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Refining of edible oils: A critical appraisal of current and potential


technologies

Article  in  International Journal of Food Science & Technology · September 2014


DOI: 10.1111/ijfs.12657

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International Journal of Food Science and Technology 2015, 50, 13–23 13

Review
Refining of edible oils: a critical appraisal of current and potential
technologies

Chandrasekar Vaisali, Sampath Charanyaa, Prasanna D. Belur* & I. Regupathi


Department of Chemical Engineering, National Institute of Technology Karnataka, Surathkal, Srinivasnagar, Mangalore 575 025, India

(Received 28 April 2014; Accepted in revised form 5 August 2014)

Summary The major sources of dietary lipids are edible oils, which include both vegetable and fish oils. Crude oil
extracted from vegetable and fish sources contain mono-, di-, triacylglycerols along with impurities, which
necessitates refining. The main objective of refining is to remove the contaminants that adversely affect
the quality of oil, thereby reducing the shelf life and consumer acceptance. However, this refining process
needs to be tailored as the composition of crude oil is highly variable, depending upon the plant/fish spe-
cies, geographical location of the source and method of oil extraction. Recently, extensive efforts have
been made to develop refining technology, using either conventional physical/chemical processes or several
unconventional processes including biological and membrane processes. The first section of this review
gives a brief description of general composition of some commonly used vegetable and fish oils, followed
by the review of various refining methods and their effects on the oil constituents. Finally, an effort is
made to understand the technological gaps in the existing methods and possible directions of research to
overcome the said gaps.
Keywords Bleaching, deacidification, degumming, deodorisation, edible oil, fish oil, n-3 polyunsaturated fatty acids, refining.

acid (EPA) and docosahexanoic acid (DHA) per day


Introduction
in the form of fatty fish or its supplements is adequate
Among carbohydrates, proteins and lipids which are to elicit desirable benefits such as reducing platelet
available through food to humans, lipids are the most aggregation and lowering plasma triglycerides (Gogus
concentrated source of metabolic energy. The type of & Smith, 2010).
fat consumed plays a major role in the health of an Vegetable oils and animal fats (meat, pork etc.) are
individual as higher intakes of trans and saturated fats the major source of dietary lipids. According to Uni-
are known to have adverse effects, viz. promote insulin ted States Department of Agricultural (USDA), the
resistance, inflammation and increase in LDL total oil production has increased from 140 million
(low-density lipoprotein) cholesterol, develop risk of metric tons in 2010–161 million metric tonnes in 2013
diabetes and cardiac death (Mozaffarian et al., 2006; to meet the demand. Palm, olive, soybean, sunflower,
Bendsen et al., 2011). The ill effects of trans-fats have coconut, corn, cottonseed and peanut are some of the
been proved unlike saturated fats. A systematic review oils of vegetable origin that are most widely used,
and meta-analysis on the association of coronary dis- while body oils and liver oils from aquatic organisms
eases and fatty acids carried out by Chowdhury et al. contribute to edible oil of marine origin (FAO). The
(2014) concludes that there is no clear evidence to domestic use of fish oils is yet to be practised world-
claim that intake of saturated fats cause cardiovascular wide as there is no commercially viable production
diseases. The beneficial applications of essential fatty technology available to produce edible fish oil without
acids like unsaturated fatty acids on human health losing n-3 PUFA and other valuable components.
have increased the market and market value for the Hence, there is an ongoing effort to develop refining
edible oils (FAO/WHO consultation 2011). It has been technology for every variety of edible oils (vegetable/
proposed that an intake of 0.25 to 1.8 g of n-3 polyun- fish) so as to produce nutritionally rich, colourless,
saturated fatty acids (PUFA), such as eicosapentanoic odour less, neutral and bland tasting oil.
The available reports on edible oil refining are
*Correspondent: Fax: +91 824 2474033; mostly focused on oil processing with reduced oil loss
e-mail: prsnbhat@gmail.com (De & Bhattacharyya, 1999; Mag, 2007; Dijkstra,

doi:10.1111/ijfs.12657
© 2014 Institute of Food Science and Technology
14 Refining of edible oils C. Vaisali et al.

