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NEUTRALISATION

There are basically two types of refining. One is chemichal, or caustic, revfining method the
other is physical, or steam, refining method. The purpose of refining is to remove
nonglyceride impuritiesthat consist principally of free fatty acids and significant quantitites of
mucilaginous subtances, phosphatide, chlorophyll, and color bodies. The refining porcess
removes the objectionable impurities in the oil with the least damage to either the glycerides,
the tocopherols, or other natural antioxidants.
4.1. Chemical or caustic refining
this method of refining converts the free fatty acids to oil insoluble soaps, removes all
substances that become insoluble on hydration, and removes some of the color bodies present
in the oil. Reactions are at a relatively low temperature, allowing fer the refining equipment
to be fabricated essentially from iron or preferably, mild steel.
The technology of caustic refining is concerned (1) with the proper choice of alkali to be
used, (2) the quantity of alkali strength used and (3) the refining technique used to produce
the desired purification without excessive saponification of the neutral oil. The method used
for efficient separation of the refined oil from the soapstock is also a concern.
The major disadvantage of the method of refining is the loss of a small portion of neutral oil
in addition to the free fatty acid as a result of saponification. This loss can be minimized,
however, by utilizing good technology.
Sunflower oil can be alkali refined using either a batch method or a continuous method of
refining. The batch method requires less capital investmen, but (1) the yield of refined oil is
considerably less than via the continuous method, (2) the throughput rate is less
4.2. Calculation of caustic
Caustic calculation discussed here is the method of determining the quantity and
concentration of the caustic solution required for alkali refining as it is applicable to both the
batch and continuous methods. The correct amount of caustic (NaOH) used is important to
obtain good yields and a quality finished product. If the feed to the refinery is in volume
(liters) the quantity must be converted to mass using the specific gravity of the oil being
refined. Also, the volume caustic (liter) should be adjusted based on the specific gravity of
the solution being used.
The quantity of caustic requared for neutralization can be determined in the following
manner:
1. Multiply the percent free fatty acid of the oil by 0.142. this gives the percent of solid
sodium hydroxide required for neutralization.
2. To this percent, add a slight excess quantity, as the quantity calculated in step 1 is the
theoretical quantity. The excess will usually range between 0.005 and 0.20%, depending
on the percent of free fatty acid present in the oil and also the quantity of nonoily
constituents present in the crude oil.
3. Add the calculated in step 1 to the desired excess established in step 2.
4. The quantity of oil in pounds or kilograms is multiplied by the total percent arrived at in
step 3. This gives the number of pounds or kilograms of silod sodium hydroxide required
for the refining.
5. The quantity of solid sodium hydroxide requared is divided by the required quantity of
caustic solution to be used in refining.
The percent of excess caustic is important because a large excess will contribute to a
high loss of refined oil. This is particularly true if the refining is being accomplished at a
temperature of 760C (1690 F) or higher. Some excess caustic is required to obtain a good soap
formation, remoal of nonhydratable phosphatides, and aminimum carryover to the wash
water centrifuge and into the oil. If the parts per million of soap in the washed and dried oil is
high, it may be necessary to increase the quantity of excess caustic slightly to lower the soap
content. The oil sample for the soap determination should be obtained from the vacuum dryer.
A start with an axcess of 0.10-0.15% is recommended if the percent free fatty acid of
the crude oil being refined is in the range of 0.77-1.2%. the quantity of the excess caustic
should then be adjusted, if necessary, after the process has reached an equilibrium. If the
percent free fatty acids in the crude oil is lower than 0.7%, it may be posibble to use an
excess of 0.05-0.10%. if the free fatty acids are greater than 1.2%, the excess must be
increased to between 0.15 and 0.20% would represent an extremely high quantity; it may,
however, be necessary for some refining.
