Review On The Extraction Methods of Crude Oil From
Review On The Extraction Methods of Crude Oil From
Review On The Extraction Methods of Crude Oil From
from all Generation Biofuels in last few Decades - On Boiling of Crude Oil under Elevated
Pressure
Anastasiya V Pimenova and Denis S
Goldobin
To cite this article: G Bhargavi et al 2018 IOP Conf. Ser.: Mater. Sci. Eng. 330 012024
- A fuzzy goal programming model for
biodiesel production
D S Lutero, EMU Pangue, J M Tubay et al.
1. Introduction:
The ever growing demand for the energy fuels, economy of oil, depletion of energy resources and
environmental protection are the inevitable challenges required to be solved meticulously in future
decades in order to sustain the life of humans and other creatures in this world. Switching to alternate
fuels that are renewable, biodegradable, economically and environmentally friendly can quench the
minimum thirst of fuels demands, in addition to mitigation of climate changes. At this moment,
production of biofuels has got prominence [1]. The term biofuels refer to the fuels derived from living
matter either from animals or plants, specifically concern to Biodiesel and Bioethanol. Biodiesel is
nothing but mono alkyl esters of long chain fatty acids derived from vegetable oils or animal fats.
Triacylglycerols or colloquially triglycerides are the precursors from which biodiesel has been produced.
Triacylglycerols are one of the forms of lipids. For the extraction of lipids (oils or fats), a major
component for biodiesel production, several extraction techniques have been put forward. Triglycerides
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are converted into biodiesel by tranesterification using alcohol with or without a catalyst. Biodiesel is
being used as one of the promising alternate fuel sources for diesel engines [2-4]. Biodiesel is renewable,
environmentally friendly, safe to use, biodegradable and it has become a major focus on intensive global
research and development of alternate energy. Although the composition of biofuel is complex, it includes
mainly palmitic acid, stearic acid, oleic acid, linoleic acid and other fatty acid esters [5-7].
2. Generations of Biofuels:
Hitherto, an immense research in the exploration and development of alternate biofuel resources with
desired qualities has been carried out. Based on the resource type, four generations of energy crops have
been categorized as first, second, third and fourth generations.
The First Generation biofuels are produced directly from food crops by extracting oils as raw
material for biodiesel or bioethanol production through transesterification and fermentation respectively.
Bioethanol, fatty acid methyl ester (biodiesel) and pure plant oil are the different types of biofuels
currently play a major role at the global level, all belong to the first generation fuels [8]. Crops such as
wheat and sugar are the most widely used feed stocks for bioethanol, while rape seed has been proved a
very effective crop for biodiesel. However, first generation biofuels have a number of associated
problems. There is a serious debate over their actual efficacy in reducing greenhouse gases (GHG) and
CO2 emissions due to the fact that some biofuels can produce negative net energy gains, releasing more
carbon in their production than their feedstock’s CO2 capturing capacity during their growth. However,
the most contentious issue with first generation biofuels is ‘fuel vs food’. As the majority of biofuels are
produced directly from food crops, the rise in demand for biofuels has led to an increase in the volumes of
crops being diverted away from the global food market. This has been blamed for the global increase in
food prices over the last few years. This is the foremost reason for the inception of second generation
fuels [9-11].
Second Generation biofuels have been developed to overcome the limitations of first generation
biofuels. They are produced from non-food crops such as wood, organic waste, agriculture waste and
specific biomass crops, therefore eliminating the main problem with first generation biofuels. Second
generation biofuels are also aimed at being more cost competitive in relation to existing fossil fuel. Life
cycle assessment of second-generation biofuels has also indicated that they have increased ‘net energy
gains’ compared to first generation biofuels [10, 12-14]
Third Generation of biofuels is based on improvements in the production of biomass. It takes
advantage of special energy crops such as algae as its energy source. The algae are cultured to act as a
low-cost, high-energy and entirely renewable feedstock. It is predicted that algae will have the potential to
produce more energy per acre than conventional crops. Algae can also be grown using land and water
unsuitable for food production, therefore reducing the strain on already depleting water sources. A further
benefit of algae based biofuels is that the fuel can be manufactured into a wide range of fuels such as
diesel, petrol and jet fuel. However, scale up of algal systems for biofuel production is not very
economical [15, 16].
