J Food Sci Technol (July 2015) 52(7):4613–4618

DOI 10.1007/s13197-014-1461-0

ORIGINAL ARTICLE

Effect of refining on quality and composition of sunflower oil

U. S. Pal & R. K. Patra & N. R. Sahoo & C. K. Bakhara &
M. K. Panda

Revised: 18 June 2014 / Accepted: 27 June 2014 / Published online: 9 July 2014
# Association of Food Scientists & Technologists (India) 2014

Abstract An experimental oil refining unit has been devel- because of its high polyunsaturated fatty acid content, bland
oped and tested for sunflower oil. Crude pressed sunflower oil flavour, good storage stability and low viscosity (Semwal
obtained from a local oil mill was refined using chemical et al. 1996). Refined sunflower oil has emerged as one of
method by degumming, neutralization, bleaching and the most popular cooking oil in India. Sunflower seed pro-
dewaxing. The quality and composition of crude and refined duced a highly desirable polyunsaturated oil for human con-
oil were analysed compared. Reduction in phosphorous con- sumption. Its high proportion of valuable linoleic acid has
tent from 6.15 ppm to 0, FFA content from 1.1 to 0.24 % (oleic steadily increased the importance of sunflower oil in recent
acid), peroxide value from 22.5 to 7.9 meq/kg, wax content decades.
from 1,420 to 200 ppm and colour absorbance value from Crude sunflower oil is obtained from partially dehulled
0.149 to 0.079 (in spectrophotometer at 460 nm) were ob- seeds by mechanical pressing followed by hexane extraction
served from crude to refined oil. It was observed that refining and water degumming. Quality and stability are the major
did not have significant effect on fatty acid compositions as factors in the production, acceptance and marketing of vege-
found in the percentage peak area in the GC-MS chromato- tables oil products. These properties depend mainly on seed
gram. The percentage of unsaturated fatty acid in both the oils quality, seed treatment prior to extraction, extraction method
were recorded to be about 95 % containing 9-Octadecenoic and processing conditions. They are influenced by the pres-
acid (Oleic acid) and 11,14-Eicosadienoic acid (elongated ence of some minor components, such as free fatty acids,
form of linoleic acid). The research results will be useful to tocopherols, phospholipids, trace metals and waxes which
small entrepreneurs and farmers for refining of sunflower oil have pro or anti oxidant properties. The stability and quality
for better marketability. of vegetable oils are influenced by the presence of minor
constituents such as phosphatides (Carelli et al. 1997) and
Keywords Crude . Refined . Sunflower oil . Fatty acid waxes (Carelli et al. 2002). Processing of oils causes alter-
profile . FFA content . GC-MS ations in their chemical composition, affecting their quality
and oxidative stability (Brevedan et al. 2000).
Vegetable oils are refined in order to remove the non-
Introduction glyceride impurities that are present in the crude oil. Some
of these impurities are naturally present in the seeds or formed
Sunflower oil is used as a premium salad oil due to the during harvesting and storage of seeds or during extraction of
presence of high ratio of polyunsaturated-to-saturated fatty crude oil and subsequently during its refining. Oil refining
acids. Refined sunflower oil has found wide acceptance processes for vegetable oils are designed to remove these
impurities from the oil or reduce them to a level where their
deleterious effects on oil stability are minimum and made
U. S. Pal : R. K. Patra : N. R. Sahoo (*) : C. K. Bakhara : suitable for human consumption. Vegetable oil undergoes
M. K. Panda degradation almost immediately after the seed is crushed.
AICRP on Post Harvest Technology, College of Agricultural
The oil starts to show the sign of primary oxidation as mea-
Engineering and Technology, Orissa University of Agriculture and
Technology, Bhubaneswar 751003, Odisha, India sured by its peroxide value. Under certain circumstances the
e-mail: [email protected] oil may develop a darker colour or higher free fatty acids and
4614 J Food Sci Technol (July 2015) 52(7):4613–4618