2009, 2010). As it is mandatory to know the composi- cess is to retain n-3 PUFA, while eliminating other
tion of oil before designing a refining process, this undesirable components of raw oil.
review gives a brief description on the general compo- The difference between fish oil and vegetable oil that
sition of oil and highlighting the difference between has significant effect on choice of refining strategy is
fish and vegetable oils. This review further describes the fatty acid profile. In fish oil, the major unsaturated
alternative approaches for the most crucial refining fatty acids belong to the n-3 family (EPA 20:5 n-3 and
process, viz. degumming and deacidification tried by DHA 22:6 n-3) having nutritional and medical signifi-
various researchers along with their merits and demer- cance. While EPA and DHA are readily available in
its. Finally, the effects of these processes on the oil fish oil (Table S1), vegetable oils posses alpha lenolen-
quality have also been discussed, providing an insight ic acid (Table S2) that act as precursors for EPA and
in making a choice of effective method specific for DHA synthesis in human body (Davis & Etherton,
particular oil. 2003). While fish oils have overtaken vegetable oils in
their commercial importance, vegetable oils are still
widely used due to their various attributes, viz. appear-
General composition of edible oil
ance, taste, smell, cultural preference and ease of pro-
The composition of fats and oil differs greatly based duction. Also, the oxidative and thermo stability of
on the species, strain, environmental conditions and highly unsaturated compounds restricts use of certain
also the extraction procedure used. Before 19th cen- harsh refining processes that are widely used
tury, many oils were used without refining which industrially.
included olive, lard, tallow, linseed and certain cold The nonfatty components of oil contribute to the
pressed oil (Dijkstra, 2013). After the advent of solvent unsaponifiable matter. The unsaponifiable matter con-
extraction, many seed oils are extracted by this tech- stitutes up to 1–10% of vegetable oil and in some fish
nique while boiling and expression methods are used liver oil it is found in higher quantities (Channon,
for fish oil extraction (Bhosle & Subramanian, 2005). 1928). This unsaponifiable portion of oil is made up
The oil processing industry is a large scale operation, of many components, such as tocopherols, phytoster-
using bulk raw material from different seasons and ols, polyphenols and carotenoids in case of vegetable
with varying freshness and composition and thus con- oil and compounds, such as squalene, tocopherols,
tains essential components along with impurities, such fatty alcohols and sterols in fish oil (Channon, 1928;
as free fatty acids (FFA), phospholipids and volatile Ghazani & Marangoni, 2013). The presence of these
compounds (Table 1). components have beneficiary effects, hence the choice
of refining process should ensure minimal loss of
these components.
Essential components
Acylglycerols (mono-, di-, triglycerides) contribute to
Undesirable compounds
the major portion of fats and oils (Table S1) with high
nutritional significance (Sun et al., 2002). The fatty FFA are derived from lipids by cleavage of ester
acids shown in Fig. S1 are some of the essential fatty bonds due to enzyme (lipase) action, heat and mois-
acids that play a vital role in different stages of ana- ture (Akoh & Min, 2002), which happens after the
bolic and catabolic reactions in human body. n-3 harvesting of raw material for oil extraction. FFA in
PUFA are chemically reactive, having low stability to oils can act as pro-oxidants which initiate the oxida-
heat, light, atmospheric oxygen and impurities, posing tion mechanism in lipids and also decrease the smoke
oxidation problems during storage (Chaiyasit et al., point of cooking oils. Chaiyasit et al. (2007) has criti-
2007). Thus, the major challenge for the refining pro- cally reviewed the effect of interaction of FFA with

Table 1 General composition of edible oils and their overall effect on oil quality

Quantity

Type of components in oil Character Crude Refined Effect on oil quality

Acylglycerols Desirable 90% >99% Improve


Tocopherols, squalence, sterols Desirable 200–800 ppm 50–300 ppm Improve oxidative stability
Phospholipids Undesirable 100–500 ppm <10 ppm Settling at bottom during storage
Free fatty acids Undesirable 5–20% <1% Act as pro-oxidant leading to oxidation of acylglycerols
Metal ions and metal complexes Undesirable 2–15 mg kg 1
<1 mg kg 1 Harmful for consumption and act as pro-oxidant
Oxidised products Undesirable 2–6 meq kg 1
<1 meq kg 1 Rancidity and harmful
Moisture Undesirable 1–3% <1% Act as pro-oxidant

International Journal of Food Science and Technology 2015 © 2014 Institute of Food Science and Technology
Refining of edible oils C. Vaisali et al. 15

Degumming Deacidification Bleaching Deodorization

Enzymatic Activated
Physical Biological adsorbents
Membrane Adsorption
Natural
Solvent
Alkali adsorbents Steam
Chemical Extraction
1. Water stripping
2. Acid Re-esterification Membranes
3. Soft degumming 1. Chemical 1. Coupled with solvent extraction
Figure 1 Overview of existing and potential
4. Total Degumming 2. Enzymatic 2. Coupled with supercritical fluid extraction
technologies for edible oil refining.

