a lot of the energy is still unutilized and lost as
can be avoided. According to their observations, the required molar heat. This can be circumvented by attempting to use this heat for pre-
ratio on methanol:oil was 200:1, while catalyst (alkali) was provided at heating the product mixture before the distillation of the supercritical
100% w/w concentration for good ester yield. Acid catalysts showed reactant which remains mixed with the product. For the process to be
poor performance with lower ester conversions even at prolonged re- cost-effective, the simultaneous recovery of the supercritical reactants
action times spanning over 18–69 h. Kasim et al. [325] also used the should be attempted, this cuts down on processing time as well as
reactive extraction for the production of fuel-grade methyl esters from material costs [295]. The channeling of the heat lost by means of a heat
Jatropha curcas seeds, which were crushed to a suitable particle size exchanger system for reactant recovery would be best for reducing
(0.5–4 mm). Optimum yield was obtained under the following condi- energy losses, when the process is used in an industrial scale. The su-
tions: seed particle size < 0.71 mm, speed of mixing at 300 rpm, tem- percritical process can be brought down to processes such as sub-critical
perature of reaction maintained at 30 °C, 30 min reaction time, 0.15 N two step approach that cuts down on some of the high temperature and
NaOH concentration and methanol:oil molar ratio of 400:1. Najda- pressure requirements, making the process more energy efficient, as has
novic-Visak et al. [327] used spent coffee grounds with methanol in the been discussed in Section 6.5.3. Another improvement in this field
presence of NaOH for the production of low-cost biodiesel using in-situ would be the use of software designed optimization techniques in future
transesterification. Highest yield obtained was 96.0% under reaction research works, like CCD-RSM for better optimization or with fewer
conditions of methanol:oil molar ratio = 400:1, reaction temperature of runs as can be carried out using the Taguchi approach. A problem that
333 K, NaOH concentration of 0.2 mol L−1 and a reaction duration of is yet to be addressed is the lack of sufficient cost analysis data for both
90 min. Haas et al. [328] used a direct transesterification process for the supercritical and superheated transesterification techniques attempted
production of alkyl esters from soybeans. 95% of the lipids in soy flakes and reported so far, which when done can help in bridging the gap
were extracted under room temperature. At 60 °C, maximum ME yield between the laboratory scale experiments reported and the estimation
was obtained under molar ratio of methanol:acylglycerol:NaOH of of the method developed in an industrial scale.
226:1:1.6 with an incubation period of 8 h. A high yield was also noted Another problem associated with this process is the degradation of
333
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Energy Conversion and Management 182 (2019) 307–339

Contents lists available at ScienceDirect

Energy Conversion and Management

Progress and future of biodiesel synthesis: Advancements in oil extraction T

Fig. 1a. Global energy consumption scenario (sector-wise).

Fig. 1b. Global marketed energy (overall).

Carbon dioxide (CO2) 95 Coconut 63–65

2.2.2. First generation feedstock to place in addition to being scattered in availability

1. Since they are relatively low on biomass microalgae provide more

3.1. Steam distillation 3.3.1. Chemical leaching

Fig. 3. Generalized setup for Steam distillation.

3.4. Enzymatic oil extraction

The procedure of enzymatic oil extraction is proving to be pro-

The time may be depicted as in Eq. (6):

4. Conventional approaches for biodiesel production 4.2. Micro-emulsions

4.1. Pyrolysis Micro-emulsions represent colloidal dispersions of optically iso-

Fig. 6. An overview of the diﬀerent approaches to biodiesel production.

Fig. 7. Mechanism of acid catalysed transesteriﬁcation for triglycerides and FFAs.

4.3.4. Impact of catalyst concentration

Castor oil Concentrated H2SO4 50 2.09 1 15:1 700 73.27 [136]

4.4.1. Impact of reaction temperature and time

Fig. 10. Saponiﬁcation of FFAs by radicals

ratio was increased to 8:1 under a reaction time of 2 h, the improve-

above, helped overcome the mass transfer diﬀusional resistances en-

leaching directly resulted in the saponiﬁcation of the oil which desta-

4.5. Enzyme catalysed transesteriﬁcation

Immobilized lipase (from whole R. mucilaginosa

the eﬀectiveness of the approaches are hampered due to the generation

Candida antarctica B lipase (immobilized on

of waste water, which needs to be treated before safe disposal. When

Lipase [from Candida antarctica Lipase B

Lipase (from Chromobacterium viscosum)

compared to acids and alkali as catalysts, enzymes oﬀer certain beneﬁts

crative choice for reducing production charges, which can be appre-

fortunately have questionable quality for use as raw material, as well as

being complicated to transform using catalysts [141,142]. Nevertheless,

[143–145]. The various relevant research works reported on enzyme

Table 8. When paralleled to acids or alkali (both homogeneous and

Waste cooking oil

heterogeneous), enzymes have been more successfully utilized as cat-

alysts, since they:

1. Addition of methanol over a few steps [284,286,287]

Using solvents like chloroform, benzene, n-heptane and hexane can

Canola oil Propan-1-ol 400 20 40:1 10 94.4 [248]

Fig. 12. Hydrolysis of triglycerides by water to form FFAs.

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