eventually an unpleasant flavour. Gums, phosphatides and The centrifugal pump is connected to the tank outlet to force
mucilaginous substances act as emulsifier increasing loss of the oil through the pressure leaf filtration unit to filter the wax.
oil and decompose at high temperature, increasing colour of
the refined oil. Free fatty acids increase foaming, reduce Testing of the refining unit
smoke point and diminish keeping properties of oil.
Presence of compounds such as phosphatides, free fatty Mechanically pressed crude sunflower oil was obtained from
acids, odiferous volatiles, colourant, waxes and metal com- a local oil mill. The crude oil was kept in tin container away
pounds in oil negatively affect taste, smell, appearance and from the light, high temperature and oxygen to avoid auto
storage stability of the refined oil and hence must be removed oxidation. The oil was refined in the developed experimental
to yield a stable product with a bland or pleasant taste unit as per the process flow diagramme shown in Fig. 1.
(Aluyor et al. 2009). In modern society, consumers can not
use crude oil directly without proper processing due to the Degumming The crude oil in the open conical tank was
unacceptable colour and odour. This has led to efficient heated to 45 °C and degummed by adding 0.2 % phosphoric
refining process which involves removing these unpleasant acid (50 % w/w strength) with slow agitation for 30 min. Then
impurities with the least possible effect on the desired com- the oil was settled for 30 min and the water with dissolved
ponents (tocopherols, phenols, sterols) with the minimum gum was drained out.
losses of oil (Verhe et al. 2006).
Chemical refining includes degumming, neutralizing, Neutralisation The temperature of oil was further increased to
bleaching, winterizing and deodourising stages (Tasan and 71 °C and mixed with desired quantity of sodium hydroxide
Demicri 2005). When used for salad oil, the refined oil was solution (12 %) as per FFA content of the oil with slow
winterized for wax removal and then deodorized. Though
chemical refining decreased yield, higher investment cost,
high chemicals used and higher waste, but has less effect on Crude sunflower oil
oil desirable components and oil stability (Suliman et al.
2013). The objective of refining is to remove the objectionable
impurities with the least possible damage to the neutral oil and Degumming at 45ºC 50 % Phosphoric acid
@0.2%
minimum loss of oil during processing.
Several authors have investigated the influence of in-
Neutralisation at 71 ºC 12 % Caustic solution
dustrial processing, especially the refining process on qual-
ity and stability of different vegetable oils. Effect of press-
ing conditions on nonrefined sunflower oil has been pre-
Settling
sented by Turkulov et al. (1998) and the influence of water
Gum, Soap
degumming in phosphatide content has been discussed by
Crapiste et al. (1998). Hot water wash &
Settling 20 % hot water
The aim of the present work was to develop a mini oil
refining unit and investigate the effect of chemical refining Soap water
process on composition and quality characteristics of refined
Drying at 77 ºC under 75
oil as compared to crude oil. mm Hg vacuum Water

Materials and methods Bleaching under 75 mm Hg Bleaching earth @1.5 %

Development of oil refining unit

Filtration Spent earth
An experimental oil refining unit has been developed for
minimal refining of sunflower oil. The unit consists of (i)
one open mild steel tank with conical bottom for Dewaxing (Cooling to 15ºC)

degumming/neutralization, (ii) one closed oval tank for vacu-

um drying/bleaching and (iii) one filter for filtration of oil. The Filtration Wax
oil dewaxing section consists of a well insulated oil tank,
cooling coil, water cooler and filtration unit. The helical pipe
is immersed in the oil in the tank and the cold water from the Refined oil

cooler is recirculated for cooling the oil to crystallize the wax. Fig. 1 Process flow diagramme for refining of sunflower oil
J Food Sci Technol (July 2015) 52(7):4613–4618 4615