Fourth Generation Bio-fuels are aimed at not only producing sustainable energy but also a way
of capturing and storing CO2. Biomass materials, which have absorbed CO2 while growing, are converted
into fuel using the same processes of second generation biofuels. This process differs from second and
third generation production in a way that, at all stages of production, the carbon dioxide is captured using
processes such as oxy-fuel combustion. The carbon dioxide can then be geo-sequestered by storing it in
old oil and gas fields or saline aquifers. This carbon capture makes fourth generation biofuel production
carbon negative rather than simply carbon neutral, as it ‘locks’ away more carbon than it produces. This
system not only captures and stores carbon dioxide from the atmosphere but also reduces CO2 emissions
by replacing fossil fuels [17, 18].
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This review provides theoretical background on the mechanical and chemical methods of
extraction from all generation biofuel sources. The practical issues of each extraction method such as
efficiency of extraction, extraction time and type of oil source and its pros and cons are discussed. Finally,
potential applications of those extraction methods are reviewed.
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be adjusted by managing the gap using adjustable restriction cone. A pressure as equal to small scale
expellers can be achieved in ram press. It has the processing capability of approximately 4kg/hour. The
ram press is specifically designed for deoiling of sunflower seeds. Currently, ram press is being used for
the extraction of oil from groundnuts, copra and sesame. The extraction efficiency of ram presses varies
from 57-62% [20]. In case of Jatropha, 65% of oil can be extracted through ram press. Though ram press
is found inefficient for large scale oil extraction, still it is being used to produce oil energy source in rural
areas [21]. The advantages with the use of ram press are, i) requires minimal operational skill, ii) low
maintenance and repair, iii) low cost equipment and iv) simple and affordable in rural areas [22].
3.1.2. Bridge press. The design of a bridge press consists of a press plate, which is placed at the bottom of
a screw rod. The setup looks like a nut set that moves in to the bridge of the cage. A single horizontally
positioned head bar with two levers moves the screwed rod. Thrust bearing ease the movement of
screwed rod against pressure plate. Figure 2 shows the bridge press designed by NRI (Natural Resources
Institute) [19].
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be loaded to the mortar. Bullock driven ghani has the capacity of 10kg seed/2hr. Motor driven ghanis
(power ghanis) are found to be efficient compared to bullock driven ghanis, as the animals become tired
of working continuously for 3-4hr. Usual throughput of motor ghanis is about 100kg seed/day. Use of
ghanis for oil extraction is advantageous as they do not require costly equipment. In addition, no
pretreatment of seeds is required and the extracted oil stands for its quality. Figure 4 shows a typical
power ghani set up [19].
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Chemical extraction methods mostly involve organic solvents. Hence, chemical extraction is also termed
as solvent extraction. Solvent extraction is mostly widely used and commercial method for the separation
of oil and fats (lipids). Though the effect of ultrasound waves and microwaves is mechanical, the current
review considered ultrasonic assisted extraction and microwave assisted extractions under solvent
extraction as mostly these techniques are being used in conjunction with the use of solvents.
If it is intended to extract high yield of oil from the oleaginous material using mechanical
methods, the oil source has to be dried to low moisture content or exposed to high temperatures,
resulting in the darkening of extracted oil. On the other hand, during extraction by most of the
expellers or presses, the meal which can be used as fodder or human nutritional food will
experience high temperatures and make it unsuitable for the purpose. In addition, mechanical
method of extraction has low efficiency and leaves high oil content in the seed cake. Mechanical
methods are found unsuitable for complete oil extraction from low oil containing seeds such as
soybeans. To overcome the disadvantages associated with mechanical methods, solvent methods
have been developed. Even, solvent extraction is extensively being used to extract residual oil
present in the seed cake from mechanical extraction [28]. Solvent extraction is the isolation of
specific or desired components from solid or liquids by using a solvent. There are different types
of solvent extractions, most common are liquid – liquid and solid-liquid extractions. The focus of
this review is circumscribed to solid-liquid extraction as most of the oleaginous materials are
solids and are directly used for oil extraction.
