J Am Oil Chem Soc (2012) 89:175–177
DOI 10.1007/s11746-011-1886-9
LETTER TO THE EDITOR
Neutral Oil Loss During Alkali Refining
Albert J. Dijkstra
Received: 10 March 2011 / Revised: 18 May 2011 / Accepted: 10 June 2011 / Published online: 7 July 2011
Ó AOCS 2011
Dear Sir,
While attending a Short Course held in the US last
February, I met a refinery manager with whom I discussed
the differences between the Long Mix neutralization pro-
cess as commonly used in the US and the Short Mix pro-
cess, which is more common in Europe. At one stage he
mentioned that his refining loss factor was 1.15 and I asked
him to explain that in more detail; his loss struck me as on
the low side.
He then told me that he first of all determined the total
neutral oil content (expressed as a percentage) of his crude
oil while using a laboratory method according to AOCS
Official Method Ca 9f-57. This neutral oil content gave
him the inevitable loss on alkali refining by subtracting the
neutral oil content from 100%. Then in the plant, he
determined the actual refining loss by subtracting the
‘‘Refined oil yield’’ (wt) from the ‘‘Crude oil input’’ (wt)
and finally, he arrived at this loss factor by dividing the
actual refining loss (expressed as a percentage) by the
inevitable loss (also expressed as a percentage). What he
did was standard procedure as described in the handbooks
[1].
I then told him that in Europe, it is more common to
calculate a ‘‘Theoretical loss’’ (TL) defined as (in per-
centage of crude oil):
TL = FFA ? Phosphatides ? Moisture
? Impurities ? 0.3
This TL is used by suppliers of centrifugal separators in
guarantees that limit the actual loss to 1.25 9 TL ? 0.3 (%)
in which equation the factor of 1.25 is higher than the loss
factor of 1.15 quoted by my refiner. However, I should
A. J. Dijkstra (&)
Carbougnères, 47210 St Eutrope-de-Born, France
e-mail: albert@dijkstra-tucker.be
point out that the definition of this TL is far from ideal
because it is not clear how the phosphatide content is
defined. It can be calculated from the phosphorus content
of the oil but what conversion factor should be used? For
the acetone insoluble (AI) of lecithin, a factor of 31 is used
since the AI also includes carbohydrates and glycolipids.
Looking at the phosphatides themselves (those that are left
after water degumming), a conversion factor close to 24
would be more appropriate [2].
In addition, the equation to calculate the actual loss from
the TL assumes the FFA and the phosphatides entrain the
same relative amounts of neutral oil. It even assumes the
moisture and impurities present in the crude oil to entrain a
quarter of their weight in neutral oil. This equation is
clearly an oversimplification but data on which to base a
more accurate one are lacking. As pointed out to the author
during the reviewing stage, such a more accurate equation
might also have to take the partial glyceride content of the
crude oil into account.
To obtain a better understanding of these loss factors, I
decided to study the literature and that turned out to be a
fascinating and intriguing exercise indeed. So I came
across a most informative article from 1955 [3] stating that
‘‘the oldest and best known method is that devised by
David Wesson’’. The article gives a number of references
from 1922 and 1926 the latter one of which [4] I only got
hold of recently, but the method is so important that vari-
ous authors [3, 5–7] have described the method in detail:
‘‘Dissolve 10 g of oil, weighed to 0.1 mg, in 50 cm3
petroleum ether (bp \80 °C) and transfer into a
separating funnel. Add 10 cm3 of a 14% potassium
hydroxide solution and shake vigorously for 3 min.
Add 25 cm3 of 50% ethanol, shake and allow to
settle. Collect the aqueous ethanol extract in a second
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separating funnel and extract three times with 20 cm3
of petroleum ether. Combine all the petroleum ether
extracts and wash them three times with 15 cm3 50%
ethanol and evaporate to dryness, first under atmo-
spheric pressure and then under vacuum until con-
stant weight. The absolute refining loss is then
calculated from the difference in weight between
crude and the neutral oil recovered.’’