other components and the mechanism of oxidation has Edible oil refining
also been discussed. As evident from Fig. S1, the
essential fatty acids mostly contain double bonds and The production of oils and fats from vegetable and
are particularly more susceptible for free radical marine sources with a bland and neutral taste even
attack, which eventually lead to rancidity. FFA con- after several months of storage, while retaining their
tent is one of the most important factors that influ- nutritionally important constituents is the challenge,
ences overall quality of oil and hence the price. every edible oil industry faces today. To achieve such
Phospholipids are a class of lipids that are major characteristics, detrimental and flavour producing
constituents of the cell membrane hence found in high compounds have to be removed, while retaining some
concentrations (30–50% w/w) in vegetable oils due to of the most desirable components. Many unit opera-
the thick cell wall of plant cells (De & Bhattacharyya, tions serve this purpose, with sedimentation being one
1999). These components are extracted into the oil of the simplest. However, it is seldom used in indus-
along with other essential components. Phospholipid tries as it is a batch process that takes longer duration
rich oil when exposed to air or sunshine, leads to col- and speeds up the oxidation process. There is also a
our deepening and oxidative rancidity which in turn possibility of sedimentation of desirable components,
hinders the distillation and deodorisation during oil reducing the oil quality (Botha et al., 2000). Hence,
refining (Dijkstra, 2009). This makes the removal of the refining process has to be designed in such a way
phospholipids imperative during the refining stage. that the undesirable compounds are eliminated, mini-
Along with these major contaminants, minor compo- mising oil loss and maximising the availability of bene-
nents, such as metal ions, volatile matter should also ficial constituents. A schematic representation of the
be removed effectively so as to ensure edible quality of various available refining strategies is provided in
oil. Fig. 1.

Table 2 Efficiency of different deacidification processes and their limitations

Initial FFA Final FFA


Methods (%) (%) Limitation Authors

Alkali neutralisation 15.7 0.09 High loss of neutral oil Wang et al. (2001)
Physical refining 2.75 <0.1 Stringent pretreatment requirements Martinello et al. (2007)
Re-esterification
1. Chemical 37.6 1.50 Random and costly Ebewele et al. (2010)
2. Enzymatic 30.0 3.50 High cost of enzyme Bhattacharya & Bhattacharyya
(1989)
Biological refining na na Short chain fatty acid not utilised Cho et al. (1990)
Solvent extraction 16.5 0.33 Incomplete deacidification and high capital Kale et al. (1999)
cost
Supercritical fluid 37.7 7.80 Costly Turkey et al. (1996)
extraction
Membrane Technology na na Molecular weight difference is too low for Bhosle & Subramanian (2005)
effective separation

© 2014 Institute of Food Science and Technology International Journal of Food Science and Technology 2015
16 Refining of edible oils C. Vaisali et al.