Chemical properties of the extractant as well as the analyte influence the phenomena of extraction.
Mostly, solubility, hydrophobicity or hydrophilicity, vapor pressure, molecular weight and acid
dissociation are the fundamental properties of an analyte that decide the selection of solvent for extraction
[29]. Particle size (reduced particle size limits the barrier between two phases), agitation speed and
temperature of extraction influences the efficiency of the solvent extraction.
3.2.1. Folch method. Individual organic solvents or combinations of organic solvents are used to extract
specific class of lipids from a mixture of organic compounds. Folch and firm had developed a solvent
lipid extraction method from animal tissue with the use of Chloroform and methanol (2:1volume basis).
The procedure of Folch et al [30] method is as follows; initially the cells (mostly tissues) are
homogenized and equilibrated with 25% volume of saline solution, followed by rigorous mixing. The
resultant mixture on gravity separation forms two distinguished layers, where the upper phase
accommodates lipids. Folch et al method is the oldest method for lipid extraction and forms the basis for
the development of existing advanced solvent extraction methods. Though the method is rapid and ease,
less sensitive compared to other total lipid extraction methods.
Bligh and Dyer method:
It is the widely adopted method for the extraction of lipids and the mode of extraction is similar to that of
Folch et al method. The main difference between the Folch and Dyer methods is the difference in the
solvent/solvent and solvent/tissue ratios. Bligh and Dyer [31] method involves the simultaneous
extraction and separation of lipids. In addition, proteins form a precipitated layer between the two liquid
phases. The procedure involves the use of chloroform and methanol in 1:2 (v/v) and finally the lipids can
be further separated from the chloroform phase. This method is most widely being used for the extraction
of lipids or fats from third generation biofuel sources (algae). To improve the efficiency of this method,
researches have adopted the use of one molar NaCl as an alternate to water. The use of NaCl prevents the
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binding of acidic lipids to the denatured lipids. Later, it was found that the addition of 0.2M phosphoric
acid and HCl reduced the separation time of lipids [32].
3.2.2. Soxhlet extraction. Soxhlet extraction is one of the most traditional techniques still being used for
the separation of a wide range of volatile compounds to oils from solid samples. In mid 19 th century,
Baron Von Soxhlet has introduced this method, after whom the method is named. Soxhlet extraction is a
popular method and is being considered as a reference for several existing modern extraction techniques.
Figure 6 [33] shows the set up of a typical Soxhlet apparatus, mainly consists of a round bottom
flask, a thimble holder and a condenser.
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Different solvents yield different natural compounds from the material taken and also the extract
composition differs from solvent to solvent. Therefore, selection of a solvent for oil extraction is a most
critical step for Soxhlet extraction [39]. Hexane, an extensively used solvent for oil extraction has
peculiar characters such as excellent oil miscibility, distinguishable boiling point range (63-69°C) and
easily recoverable. However, the Environmental Protection Agency (EPA), USA has categorized n-
hexane as top most hazardous solvent among 189 air pollution causing solvents [40]. This is also one of
the challenges experienced by Soxhlet extraction.