The method aims at recovering the triglycerides present
in the sample by neutralizing the fatty acids, extracting the
soaps thus formed together with other non-triglyceride
constituents into aqueous alcohol. To avoid neutral oil
being lost as a result of poor separation, the alcohol is
extracted several times with petroleum ether and then, to
avoid non-triglyceride constituents being included as a
result of poor separation, the combined petroleum ether
extracts are washed again with aqueous alcohol. Apart
from being quite laborious and having a poor reproduc-
ibility [3], the Wesson-method also raises a fundamental
question: what happens with the partial glycerides? Are
they removed from the combined petroleum ether extracts
when these are washed again with 50% aqueous alcohol? If
they are, the Wesson-loss overestimates the loss on alkali
refining during which process partial glycerides are not
removed but remain in the oil.
This may well be the case. When 2% FFA was added to
oil that had been neutralized and bleached, the Wesson-
method applied to this acidified oil showed an inevitable
refining loss of 2.2% which is 0.2% in excess of the FFA
added [8]. This neutralized and bleached oil certainly
contained partial glycerides so that this excess loss of 0.2%
could be explained by assuming the Wesson-method to
remove at least some of these partial glycerides. In theory
this ‘‘loss’’ could also be due to the saponification of
neutral oil during the Wesson-treatment but fortunately,
experimental evidence has been published that rules out
this saponification [6]. An article from 1952 [9] points out
that it had already been shown in 1946 [6] that adding
known amounts of free fatty acids to oil that had undergone
a Wesson-treatment and then determining the Wesson-loss
of this acidified oil yields loss data that correspond exactly
to the amounts of FFA added. Accordingly, there is no
saponification during the Wesson-treatment. It can there-
fore be concluded that the Wesson-loss overestimates the
minimum or inevitable loss on alkali refining because
partial glycerides present in crude oil are extracted in the
Wesson-test and counted as a loss, whereas during alkali
refining, these partial glycerides remain in the neutral oil.
Given the shortcomings of the Wesson-method, it is not
surprising that attempts have been made to develop an
improved method to determine the inevitable loss on alkali
refining. Based on the observations during miscella refining
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J Am Oil Chem Soc (2012) 89:175–177
by Kaufmann et al. [10, 11], a chromatographic method
was developed [12] using alumina as adsorbent. Sadly
enough, this chromatographic method was also found to be
inaccurate since it indicated losses when the Wesson-
method, which itself overestimates the losses, showed no
losses [9]. Separation during column chromatography was
poor. The eluate was found to still contain FFA and/or
phosphatides and the column was found to retain some
triglycerides [13]. Even more sadly, this method forms the
basis of the AOCS Official Method Ca 9f-57, ‘‘Neutral oil
and loss’’.
Improvements to the chromatographic method have
been made [13] especially with respect to sample size. This
should take the non-triglyceride content of the sample into
account so as not to overload the chromatographic column
but even so, the loss according to the chromatographic
method arrives at slightly higher values than the Wesson-
method [2] and since the latter also overestimates the
inevitable loss, the improved chromatographic method
does this even more.
Being able to measure how much oil is inevitably lost
during alkali refining is essential for sound process control.
Let us therefore re-assess the problem. We are looking for
a method that separates hydratable phosphatides, non-
hydratable phosphatides, free fatty acids, water-soluble
impurities like carbohydrates and glycolipids, moisture and
impurities on the one hand from triglycerides, partial glyc-
erides and unsaponifiables on the other. In fact, we are
looking for a separation method that we also aim for during
alkali refining and we do not want to lose any neutral oil
and/or partial glycerides.
Looking for such a method means looking in the liter-
ature. In 1942, a process was disclosed [14] in which
‘‘unwanted constituents such as free fatty acids, coloring
bodies, mucilaginous materials, etc.’’ were removed from
fatty oils by extracting them in a counter-current manner
with a solution of ammonia in a mixture of water and
isopropanol (IPA). It is also known that when aqueous IPA
is used to extract soy flakes, phosphatides are extracted as
well [15]. It was also noted that soaps are readily soluble in
a water/IPA (70/30) mixture [16].