agitation for 15 min followed by settling for 30 min. The soap were methylated with sodium methoxide and the fatty acid
stock with residual gum was removed by draining. The neu- methyl esters (FAME) were analyzed in GC-MS for identifi-
tralized oil was washed with 20 % hot soft water at 75 °C and cation of different components.
residual soap was removed by settling.
GC Programme
Vacuum drying and bleaching The washed oil was heated at Column: Elite-5MS (5 % Diphenyl/95 % Dimethyl poly
77 °C under 75 mmHg vacuum for 30 min to remove the siloxane), 30 × 0.25 mm × 0.25 m df
moisture traces. The oil was next mixed with 1.5 % bleaching Equipment: GC Clarus 500 Perkin Elmer
earth (w/w) with vigorous stirring for 30 min under vacuum Carrier gas: 1 ml per min, Split: 10:1
for bleaching. Then oil was cooled to 60 °C and filtered to Detector: Mass detector Turbo mass gold-Perkin Elmer
obtain the bleached oil. Software: Turbomass 5.2
Sample injected: 2μl
Dewaxing The bleached oil was cooled gradually at 15 °C for
4 h for crystallization of wax and filtered to remove the wax. Oven temperature Programme
110 ° C −2 min hold
Quality analysis of sunflower oil Up to 200 ° C at the rate of 10 ° C/min-No hold
Up to 280 ° C at the rate of 5 ° C/min-9 min hold
The crude oil, refined oil obtained from the experimental Injector temperature 250 ° C
refining unit and commercially available refined sunflower Total GC running time 36 min
oil sample were analysed for moisture content, specific grav-
ity, kinematic viscosity, total phosphorous content (indication MS Programme
of phospholipids), Free Fatty Acid (FFA) content, peroxide Library used NIST Version-Year 2005
value, colour value and wax content using standard procedure Inlet line temperature 200 ° C
(Ranganna 2004) as given below for comparison with the Source temperature 200 ° C
Bureau of Indian standards (BIS) specifications. Electron energy: 70 eV
The specific gravity of oil samples were measured by Mass scan (m/z): 45–450
pycnometer method and viscosity by Kinematic Viscometer Solvent Delay: 0–2 min
at 40 °C. Moisture content was determined by oven drying at Total MS running time: 36 min
105 °C for 24 h.
The free fatty acid content was measured using the titration
method with 0.1 Normal sodium hydroxide solution and
phenopthaline indicator and expressed as % oleic acid. The Results and discussion
absorbance of oil was measured at wavelength of 460 nm in a
spectrophotometer using Carbon tetrachloride as blank which Quality of sunflower oil
was taken as an indicator for colour comparison. Peroxide value
was determined by Sodium Thiosulphate titration method. The physico-chemical parameters of crude sunflower oil,
Phosphorus content (an indicator of phospholipid content) refined oil obtained from the experimental unit and commer-
of oil was determined by wet digestion using di-acid mixture cial refined oil sample is given in Table 1. The oil samples
(nitric acid and perchloric acid @ 3;2). Phosphorus content in were found to be completely moisture free after refining and
the digest was estimated spetrophotometrically at 470 nm less than the maximum limit of 0.1 %. The specific gravity
wavelength after developing yellow colour with vanado- of crude and refined oil at 20 °C were found to be same
molybdate reagent. The standard curve was prepared using 0 (0.92) with the commercial sample. The kinematic viscosity
to 20 ppm phosphorus prepared with analytical grade of oil decreased from 38.8 to 36.2 cs after refining which
KH2PO4. was as par with the commercial sample. The reduction in
The wax content was determined gravimetrically by dis- viscosity was probably due to the removal of impurities
solving oil in acetone, cooling at 0ºC for 24 h and filtering during refining.
through Gooch crucible as per American Bureau of Shipping The crude oil under experiment was found to have
(ABS 227) method. 6.15 ppm of total phosphorous content (0.019 % phospho-
lipids) which was reduced almost to zero as most of the
Fatty acid profile by GC-MS Analysis phospholipids were removed by degumming and neutraliza-
tion process during refining. The phospholipids content of
The fatty acid profile of both crude and refined sunflower oil pressed and pressed-degummed sunflower oil were reported
was determined by Gas Chromatography. The given samples to be 0.737 and 0.132 % indicating a decrease in
4616 J Food Sci Technol (July 2015) 52(7):4613–4618

Table 1 Physico-chemical pa-

rameters of crude, refined and Quality parameters Crude oil Refined oil (from Commercial BIS standard
commercial oil (n=3) the developed unit) sample value