3.2.3. Supercritical fluid extraction (SFE). In general, solvent extractions (Soxhlet) are associated with
the limitations of longer durations, large quantity of solvent requirement and incomplete expulsion of
hexane from the oil. Hence, finding alternate innovative technologies that could overcome these
limitations is imperative [41]. In considering the environmental issues tagged with solvent extraction, U.S
E.P.A has promoted the pollution prevention technologies through green chemistry. Initially, in 1980’s,
SFE has been developed as laboratory method and an alternate to organic solvents use for the extraction
of lipids. Later, it has been developed as an industrial scale technique and subsequently replaced the usual
direct solvent extraction methods. Gases such as CO2, propane, toluene, ethane and water are used as
solvents in SFE at their supercritical conditions. A gas at supercritical conditions possesses the properties
such as density and solubility as a liquid whereas, viscosity, diffusivity and surface tensions similar to
that of a gas. These changes in the properties improve the selectivity, flow rates and mass transfer than the
normal solvents. In addition, the use of these gases as solvents in SFE makes the extraction more efficient
and environmentally benign when compared to conventional solvent extractions [42].
Carbon dioxide (CO2) is the most commonly used oil/lipid extraction solvent in SFE owing to its
acceptable critical conditions (temperature 304°K and pressure 73atm), low cost, non flammability and
non toxicity [43]. The properties of supercritical CO2 for the extraction of oils and fats are summarized as,
1) high solubility of non polar compounds, 2) high dissolution of low molecular weight components, 3)
high affinity towards oxygen containing organic substances, 4) less solubility of water at ˂100°C, 5) Less
affinity towards proteins, polysaccharides and other salts and 6) Compound of interest can be extracted by
adjusting temperature and pressure [44]. Figure 7 shows the schematic representation of Supercritical CO2
apparatus [24].
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pumps. The temperature of extraction chamber is maintained through heating jacket and thermostat. Back
pressure valve is helpful to regulate the pressure. The supercritical CO2 interacts with the material in the
extraction chamber and the extracts are collected in collector. Reduction in pressure lightens the CO2,
leaving the extracts in the collector and the CO2 is circulated for further extraction [45].
The principle involved in the SFE is that, when a solvent at its supercritical conditions interacts with
oleaginous sample, dissolution of oil occurs in to the solvent. The soluble oil can be separated from the
supercritical fluid by reducing the pressure. Factors such as temperature, pressure and extraction time
influences the extraction efficiency and also purity of the oil. When considering the total lipids, almost all
the lipids dissolve in the supercritical fluid, makes the separation process difficult. Usually adsorbents
such as silica, celite and synthetic resins are used to enhance the separation of soluble lipids from
supercritical CO2 [44]. Even though supercritical CO2 extraction is efficient than other solvent extractions
and yields quality oil, still the technique is in its infancy and has not found wide commercialized
applications for the extraction of oils. High equipment and operation costs are predominant reasons for
non commercialization of the technique. Research is being carried out to optimize the process parameters,
there by the reduction of process cost [24].
3.2.4. Ultrasound assisted extraction (UAE). As conventional solvent extraction methods have limitations
of longer duration of extraction, toxic solvents usage and low efficiency, investigations have reported that
combination of mechanical waves with the solvent extraction techniques can transcend these barricades.
Lately, ultrasonics have received a greater attention to use in the extraction processes from medicinal
tinctures to industrial biodiesel production [46]. Ultrasonic extraction can be brought about in lab scale by
using ultrasonic cleaning bath (indirect) and ultrasonic probe or horn (direct) systems. Ultrasonic reactors
are used for industrial applications. Figure 8 represents the bath (a) and probe (b) ultrasonication systems
[47].
Figure 8. Diagrammatic representation of Ultrasonic systems a) bath cleaning and b) probe [47].
The set up of both the systems should be provided with a mechanical agitator and cooling bath to control
the rise in temperature during extraction. The bath system contains transducers attached at the base to
provide ultrasound waves. The probe system has ultrasonic transducer fitted in to the extraction chamber.
During the direct extraction, the probe must be in contact with the solvent medium but not the material
being extracted because, the solid material may clog the probe [47].