Putting two and two together, it looks as if extracting
crude oil with a solution of an alkali in a 70/30 mixture of
water and IPA might remove the free fatty acids as soap,
dissolve the phosphatides and other hydrophilic constitu-
ents such as carbohydrates, and remove the water and
impurities from the oil without dissolving any triglyceride
oil. Given the high water content of the IPA, the distribu-
tion coefficient of partial glycerides will be such that they
remain almost entirely in the oil. Since IPA is a secondary
alcohol, it would not partake in transesterification either.
But what about the non-hydratable phosphatides? Given
the observation [17] that non-hydratable phosphatides are
J Am Oil Chem Soc (2012) 89:175–177
completely removed when oil is refined with strong lye (pH
14), I would guess that these compounds also move into the
water/IPA phase. There being much more water than IPA, I
would guess that the partial glycerides remain in the oil
phase. In short, I would guess a perfect separation between
the compounds concerned.
Determining the inevitable refining loss would amount
to washing a sample of the oil to be refined with a solution
of an alkali like sodium or potassium hydroxide in water/
IPA, separating the two phases, removing any IPA from the
extracted oil by vacuum or washing with water and
determining the overall weight loss of the oil sample.
Hopefully, that weight loss equals the inevitable refining
loss.
Guesses and hope require experimental verification but
sadly enough, I am no longer in charge of a laboratory. I
don’t even have access to a laboratory. So I have to ask the
readers of this Letter to the Editor who have access to a
laboratory to volunteer to do this verification work. All in a
good cause.
References
1. Erickson DR (1995) Neutralization. In: Erickson DR (ed)
Practical handbook of soybean processing and utilization. AOCS
Press and United Soybean Board, Champaign IL and St. Louis
MS, pp 184–202
2. Pardun H, Werber O (1959) Laboratoriums-Methoden zur Be-
stimmung des Raffinations-Verlustes von Ölen und Fetten. Fette
Seifen Anstrichm 61:1010–1017
3. James EM (1955) The determination of refining loss. J Am Oil
Chem Soc 32:581–587
177
4. Wesson D (1926) Crude oil analysis. J Oil Fat Ind 3:297–305
5. Mattikow M (1942) A new method of refining oils with non-
saponifying alkalies—The Clayton process. Oil Soap 19:83–87
6. Desnuelle P, Micaelli O, Naudet M (1946) Sur quelques aspects
de la neutralisation des huiles d’arachide par les alcalis. Industries
des Corps Gras 2:304–309
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pertes subies pendant la neutralisation des huiles par les alcalis.
Oléagineux 5:161–163
8. King RR, Wharton FW (1948) A comparison of Wesson loss and
cup refining loss. Analyses of crude cottonseed and soybean oils.
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9. Hartman L, White MDL (1952) Wesson loss as a measure of the
degree of refining. J Am Oil Chem Soc 29:177–180
10. Kaufmann HP (1940) Adsorptionstrennungen auf dem Fettgebiet
IV: Die Trennung von Glyceriden durch Adsorption. Fette u
Seifen 47:460–462
11. Kaufmann HP, Schmidt O (1940) Adsorptionstrennungen auf
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12. Linteris L, Handschumacher E (1950) Investigation of methods
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13. Naudet M, Desnuelle P, Locatelli R, Bonjour S (1953) Étude
analytique de la neutralisation alcaline des huiles II. Dosage des
glycérides (huile neutre) dans les huiles brutes et neutralisées.
Bull mens ITERG:274–280
14. van Dijck WJD (1942) Process for refining fatty compounds. US
Patent 2,268,786
15. Baker EC, Sullivan DA (1983) Development of a pilot-plant
process for the extraction of soy flakes with aqueous isopropyl
alcohol. J Am Oil Chem Soc 60:1271–1277
16. Keurentjes JTF (1991) Physical chemistry and engineering of
membranes for fat/fatty acid separations, Ph.D. thesis, Land-
bouwuniversiteit Wageningen, the Netherlands
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