Degumming
continuously searched for and used (Clausen, 2001).
Enzymatic degumming has gained importance recently
Degumming is the initial step in edible oil refining as it is highly effective and involves milder reaction
which removes phospholipids and some portion of conditions compared to chemical processes (Mei et al.,
trace metals along with mucilaginous substances. It is 2013). It catalyses the conversion of phospholipids to
crucial as it determines the stability of the oils during diacylglycerols which provides a relatively good yield
storage. The phospholipid content should be suffi- of oil compared to conventional processes (Dijkstra,
ciently low as they are more prone to hydrolysis than 2010). According to Dijkstra (2010), enzymes are inca-
acylglycerols (Koning & Evans, 1991). Hence, removal pable of catalysing the hydrolysis of nonhydratable
of phospholipids followed by FFA removal becomes phospholipids at an industrial scale, and hence the
the logical choice of refining stages. process has to be combined with other chemical treat-
ments. Despite being highly advantageous, enzymatic
Chemical treatments
degumming was never practised in commercial scale
due to the high cost of enzymes. These drawbacks led
The most widely used degumming method in industry to the search for techniques which are cost effective
today is water degumming followed by acid treatment with mild operating conditions.
(Dijkstra & Opstal, 1987). Water treatment ensures the However, there is a renewed interest in enzymatic
removal of hydratable phospholipids, while treatment process in recent years due to the availability of differ-
with acid works on the nonhydratable phospholipids ent commercial and cost effective enzymes. Steady pro-
(Dijkstra & Opstal, 1987; Mei et al., 2013). While gress made in the area of enzyme engineering and
there is significant loss of acylglycerols by this method, technology in the discovery and development of rele-
this degumming process is still followed due to the use vant enzymes is also encouraging researchers to focus
of cheap chemicals, profitable disposability of gums upon enzymatic process (De Greyt, 2012). Continuous
and market acceptability of oil quality (Dijkstra & attempts are being made to optimise the process
Opstal, 1987; De & Patel, 2010; De Greyt, 2012). Fur- parameters for maximum hydrolysis so that industrial
thermore, a Total Degumming Process (TOP) was standards can also be achieved (Jahani et al., 2008;
introduced where neutralisation of acid using an alkali Jiang et al., 2011; Liu et al., 2012). Dayton et al.
is done to avoid migration of phospholipids back into (2011), documented that phosphatidylinositol specific
oil (Zufarov et al., 2008). However, increased oil losses phospholipase C (PI-PLC) with thermostability and
made TOP less attractive to oil mills in contrast to fatty acid specificity has been disclosed along with
bio-diesel plants, which still uses this method (Dijk- methods for using them. The thermo stable property
stra, 2009). As chemicals like EDTA have the ability of PI-PLC led to its commercial significance and meth-
to chelate metal ions, they were effectively used for oil ods were developed to make the process feasible at the
degumming by a process called soft degumming (Cho- industrial level by use of immobilisation techniques
ukri et al., 2001). Although this process could be effec- (Zhau et al., 2012).
tively used for degumming as long as the initial Researchers also probed the possibilities of
phosphatide contents are low, the use of chelators like decreasing the reaction time and increasing the effi-
EDTA raised acceptability issues (Dijkstra, 2013). ciency of degumming by using recombinant enzymes
With increasing knowledge on the inevitability of or different combinations of enzymes at high temper-
degumming process many novel process were intro- atures (Bo et al., 2012 and Dayton et al., 2013; Hu-
duced, including use of mono-ethanolamines (Zufarov ang et al. 2014). Jiang et al. (2014) studied the effect
et al., 2009) and mechanical methods which applies of ultrasound on the enzymatic degumming and
ultrahigh shearing and mixing operations (Myong found that even the residual phospholipids can be
et al., 2008). However, very few oil mills use these pro- reduced to <10 ppm. But the major disadvantage
cesses industrially as they are costly and the loss of was the oxidative instability of the oil after process-
neutral oil is high (Dijkstra, 2009). The efficiency of ing. This recent interest in enzymatic process and
any chemical process discussed above depends on the the attempts to perfect it can pave the way to a
nature and quantity of phosphatides in oil (Dijkstra, potential industrial process of degumming involving
2013). Hence, a careful analysis of oil prior to refining milder conditions.
will help in choosing the best route of refining.
Membrane degumming
Enzymatic degumming
Another alternative degumming method that has been
The first enzymatic process launched in 1992, by using given much importance is the use of membrane tech-
porcine enzyme (PLA2) was considered unethical. nology. Degumming with membranes is an efficient
Hence, alternate enzymes of microbial sources were process as it minimises the number of steps, energy

International Journal of Food Science and Technology 2015 © 2014 Institute of Food Science and Technology
Refining of edible oils C. Vaisali et al. 17