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The extraction is facilitated by two physical phenomena; diffusion through the cell walls and washing out
of intracellular contents through the broken walls. The walls of glands or cells are said to be very
sensitive (mostly plant based) and are easily breakable upon exposure to ultrasound. This forms the basis
for the extraction of fats and lipids as well as essential oils from variety of materials. The efficiency of the
process can be increased by reducing the size of the material, which improves the solvent interaction with
the material and there by the cavitation assisted extraction. Ultrasonic system either bath or probe when
used for the extraction of dried samples, the extraction is not only brought about by mechanical means. It
involves two stages, at first, the material is steeped to facilitate swelling and hydration processes. In the
next stage, the intracellular contents are transferred in to the solvent by diffusion and osmosis phenomena.
Extraction efficiency of ultrasonic assisted process is found higher than the extraction facilitated through
mechanical stirring [46,47].
The principle involved in ultrasonication is based on the phenomenon of cavitation. When high frequency
(20kHz) ultrasound waves are pulsed in to the sample containing solvent medium, bubbling occurs
throughout the medium. The grown bubbles with negative pressure implode at the surface of the cells,
causing a mechanical stress on the cells. Collapse of cavitation bubble at the surface of cells causes cell
wall damage and leads to the transfer of intracellular contents to the solvent medium. During the process
of bubble implosion, shock wave impulses are generated and which creates a microenvironment of high
temperature and pressure at the surface of the sample. These shock waves and energetic micro liquid jets
enhance the solubilization of metabolites in to the solvent medium and hence improve the extraction [48,
49]. The efficiency of ultrasonic extraction depends on the temperature, frequency of waves and duration
of ultrasonication [49]. UAE can be applied to both solid and liquid samples but care should be taken
while using solid samples. Cavitation bubble collapse may cause decomposition of analyte if entrapped in
to the bubble. Even though ultrasonic assisted extraction is rapid and efficient than conventional Soxhlet
extraction, it also involves large quantities of hazardous and expensive organic solvents [50].
3.2.5. Microwave assisted extraction (MAE). In conventional methods of solvent extraction mass transfer
of analytes from the sample to solvent is by diffusion and osmotic processes, which limits the rate of
extraction. In such conditions, process intensification can improve the extraction kinetics and efficiency.
Microwave assisted extraction, an unconventional intensification technique has been developed to
improve the yield, quality and efficiency of the conventional solvent based processes. In recent times,
MAE has become a promising, economically tenable, simple and efficient process to separate selective
compounds at higher rates in less time. MAE is a green extraction technique, which involves the use of
water or alcohols as solvents at controlled pressure and high temperatures. Water has high dielectric
constant due to its highly polar nature. Hence, traditionally it is not considered as an extraction solvent for
non polar organic components. However, at elevated temperatures and controlled pressures, water will
attain the properties of alcohols and can dissolve wide range of low to medium polarity compounds
during extraction [51]. Figure 9 shows the diagrammatic representation of microwave assisted solvent
extraction apparatus [52].
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The efficiency of a solvent to be used as an extraction medium in MAE depends on the dissipation factor,
a measure of solvent ability to absorb microwave energy and dissipate it to the surrounding molecules as
heat. Microwave based extraction work on targeting the moisture entrapped in the sample of extraction.
When microwave heats up the moisture trapped inside the cells of the sample material, moisture tries to
evaporate, thereby creating an extensive pressure on the cell walls through swelling. The inside pressure
pushes the cell wall, leads to stretching and rupturing of walls and releases intracellular contents to the
solvent. Thus, improves the extraction yield. The efficiency of MAE can further enhanced by using
solvents with high heat dissipation capacity [53]. The mechanism of MAE involves the following steps, i)
Desorption of analytes from sample matrix under applied pressure and elevated temperatures, ii)
Diffusion of extraction solvent in to the sample matrix and iii) Dissolution of analytes in to the extraction
solvent. The bolstered efficiency of solvent extraction with the use of microwaves is due to improved
solubility of analytes into the solvent, reduction of mass transfer limitations and enhanced disruption of
surface equilibrium [38]. Efficiency of MAE depends on solvent nature and volume, extraction time,
microwave power, sample particle size, moisture content, temperature and pressure of extraction. MAE
has advantages of environmentally friendly, cost effective, low quantities of solvents usage and reduced
extraction times. On the other hand, it has the limitations of low efficiency when the extraction solvent or
analyte are non polar or volatile. Also, as the technique involves high temperatures, decomposition of
thermo labile compounds may occur [54].