4.3. Used of Phosphoric Acid
Phosphoric acid will remove the calcum and magnesium content of the oils as insoluble
phosphates. The treatment quantity will vary from 0.02 to 1.0% ussally about 0.2% of 85%-
phosphoric acid. Temperature during the treatment will vary from 70 to 900C (158 to 1940F).
Phosphoric acid may also be used to remove some phosphatides that were not removed
by water degumming. These can be removed before alkalirefining by treatment of the oil is
necessary if the oilis the oil going to be physically or steam refined.
Phosphoric acid can be used as a metal (iron) scavenger. When used as a metal
inactivator the level is critical. Reasons for not usingphosphoric acid treatment include the
following.
Lecithin cannot be used for human consumption if it has been treated with phosphoric acid.
phosphoric acid nay cause charring at high temperatures when used as a stabilizer for adible
oils; it may also react with oxidized fats to yield a dar colored polymeric substance.
Experience with sunflower oil indicates that extraneous flavors develop when 0.01% of
phosphoric acid is added on the cooling side of development of melon fruity or cucumber off-
flavors for the aged oil.
Additionalcaustic will be required to neutralize the excess phosphoric acid if phosphoric acid
is added before caustc refining; this increases the cost of producing alkali refined oil.
4.4. Phophoric Acid Used in Alkali Refining
The use of low levels of phosphoric acid in conjunction withcaustic refiningof
sunflower oil has been suggested and/or recommended in several technical documents.
However when a phosphoric acid treatment is done it is essential that a correct quantity of
coustic be used to neutralize the phosphoric acid abd to remove the free fatty acids present in
the oil.
Phosphoric acid treatment is usually employed to assistin removed the
nonhydratablephosphatides present in the oil. The quantity of phosphatides that contain
calcium and magnesium s relatively low in sunflower oil and consequently the phosphoric
acid treatmentis not ordinarilyrequired when using the long-mix refining system. The acid is
usually added in a water solution if the phosphoric acid treatment is imployed. It is
recommended that the oil and acid solution be agitated for approximately 30 min (i.e. a long-
mix system) before adding the caustixc solution for neutralizing the acid and free fatty acids
of the oil.
The phosphoric acid treatmenis quite often used when a multimix refining process has
been installed. Due to the short contact period occurringin this treatment it is importantthat
the correct quantity of causticsolution is used to obtain a good refined oil.
The long-mix refining system is usually recommended for refiningsunflower oil. The
longer retention time (3-6 min) in the long-mix system removes more of the color bodies and
permits the use of a mildercautic solution and a lower refining temperature. This systm
produces a good yield and a highquality oil.
4.5. Batch Refining
Batch refining is conducted in a mild steel, steep cone-bottom tank (about a 60 o cone
angle) aquipped with an agitator (slow speed) and paddle-type blades that are pitched to lift
the product from the bottom of the tank to the top of the liquid level. It should also heve
internal steam coils and a method of spraying the caustic solution and water on the surface of
the oil. It is desirable to have small drawoff valves for obtaining samples located about 15 cm
(6 inches) above the start of the straight side of the tank and another one about 15 cm ( 6
inches) below the top of the cone bottom. A drawoff valve of approximately 5 cm (2 inches)
diameter should be located at the bottom of the cone. A thermometer should be located about
halfway up on the straight side of the tank. It is desirable to have a vacuum system for this
vessel, so the oil may be dried after it has been refined, providing there is no vacuum
bleaching tank.
A quantity of crude oil is pumped into the refening tank without the agitator running.
The quantity pumped into the refining tank should be about 70% of the capacity of the vessel
being used for refining. The reason for this is that room must be allowed for expansion during
the heat-up period as well as for the liquids added during the refining procedure. After the oil
has been pumped into the refining vessel, the agitator is turned on and the steam is allowed to
flow into the coils. When the temperature of the oil at 32 oC (90oF) the desired quantity of
caustic solution is sprayed on the surface of the oil. Heating is continued during this
neutralization step and is heated at a rate such that the oil will reach 71 oC (160oF) in 1 h.