consumption and involves nonadditions of chemicals. Deacidification


Hydraulic pressure acts as the driving force for perme-
ation in a membrane process and the nature of the Deacidification is a crucial step as the presence of
membranes determines the components to be rejected FFA results in the development of rancid flavour and
(Subramanian et al., 2001). The separation of speeds up oxidation process (Chaiyasit et al., 2007).
triacylglycerols (900 Da) from phospholipids (800 Da) Similar to degumming, many deacidification proce-
by ultrafiltration poses difficulties due to the small dif- dures have been proposed for industrial oil refining
ference in their molecular weights (Subramanian et al., (Bhosle & Subramanian, 2005). It is evident from our
2004). This was overcome as the phospholipids tend to description of the composition of fish and vegetable
form reverse micelles in nonpolar media (Hancer et al., oils that fish oil contains a higher degree of unsatu-
2002; Ribeiro et al., 2008). This process is highly effec- rated fatty acid content leading to high FFA content.
tive as the micelle formed imprisons certain amount of Hence, this step is more relevant and critical for fish
pigments and free fatty acids (Coutinho et al., 2009). oil refining in comparison with vegetable oils.
The membrane efficiency is characterised by the per-
meate flux and phospholipid rejection (Table S3). The Conventional alkali treatment
only variable that has any effect over these factors is
the transmembrane pressure (Gracia et al., 2006a,b; In conventional deacidification, alkali like sodium
Ribeiro et al., 2008). Membrane process for degum- hydroxide is added to the degummed oil, thereby pre-
ming can be carried out with both solvent/oil micelle cipitating FFA as soap stocks which are removed by
(Lin et al., 1990; Ribeiro et al., 2008) or with crude centrifugation or water washing (Bhosle & Subramani-
oil alone (Pioch et al., 1998; Manjula & Subramanian, an, 2005). Despite the fact that oil loss is more and
2009). The major problem in this process is the poor the wastewater generated is difficult to treat in such
flux as seen in Table S3, in solvent free conditions and processes, it is still widely used in industries as it gives
the instability of membranes while degumming micelle. refined oil of acceptable quality. Nevertheless, there is
Although micelle degumming was industrially prac- a serious interest in new approaches that will make
tised for a brief period of time, it was soon abandoned chemical refining more efficient and attractive (De
due to membrane fouling (De Greyt, 2012). The differ- Greyt, 2012). Tang et al., 2013 modified the process
ent polymeric composite membranes and their effi- by making use of perforated distribution plates to
ciency in removing undesirable compounds from increase the contact of FFA with alkali thus reducing
vegetable oil have been reviewed by Subramanian the oil loss. De & Patel (2011) investigated a modified
et al. (2004) based on which a pilot plant study on the alkali treatment, where calcium hydroxide was used at
degumming of rice bran oil was carried out (Subrah- high temperature and low pressure resulting in FFA
manyam et al., 2006). In a review by Cmolik & Pok- reduction to 0.8% in 2 h. A recent advancement in the
orny, 2000, authors have extensively analysed the field of alkali treatment is the use of so-called nano-
various degumming process and concluded that use of reactors. These are basically hydrodynamic cavitation
selective membranes poses more advantages in lab reactors, through which oil to be treated along with
scale process than conventional techniques which are alkali is passed under high pressure 40–80 bar. The
costly processes. Even with the availability of reason- combined effect of high pressure and unique design of
able knowledge on the parameters affecting the effi- reactor creates strong shear forces providing efficient
ciency of membrane process (Micro filtration/Ultra neutralisation (De Greyt, 2012). The process is claimed
filtration), optimised membrane processes for different to be advantageous as there is a significant reduction
oils and the correlation between the components of oil in the use of acid (90%) and caustic soda (over 30%).
and membrane performance are still unavailable. Despite the fact that Alkali treatment employing
Hence, there is a need for the development of opti- nano-reactors was found to be efficient, it failed to get
mised robust membrane process for each kind of oil acceptance by industry due to high energy require-
to realise the potential of membrane process for oil ments and applicability to only batch process (De
refining at commercial scale. Greyt, 2012).
The effect of degumming on the essential compo-
nents of vegetable oil has been studied by many Physical deacidification
researchers (Gracia et al., 2006a,b; Naz et al., 2011;
Bauer et al., 2012). All these works report a high In physical refining, removal of FFA and odour giving
reduction in the tocopherols of vegetable oil by chemi- compounds takes place in a single operation due to
cal degumming process while membrane processes also the difference in the volatility of different components
give negative retention (25%) of tocopherols and car- (Sampaio et al., 2011). Deacidification is achieved by
otenoids (Subramanian et al., 2004; Coutinho et al., heating oil to desired temperature under vacuum fol-
2009). lowed by the passage of steam which removes the free

© 2014 Institute of Food Science and Technology International Journal of Food Science and Technology 2015
18 Refining of edible oils C. Vaisali et al.