Ibrahim et al [55] have designed a screw press and processed Egyptian jatropha seeds for extraction of oil.
Optimum oil yield was found to depend on temperature, time, motor power and torque. The favorable
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conditions for maximum oil extraction from Egyptian jatropha were reported as 100°C and 60 rpm. It was
also reported that, operation of screw press beyond 100°C has increased the free fatty acid levels in the
extracted oil. A comparative study on the oil extraction capacity and oil quality from wild apricot kernel
by Kate et al [56] was reported as: oil extraction by means of traditional manual kneading was laborious
and required repeated processing of the same paste. Also, extraction was found to be not complete and
wastage of oil was noticed. Whereas, with motor driven expellers, oil quality was improved due to
decorticators at less labor requirement and has a throughput of 150kg/hr. The firm has concluded that
wild apricot kernel extraction by expeller press has high efficiency than the traditional manual kneading
method. In another study, optimization of mechanical extraction of Jatropha curcas seed was studied and
the effects of temperature, rotational speed of screw press and press cylinder size on chemical properties
of jatropha oil to be used as stove combustion fuel were reported. Optimum operation of screw press was
found based on oil recovery, analyzing time and residual oil in the seed cake. The optimum conditions for
jatropha seeds were reported as 260 rpm and press with 1mm holes [57]. A comparative oil extraction
study was carried out with Australian native beauty leafs seed (Calophyllum inophyllum). Oil extraction
was carried out with electrically driven screw press and n-hexane solvent extraction. The results have
shown that the oil can be extracted by screw press at low cost but higher yields can be obtained with
solvent extraction [58]. Algal oil extraction was carried out with mechanical expeller and hexane solvent
extraction. Solvent extraction has recovered the oil completely from the algae, leaving 0.5%-0.7% in the
residue whereas, only 75% of oil recovery was reported with expeller method. It was demonstrated from
the study that, solvent extraction can be an effective method for the oil extraction from algae but has the
disadvantage of high cost [59]. Ali et al [34] have conducted a comparative study on the extraction of oil
from flax seeds by mechanical expeller, solvent extraction, microwave assisted, ultrasonic assisted and
combine microwave and ultrasonic assisted extractions. The maximum oil yields on % weight basis were
obtained as 22.6%, 36.3%, 10%, 42% and 27.8% respectively. The relative ratios of energy consumption
were calculated based on the energy requirement and energy recovered from each process. Net energy
ratio was found to be highest 25.21% for microwave assisted extraction and thereby concluded that
microwave assisted extraction is an efficient and energy feasible method to extract oil from flax seeds.
The extraction efficiencies of microwave assisted extraction and ultrasonic extraction were compared
with conventional solvent extraction for soybeans using different solvents such as hexane, isopropanol
and mixture of both. It was found that the extraction yields were high for both ultrasonic assisted and
microwave assisted extractions in mixed solvent of hexane and isopropanol [60].
5. Conclusion:
The efficiency of oil/lipid/fat extraction depends on the method adopted and the material source.
Mechanical methods have advantages of producing high quality oil. Solvent processes reduce the
extraction time and mechanical wave based systems are capable of increasing the efficiency as well as
yield of extraction. The other side, each method has its own drawbacks. The process of extraction for
biofuel production has experienced a tremendous change and in particular advancements with the
development of unconventional extraction techniques such as ulatrasonication, microwave and
supercritical fluid extraction techniques. However, the limitations associated with these techniques still
demands further research in the field to satiate the alternate fuel energy needs.
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