When that temperature is reached, the steam and the agitator are turned off. The contents of
the refining tank are allowed to come to a rest and the soapstock and nonoily constituents are
allowed to settle to the bottom of the tank. The settling time is usually 30 min for good
refining. A sample drawn at a valve [located either at a point 15 cm (6 inches) above or below
the straight side of the tank] will indicate if the soaps have settled or are still settling. When
the oil has been correctly soapstock. Also, inspect the surface of the oil in the refining tank, as
occasionally the soap will float, which is caused by the air being entrained in the oil and
combining with the soap. If the soapstock is floating, the oil usually requires an additional
waterwashing (Figure 12.5).
Star washing the oil if the oil appears relatively free of soapstock at the bottom side
valve. The wash is done by spraying on a 5% hot water (82-88 oC; 180-190oF) wash on top of
the oil. The percentange of water is based on the weight of the oil in the refining tank. This
firs hot water wash is then allowed to settle for 30 min; then another 5% hot water wash is
applied. After the second wash, the batch is allowed to settle for about 2 h. The soapstock and
water are then drawn off slowly and are pumped to an acidulation tank. After the soapstock
has been drawn off. If a lot of heavy soapstock is present, it is pumped to theacidulation
tank. If it is just soapy water, it is handled and disposed of in the proper manner. After
drawing off this first 10% of water wash, at least three more 10% hot water washes are given
to the neutral oil.
It is desirable in the last 10% hot water wash to run the agitator to try to remove most of
the soap. If a high prercent of soap is still present in the oil, additional washes must be given
to get the quantity of residual soap down to a desirable level. After the last water wash, the
water is drawn off and the neutral oil is vacuum dried, either in the refining tank or in a vessel
that can also be used as a bleaching tank for decolorizing the oil.
4.6. Continuous Refining
A continuous method of refining requires a considerable investment in equipment;
however, it is the most efficient and aconominal method. There are a number of excellent
centrifuges available for this type of refining (Figure 12.6)
The system generally used consists of a day tank, which should hold enough crude oil
for a aminimum of 2 h based on the maximum hourly rate of the centrifuges. For example, if
there are two centrifuges rated at 15.000 kg/h, the day tanks should have a capacity of at
least 60,000 kg. The day tanks should be equipped with agitation and have a control system
for maintaining a desired level in the tanks. A heathing system should be in this tank to
maintain a uniform temperature. The oil is the pumped from the day tank through a strainer
and through a ratio controller, where the desired quantity of caustic solution is added to the
oil. From there it flows through a mixing device (usually a static mixer), a system for
retention to get a through mix.
From the retention system, the oil flows through a means of through a means of heating
the mixture to the desired refining temperature. The heater used for this operation is generally
a fin tube-type heater. From the heater, the mixture is fed to the primary centrifugest to
remove the heavy phase, which consists of the soaps, excess caustic solution, and nonoily
constituents. The ligh phase, which is the neutral oil, is also discharged from the primary
centrifuge through a continusous fin tube heater, where it is heated to about 82.2oC (180oF).
After it pesses through the heater, a controlled quantity of hot water is introduced to the
oil. This is usually about a 15% hot water (82-87.7 oC) wash. After the water has been mixed
with the oil, the oil and water mixture is passed through a static mixer to obtain a good mix.
From there, the oil and water mixture goes to a centrifuge for the removal of the water phase
from the oil. The water-washed neutral oil is then vacuum dried using a continuous vacuum
drier. The dried oil is pumped to storege or is further processed. In some instances the oil may
be given a second water wash. It is done after the first water wash and before the oil is
vacuum dried. The process would be the same as used for the first water wash.
The quantity of caustic soda solution to be used is calculated as previously shown for
the batch method. The excess and deggrees baume for the continuous refinery are similar to
that used in batch refining. A method available for determining thew excess alkali should be
used accasionally during the refining to be sure the process is in control. It is desirable to
determine the soap content after the water washing and vacuum drying. This is so slight
changes can be made in the refining conditions to minimize the soap level before further
processing the oil.