fatty acids. The variables that have major effect on this enzymatic process to overcome this drawback by
process are the temperature and steam flow rate designing a packed bed reactor with immobilised lipase
(Cvengros, 1995; Martinello et al., 2007; Sampaio for the effective re-esterification of free fatty acids. The
et al., 2011). Steam distillation is the only practical use of ion exchange acid resins was also explored as
method that is practised industrially nowadays, and is an alternate for inorganic chemical catalysts as they
always integrated with efficient degumming and have high selectivity (Boffito et al., 2013; Deboni et al.,
bleaching (Cmolik & Pokorny, 2000). Nevertheless the 2013). Due to the high capital cost involved, process-
high temperature employed in the process is undesir- ing with ion exchange resins is not followed at indus-
able, as unsaturated fatty acids tend to undergo degra- trial scale. However, further research to overcome this
dation reactions like cyclisation, isomerisation and problem, as done in the enzymatic process, can pro-
polymerisation (Fournier et al., 2007). Hence, this pro- vide a potential technology. This esterification applica-
cess is still followed industrially for low unsaturated tion can further be exploited as an effective strategy
oil like palm oil refining (Cmolik & Pokorny, 2000). for reducing the trans fat contents in fat blends
To overcome this drawback, molecular distillation (Wassell & Young, 2007; Wassell et al., 2010).
(low pressure) or short path distillation (low residence
time) were used for thermally unstable compounds
Biological deacidification
(Cvengros, 1995). The physical deacidification process
is more advantageous compared to alkali refining as it The use of microorganisms for the effective removal of
gives better product yield. The increased energy con- FFA was investigated by Cho et al. (1990). It was
sumption of the above process makes it less favour- found that Pseudomonas sp. isolated from soil samples
able. Moreover, subjecting oil to high temperature had the ability to utilise FFA without secretion of
under reduced pressure generates secondary reactions extracellular lipase. Lack of formation of respective
which ultimately alter the physicochemical characteris- glycerides was also noted. Designing media and pure
tics and organoleptic properties (Sengupta & culture maintenance is a tedious process and the
Bhattacharyya, 1992). These disadvantages in the inefficient separation of organisms from oil makes it
conventional refining process made scope for the unacceptable for edible purposes. Despite the fact that
search for new processes which are discussed further. this method involves ambient conditions, the inability
of the organism to utilise short chain fatty acids was a
major drawback. Also culture maintenance, media
Re-esterification
composition and downstream processes have to be
Re-esterification is a process in which free fatty acids taken into consideration during cost analyses.
are converted to neutral glycerides by esterification reac-
tion. This is one highly recommended method for
Extraction
deacidification of oil as there is an increase in the neutral
oil. The re-esterification reaction takes place at high Failure of enzymatic process at a commercial level has
temperatures (200–280 °C) between glycerol and excess led to the search for processes like solvent extraction
fatty acids, releases water which has to be removed that is effective in large scale applications. The differ-
(Bhattacharyya & Bhattacharyya, 1989; De & Bhatta- ence in the solubility of FFA and triglycerides is used
charyya, 1999). Chemical catalysts, such as zinc dust, as a basis for this process (Apelblat et al., 1996). It is
zinc chloride, 0.5% of naphthalein-beta-sulphonic acid advantageous as it takes place at ambient conditions
are usually used to speed up the reaction (Ebewele et al., and without loss of neutral oil. As many reports are
2010 and Kombe et al., 2013). While the process is tech- available on the effective deacidification of oil by this
nically feasible, it is not practiced in industry due to the method (Bhosle & Subramanian, 2005), researchers
high reaction temperature and the need for large quanti- started developing the liquid–liquid equilibrium data
ties of glycerol. Furthermore, usage of chemical catalyst for the oil-solvent model systems to have a detailed
raises safety concerns of the produced oil. idea on the process (Oliveira et al., 2012). In order to
In need of low reaction conditions, enzymatic re- make the technique more feasible at industrial level,
esterification has been exploited as an alternative Cheng & Lixiang (2013) developed a modified process
approach for chemical re-esterification. The potential by using heat exchangers along with filter frame to
of enzymatic re-esterification depends on different pro- remove impurities followed by centrifugal extraction.
cess parameters, such as glycerol concentration, However, solvent extraction process suffers from the
enzyme concentration, reaction time, reaction tempera- fact that removal of solvent traces from oil after
ture and moisture content in the reaction mixture extraction is tedious and energy intensive. Hence,
(Sengupta & Bhattacharyya, 1992; Rosu et al., 1999). supercritical fluids were proposed in the place of sol-
But the high cost of enzymes is a drawback for com- vents for extraction. The attractive features of super-
mercial application. Laomin et al. (2012) developed an critical fluids over the use of organic solvents are