Specific gravity (20 °C) 0.92 0.92 0.92 0.92

Kinetic viscosity (40 °C) in cs 38.8 36.2 36.5 –
Moisture content, % 0 0 0 0.1
Phosphorous content, ppm 6.15 Trace Trace –
FFA content, (% Oleic acid) 1.10 0.24 0.13 0.25
Peroxide value, meq/kg oil 22.5 7.9 23.9 10
Wax content, ppm 1420 200 20 –
Colour absorbance value 0.149 0.079 0.050 –
(in Spectrophotometer
at 460 nm)

phopspholipid content during degumming operation (Carelli wax content of commercial refined oil varied between 360 and
et al. 1997). Brevedan et al. (2000) also reported decrease in 620 ppm, indicating a strong dependence on variety, condition
phospholipids content from 0.39 to 0.10 % during of seed and refining process. Wax content of sunflower seed
degumming of pressed sunflower oil. oil are reported to be in the range of 200 to 350 ppm (Martini
Free Fatty Acid content of crude sunflower oil was found to and Anon 2000).
be reduced from 1.1 to 0.24 (% Oleic acid) after neutralization. The colour absorbance value of refined oil measured at
The residual FFA content of the refined oil was less than the 460 nm in spectrophotometer was observed to be lower
maximum specified value of 0.25 % in the BIS standard for (0.079) than crude oil (0.149) which might be due to the
pressed refined sunflower oil. During the chemical refining removal of colouring pigments during bleaching operation.
process, most of the FFA content was eliminated during the The decrease in colour pigments after bleaching step due to
neutralization stage as soap because of the alkali treatment the effect of activated bleaching earth was also reported by
which improved the quality of oil. Suliman et al. (2013) Suliman et al. (2013).
reported similar results of reduction in FFA content from 0.5 The FFA content, wax content and absorbance value of
to 0.1 % during neutralization of crude oil. According to commercial refined oil sample were found to be less than the
Demian (1990), the FFA content is used to measure the extent oil obtained from the experimental refining unit which might
to which triglycerides in oil has been decomposed by lipase be due to the precise control of process parameters and large
and other actions such as light and heat and its determination scale operations in the commercial refining unit.
is often used as general indication of the condition and edibil-
ity of oils. The presence of free fatty acid and other fatty Fatty acid profile of sunflower oil by GC-MS analysis
materials in oil bring about the offensive odour and taste in
oil on long storage (Kirk and Sawyer 1991). The low FFA From the fatty acid profile analysis of both crude and refined
content of refined oil makes the oil edible and of higher oil, it was observed that there was no significant difference in
quality. The odour of the refined oil was agreeable and had fatty acid composition of both the samples as shown in the
no offensive smell which might be due to low FFA content of percentage peak area in the GC-MS chromatogram (Fig. 2).
the oil. This indicated that refining did not have much effect on fatty
The peroxide value reduced from 22.5 to 7.9 meq/kg acid composition which was also reported by Achinewhu
during refining which was less than the standard specified and Akpapunam (2005) and Aluyor et al. (2009). It was
value of 10 meq/kg. The reduction is probably due to the concluded that there was no undesirable polymerization of
absorbance of peroxide compounds by bleaching earth. oil during the refining process in the experimental refined
However, the peroxide value of commercial oil sample unit. 11,14-Eicosadienoic acid, methyl ester and 9-
was observed to be more than freshly obtained refined oil Octadecenoic acid (Z)-, methyl ester were the major com-
from the developed unit which might be due to oxidative pounds found in the GC-MS analysis (Table 2). The percent-
reactions in market sample during storage before age of unsaturated fatty acid in both the oils were recorded to
marketing. be about 95 % containing 9-Octadecenoic acid (Oleic acid)
Reduction in wax content from 1,420 to 200 ppm was and 11,14-Eicosadienoic acid (elongated form of linoleic
observed from crude to refined oil. The reduction in wax acid). Oleic acid (52 %) is the major unsaturated fatty acid
content was due to the separation of crystallized wax from followed by Eicosadienoic acid (43 %) in both crude and
cold oil by filtration. Carelli et al. (2002) reported that total refined oil.
J Food Sci Technol (July 2015) 52(7):4613–4618 4617

(a) Crude sunflower oil

(b) R efined sunflower oil

Fig. 2 GC-MS Chromatogram of (a) crude and (b) refined sunflower oil

Conclusion dewaxing. The quality and composition of crude and refined

oil were compared. The phosphorous content, FFA content,
An experimental oil refining unit has been developed and peroxide value and wax content decreased during the refining
tested for refining of sunflower oil. Crude pressed sunflower process. There was no significant difference in fatty acid
oil obtained from a local oil mill was refined using chemical profile of both crude and refined oil. Oleic acid is the major
method by degumming, neutralization, bleaching and unsaturated fatty acid followed by Eicosadienoic acid in both