If the oil is going to be deodorized or further processed without decolorization with an
acid-activated clay, the slight addition of a weak acid solution (such as citric acid) before
vacuum drying may be desirable. However, if the oil is bleached using a bleaching clay, the
acidity in the clay will usually neutralize the slight alkalinity of the oil. Using a continuous
method of refining, one can vary the refining temperature considerably to get a good
separation of the heavy phase using the centrifuge. A temperature as low as 38 oC (100oF) has
been used to produce a good quality refined oil. It has been found that a neutralization
temperature of 57oC (135oF) gives both good refined oil and good yield.
4.7. Other Neutralization Processes
There are different types of caustic refining processes offered by equipment
manufacturers: the long-mix method and multimix method. The multimix methods, with
some modifications, are referred to as intermix, short-mix, and ultra-short-mix. They were
developed to process poor and unstable feedstocks. One of the major differences among these
methods is retention time.
The disadvantage of the multimix method is that the contact and retention time with the
caustic solution is so short that the color bodies of the oil are not reduced or changed by the
caustic solution. The removal of impurities such as gums, protein, oxidizing materials, and
color bodies is as important as the removal of fatty acids.
In the multimix methods, the oil is heated to the processing temperature of 85-95 oC
((185-203oF). The oil is then mexid with 0.05-0.15% phosphoric acid in a high shear knife
mixer for 30 s and then mixed with the caustic solution in a neutralization mixer.
Intermix Method. The intermix method is reported to be suitable for most feedstock
with a high nonhydratable phosphatide content or oils requiring rerefining. In this case 30-
60% axcess caustic above that which is consumed by the phosphoric acid is used at a strength
of 20-28oBe, the mixing is done in a high shear knife mixer for about 30 s.
Short-Mix Method. When processing oils that have a tendency to emulsify, or when the
neutralized oil is to be rerefined, the short-mix method may be preferable. In this system, 10-
40% of caustic is used at a strengh of 12-20o Be for about 3 s using a disk mixer. This type of
mixer is designed to provide intensive contact with the oil and caustic without setting off
emulsions.
Ultra-Short-Mix Methods. The ultra-short-mix method may be more suitable if
processing an oil with a high FFA, which reacts easil. When this method is used, the oil and
caustic solution are mixed directly beforebthe inlet to the separator in an in-line mixer using
10-30% excess caustic having a 2-28o Be strength. The retention time using this system is 0.3
s.
4.8. Refining Temperature
The refining tempetature is critical in obtaining good yields. A compromise must be
made between removing more of the color bodies and obtaining a low yield by using a higher
refining temperature versus obtaining an improved yield using a lower temperature and
achieving the desired color by decolorizing with an acid-activated clay.
Yields from continuous refining of relatively good grades of crude sunflower oil no
tank bottoms) at various temperature have indicated that refining at 43 oC (110oF) would
produce a refining loss approximately 1.42 times the percent of the free fatty acid. At 57 oC
(135oF), the loss factor was 1.62, while at 71oC (160oF), the loss factor was 1.84. thus,
assuming an FFA content of 1.1%, refining at 43oC versus 71oC saves 0.46% 0f oil.
Sunflower oil has been refined successfully at 57oC (135oF), using a continuous
refining method. A high quality refined sunflower oil also has been produced at a temperature
as low as 43oC (110oF). The chlorophyll content of the oil refined at 43 oC (110oF) was
somewhat higher than oil refined at 57oC (135oF). Chlorophyll was removed by decolorizing
with an acid-activited clay.