International Journal of Food Science and Technology 2015 © 2014 Institute of Food Science and Technology
Refining of edible oils C. Vaisali et al. 19

nontoxicity, cheapness, ease of separation, highly selec- 2006). Hence, several researchers worked on modifying
tive and hence used for high acid oils (Dunford et al., the existing technology by combining two or more
2003). As the process requires expensive extraction processes and by the introduction of a new stage to
equipment, reducing the cost of production is the chal- already existing techniques (Niazmand et al., 2011).
lenge. However, this process looks promising where oil All the deacidification processes though efficient have
purity is the main factor. several drawbacks (Table 2). However, further studies
on new approaches are needed considering the eco-
nomic viability to successfully replace the existing
Membrane technology
technology.
Membranes are a good alternative for all separation
processes involving chemicals. With the wide applica-
Bleaching
tion of membranes in the degumming stage, attempts
were made to utilise this application for the deacidifi- Bleaching is a relatively important process which uses
cation step. Several researchers have tried deacidifica- bleaching clays or charcoal to remove many minor
tion of oil by membranes with or without solvents, as impurities like colour compounds, oxidation products
it provides a cost effective simpler process. Despite (peroxides), also trace metals, phospholipid remains and
these efforts, there is no breakthrough in the process. soaps from neutralised oils, thus improving the oxida-
As the free fatty acids are one-third the molecular tive stability and sensory qualities of the oil (Garcia-
weight of triglycerides, the difference is too small to Moreno et al. 2013). The adsorption capacity of clays is
separate by use of membranes alone (Subramanian due to high surface area and acidity. Activated clays are
et al., 1998; Bhosle & Subramanian, 2005). Hence, most preferred for treating vegetable oils as they are
membrane application is coupled with solvent highly specific, more chemically active and efficient
extraction process. As most of the membranes are (Zschau, 2001). In a review on palm oil refining, Gibon
designed for water treatment applications, the use of et al. (2007) provided a detailed description of the dif-
membranes for deacidification with solvents alters the ferent types of bleaching processes that have been used
membrane permeability characteristics (Raman et al., in many refineries. While there is some loss of efficiency
1996). Tres et al. (2010) characterised a number of due to thermodynamic limitations (Chapman & Pfannk-
polymeric membranes for their application in deacidifi- och, 1992), bleaching with different clays or charcoal is
cation and found that some membranes like polyam- still widely followed at industrial level, as it improves
ide, polyethersulfone are stable and suitable for the quality of the final product and works well with
deacidification of oil-solvent mixture. The single limi- chemically treated oil. Hence, researchers developed
tation of this process was membrane fouling, due to methods to activate cheap natural clays for improving
deposition of oil on the membrane surface. Firman their efficiency in edible oil refining (Foletto et al., 2013;
et al. (2013) studied different nanofiltration membranes Silva et al., 2013).
for this application and simultaneously analysed the Throughout literature, researchers have been aiming
permeability characteristics of membranes for efficient at producing edible oils of commercial consumer stan-
separation. In order to further improve the efficiency, dard by use of different bleaching agents and process
Rao et al., 2013 suggested a three stage deacidification (Eyup & C ß elik, 2005; Huang & Shativel, 2010; Suseno
process to reduce FFA levels upto 95%. Although et al., 2011). The available techniques of bleaching
many reports on effective application of membranes revolve around the same application of adsorption and
for edible oil refining are available, not many indus- new approaches are in demand. Su et al. (2013) sug-
trial applications are found. Research groups are still gested the use of ultrasound enhanced bleaching,
focusing on gaining more detailed knowledge of this where pigment removal was noted even in the absence
technology for finding new applications, and of mak- of adsorbents due to heat and sonochemical pigment
ing those already being applied, more economical and degradation. The major disadvantage of this process is
technologically attractive. the inability to remove secondary oxidation products.
As deacidification process greatly influence the prod- As bleaching is considered one of the important step
uct quality, harsh chemical and physical treatments are that guarantee the final quality of the oil, it is critical
still practised to ensure complete FFA removal. They to have more new approaches for this process that are
have the highest adverse effect on the nutritional com- specific and efficient.
ponents of oil by reduction in glyceride oil containing
essential fatty acids (Bhosle & Subramanian, 2005). In
Deodorisation
the case of physical deacidification process, the
tocopherol content in vegetable oil was found to This is the final stage of refining edible oil, for the
reduce drastically (Gibon et al., 2007), and degrada- removal of odour creating components and trace ele-
tion of PUFA was noted in fish oils (Fournier et al., ments thus extending shelf life of the oil. The end prod-

© 2014 Institute of Food Science and Technology International Journal of Food Science and Technology 2015
20 Refining of edible oils C. Vaisali et al.