Table 2 Fatty acid profile of crude and refined sunflower oil sample [GC MS study] (n=3)

No. Name of the compound Molecular formula MW Crude oil Refined oil

RT Peak Area % RT Peak Area %

1 Tridecanoic acid, methyl ester C14H28O2 228 12.16 3.8 12.16 3.7
2 11,14-Eicosadienoic acid, methyl ester C21H38O2 322 14.18 43.3 14.17 43.5
3 9-Octadecenoic acid (Z)-, methyl ester C19H36O2 296 14.27 51.9 14.25 52.3
4 Octadecanoic Acid, 11-Methyl-, Methyl Ester C20H40O2 312 14.57 1.0 14.57 0.5

MW: Molecular weight, RT: Retention time

4618 J Food Sci Technol (July 2015) 52(7):4613–4618

crude and refined sunflower oil. Further studies on storage Processing. Vol II, pp 32–35, S.S. Koseoglu, K.C. Rhee and R. F.
Wilson (Ed.). AOCS Press, Champaign, IL
stability of the refined oil obtained from the developed unit
Demian MJ (1990) Principles of Food Chemistry. 2nd Ed. Van
may give more information for its adoptability. Nostrond Reinhold International Company Limited, London
England. 37–38
Acknowledgments Authors are thankful to the Indian Council of Ag- Kirk RS, Sawyer R (1991) Pearson’s Composition and Analysis of
ricultural Research, New Delhi and Orissa University of Agricultural and Foods. 9th Ed. Longmand Sci. Tech. England pp. 607–617
Technology, Bhubaneswar for providing financial assistance and Martini S, Anon MC (2000) Determination of wax concentration in
infrastructure. sunflower seed oil. JAOCS 77(10):1087–1092
Ranganna S (2004) Handbook of analysis and quality control for fruit and
vegetable products 2nd Ed. Tata McGraw-Hill Publishing Company
Limited, New Delhi
References Semwal AD, Murthy MCN, Sharama GK, Arya SS (1996) Studies on
storage stability of commercially marketed refined sunflower oil in
plastic film packs. J Food Sci Technol 33(4):352–354
Achinewhu SC, Akpapunam MA (2005) Physical and chemical charac- Suliman TMA, Jiang J, Liu Y (2013) Chemical refining of sunflower oil:
teristics of refined vegetable oils from rubber seed and bread fruit. J effect on oil stability, total tocopherol, free fatty acids and colour. Int
Plant Food 35:103–107 J of Eng Sci and Technol 5(2):449–454
Aluyor EO, Aluyor P, Ozigagu CE (2009) Effect of refining on the quality Tasan M, Demicri M (2005) Total and indivisual tocopherol contents of
and composition of groundnut oil. Afr J of Food Sci 3(8):201–205 sunflower oil at different steps of refining. J of Eur Food Res and
Brevedan MIV, Carelli AA, Crapiste GH (2000) Changes in composition Technol 220:251–254
and quality of sunflower oils during extraction and degumming. Turkulov J, Dimic E, Karlovic D, Vuksa V (1998) “Effect of hydrother-
Grasas y Aceites 51(6):417–423 mal treatment on the quality of nonrefined edible sunflower oil”- In
Carelli AA, Brevedan MIV, Crapiste GH (1997) Quantitative determina- World Conference on Oilseed and Edible Oil Processing. Vol I, pp
tion of phospholipids in sunflower oil. JAOCS 74(5):511–514 185–187, S.S. Koseoglu, K.C. Rhee and R. F. Wilson (Ed.). AOCS
Carelli AA, Frizzera LM, Forbito PR, Crapiste GH (2002) Wax compo- Press, Champaign, IL
sition of sunflower seed oils. JAOCS 79(8):763–768 Verhe R, Verleyen T, Van Hoed V, De Greyt W. (2006) Influence of
Crapiste GH, Brevedan MIV, Carelli AA (1998) “Water degumming of refining of vegetable oils on minor components. J. of Oil Palm
sunflower oils”- In World Conference on Oilseed and Edible Oil research 168–179