Cautic refining of other oils is often done at temperature higher than those
recommended for refining sunflower oil. A temperature as high as 82 oC (180oF)has been
used to refine some of the other oils. Refining at such a high temperature removes more of
the color bodies if done in conjunction with a higt excess-caustic level. But this results in a
significantly greater oil loss due to saponification of neutral oil. Though it is possible to
refine sunflower oil at the high temperature used for other oils, such is not recommended. If a
temperature higher than 57oC (135oF) is used in refining sunflower oil, the level of caustic
employed must be cautiously controlled.
4.9. Physical And Steam Refining
This method of refining is used primarily on lower molecular weight oils such as palm,
coconut, palm kernel, animal fats, and to some extent on soybean oil. This method has been
used in Europe ti lower the high free fatty acid content of an oil or fat to a level of 0.8-0.5%.
the oil is then caustic refined, bleachedan then steam deodorized. Short chain fatty acids, such
as found in plam or coconut, are remived very aesily by physical refining. With the above
oils, one may be able to lower a high free acid content oil to one aa low as 0.02-0.03%.
The oil loss could be about 1% greater tahn precent of free fatty acids in tehe starting
oil. For example, if one is refining an oil with a free fatty acid 0f 1.25%, the total loss would
be about 2.25%. there is, however, a slight tendency for the oil to hydrolyze during the
process, which will produce more free fatty acids and increase the loss.
The lower the concentration of free fatty acids in the oil, the more difficult they are to
remove by distillation. This is not a universally acceptable method of refining, as some acids
will darken at high temperatures and in some oils the color will set at high temperatures
rather than bleach. Glycetides are not appreciably damaged by long heating in the absence of
oxygen. It may be posibble, however, to strip out some tocopherols and related substances if
the oil is subjected to distoillation for a long period of time. The distillation process operates
like a single-shell deodorizer.
The objectives in physical or steam refining are to reduce the free fatty acid content,
fully deodorize the oil, operate without substantially greater utilities consumption than
standard or regular deodorization, and recover the free fatty acid from the distillate. The
principal disadvantages of steam refining method are that equipment must be constructed
from 316 stainless steel because of the acidic conditions and corrosion at the high
temperature. The process is limited by which oils can be refined. Furthermore, oil must be
thoriughly degummed and bleached before physical refining can be started. In addition, the
percent of bleaching clay requered for decolorizing is greater than when the oil is caustic or
chemically refined.
If sunflower oil is physically refined, the oil will have to be dewaxed after the steam
refining and then perhaps deodorized again to produce an acceptable product. This process
may not lend it self to oils that contain a relatively high percent of wax.
4.10. Pretreatment
Pretreatment is a phosphoric acid degumming (or treatment of the water degummed oil)
before the bleaching and steam distillation or refining. The degummed oil is pumped to a
mixing tank where it is agiteted and maintained at a temperature of 95 oC (203oF). Phosphoric
acid in an amount of 0.1-0.5% (by weight) is added to the oil. In a continuous method, the
phosphoric acid is added to the oil, using aither a proportionating metering pimp or a ratio
controller, prior to being pumped into the mixing tank.
The oil and acid mixture is agitated at the 95 oC (203oF) temperature for about 15 min.
The mixture is pumped to a slurry tank where a quentity of bleaching clay and, if necessary,
filter aid is added. The quantity of bleaching clay required will depend on the desired color oh
the oil before steam refining and doedorization. After the bleaching clay has been added, the
oil, acid, and clay mixture is trasferred to a vacuum bleaching tank where it is held for a
period of time to obtain the desired color. It is than pumpen through filters to remove the
bleaching clay and into a receiving tank.
4.11. Steam Refining
From the receiving tank, the oil is pumped through spray nozzles in a dearator tank,
which is under vacuum, to remove the dissolved air. From the deaerator, the oil is pumped
into the refining deodorizer where it is refined. From the refining deodorizer, the oil is cooled
to the desired discharge temperature and is pumped through a polishing filter to the desired
tank for further processing or storage. If antioxidants are added, it should be done as the oil is
being pumped from the polishing filter. Also, the oil should be handled or stored under a
nitrogen blanket after the deodorization.