uct of this step is high quality refined oil with light col- Conclusion
our and no odour. The odorous substances in oil are
usually by-products from lipid, protein and amino acid Refining is a necessary process that ensures the quality
degradation. This could be due to microbial spoilage, of the edible oils for human consumption. The
autoxidation or by lipoxygenase activity (Lin et al., removal of undesirable components while retaining the
1990). Deodorisation is generally carried out by conven- essential portion of oil is critical. While conventional
tional steam distillation process where compounds such methods like alkali treatment and physical refining
as undesirable flavour components, aldehydes and ke- gives good results, destruction and stripping of desir-
tone (oxidation products), residual free fatty acids are able components due to harsh chemicals and high tem-
removed. Based on the vapour pressure and volatility at perature warrant further improvement in technology.
high temperature (180–220 °C) the components are Use of eco-friendly techniques like enzymatic treat-
stripped from the oil. However, it is preferable to use ment is effective, but as the enzymes are expensive, it
temperatures below 200 °C as it affects the quality of oil is seldom practiced in industry.
by degrading essential components by cyclisation and The future prospect would be to design a sustainable
polymerisation of long chain PUFA (Camacho et al., integrated refining process with the consideration of
2001 and Fournier et al., 2006). cost. Several reports are available on investigation of
The substitution of nitrogen as stripping gas has single variety membranes for one or two steps of refin-
been investigated, as it avoids oxidation of valuable ing, but use of different set of membranes and modules
products and avoids formation of emulsion with water in combinations is yet to be assessed. It appears that
(Decap et al., 2004). As some oils are sensitive to high membranes processes are better poised to meet the
temperature, Chung & Lee (2009) investigated a novel current demand of efficient and environmental friendly
deodorisation process that involves the use of zeolites process. Although research on use of membranes has
for adsorption of trimethylamine (responsible for been going on for the past 30–40 years, very few com-
odour in fouling fish) at low temperatures. Although mercial applications have been reported. Future indus-
adsorption processes have many advantages over con- trialists and researchers are thus challenged to develop
ventional steam stripping, most of unsaturated alde- new membrane processes which are sustainable, cost
hydes and alkanedienols that are responsible for effective and efficient.
oxidation of PUFA were removed only in the steam Integration of membrane processes with conven-
stripping process. Hence, there is future scope for the tional process is worth exploring, as it can address sev-
study of application of different adsorbents for a sin- eral drawbacks of respective technologies thereby
gle step deodorisation and bleaching. Recent light on improve the overall efficiency, sustainability and eco-
the formation of monochloropropanediol esters (3- nomics of the process. Constituents like sterols and
MCPD, 2-MCPD) that cause significant health risk, tocopherols are stripped during deodorisation, and
has subjected deodorisation process to be controlled current knowledge indicates that health benefits may
and monitored stringently (Destaillats et al., 2012). be associated with their consumption and their mainte-
Hence, researchers tried to understand the mechanism nance in refined oils is advisable (and for oil stability
of formation and decomposition of MCPD ester in oil reasons as well). Refining processes that retain such
to have a better knowledge on refining strategy (Erma- components to a greater extent would be welcome.
cor & Hrncirik, 2014a,b). As there is no absolute pro- The complexity in the composition of fish oils has
cess for effective deodorisation without thermal made the application of membrane process difficult for
degradation, there is great demand for new fish oil refining. As not many reports are available on
approaches to be investigated for the complete de- the refining of fish oils, there is further scope in design-
odorisation without any loss of valuable products. ing the refining process for fish oil. Novel methods for
Although some reviews on refining of edible oil are deodorisation and deacidification of fish oil are yet to
available (Bhosle & Subramanian, 2005; Ghosh, 2007; be explored. Considering the fact that fish oil is rela-
Gibon et al., 2007; Coutinho et al., 2009; Dijkstra, tively cheap and abundantly available, efficient de-
2013; Ghazani & Marangoni, 2013), most of them dis- odorisation will help in promoting its use for culinary
cuss the refining strategies with respect to single type purposes as well.
of oil or a single stage of refining. There is no valid
report that could summarise the refining processes of Acknowledgments
all kinds of oil. Reports on refining techniques with
implications on marine oil are meagre. Due to the We gratefully acknowledge the financial support pro-
increasing importance given to n-3 PUFA of fish oils, vided by Science and Engineering Research Board
such reports on refining strategies for fish oil gives (SERB), Ministry of Food Processing Industries
industrialists better knowledge on their choice of tech- (MOFPI), Govt. of India to carry out this research
nologies to be used. (SERB/MOFPI/0016/2012).

International Journal of Food Science and Technology 2015 © 2014 Institute of Food Science and Technology
Refining of edible oils C. Vaisali et al. 21

of membrane technology to vegetable oils: a review. Food Research


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