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 3
chapter
Crude Oil De-gumming and
Acid Pretreatment
Section 3.1 Introduction
Phospholipids are essential components of vegetable cell structure. The phospholipids
are commonly referred to as gum. These are extracted from the seeds along with the
crude oil and, being oil soluble, they remain in the crude oil.
One of the primary objectives of vegetable oil refining is to reduce the phospho-
lipids content in the oil to a very low level. This is because a phospholipids content
above a certain level may cause the oil to not perform satisfactorily in many applica-
tions, primarily frying. In the oil processing industry, the phospholipids content in
the oil is expressed in terms of PPM of phosphorus. This is because there is a definite
relationship between the phospholipids content and the corresponding phosphorus
level in the oil. For example:

Percent Phospholipids = ((Phosphorus in oil (PPM) × 31.7) × 104)

Table 3.1 lists the phospholipids and phosphorus contents in common crude veg-
etable oils.

Table 3.1
Typical Phospholipids and Phosphorus Contents of Most Common Vegetable Oils
Oil Type Phospholipids Content, % Phosphorus* Content, PPM
Crude Soybean Oil 1–3 317– 950
De-gummed Soybean 0.32– 0.64 100 –200
Crude Corn Oil 0.7– 0.9 222– 285
Crude Peanut (Groundnut) Oil 0.3– 0.6 95 –190
Crude Canola Oil 1.8–3.5 570 –1104
Super-de-gummed Canola Oil 0.13– 0.16 41– 51
Crude Sunflower Oil 0.5– 0.9 159 –285
Crude Safflower Oil 0.4– 0.6 127–190

Section 3.2 Purpose of De-gumming

Crude oil is de-gummed to reduce the phosphorus content of the oil to a very low
level because the phosphorus content of the oil has a profound influence on the flavor
stability of the refined, bleached, and deodorized oil. In addition, several process-

33
34  M. Gupta

related issues are experienced when the oil contains high phosphorus past the blea-
ching stage.
Crude oil is de-gummed for various reasons. Soybean oil is water de-gummed
to recover the phospholipids to manufacture lecithin. Canola oil is de-gummed as a
general practice because the oil is sold as de-gummed or super de-gummed crude oil.
The gum recovered from canola oil is dark and does not have the same commercial
value as the soy lecithin. It is used in animal feed. Corn oil, made from wet-milling
process, is de-gummed in order to deliver higher quality crude oil that is easy to re-
fine.
Discharge of plant effluents from non-de-gummed seed oils had to be curbed
when strict environmental regulations were imposed on oil processing plants in many
countries. Besides water de-gumming, various acid de-gumming processes evolved
to treat crude oils that are either more difficult to refine or to reduce the phosphorus
content in the oil to a very low level so the physical refining process (described in
Chapter 4) could be applied for refining. Some experts claim that crude soybean can
be physically refined if the total phosphorus is reduced to 15 PPM or less. The author
believes that in order to physically refine soybean oil, the phosphorus content in the
crude oil must be 10 PPM or lower and preferably less than 5PPM.

Section 3.3 Hydratable and Non-Hydratable Phospholipids

Crude oil contains both hydratable and non-hydratable phospholipids. The hydra-
table phospholipids can be separated from the crude oil by treating with deionized
water. The non-hydratable phospholipids require treatment with phosphoric acid,
citric acid, maleic acid, citric anhydride, etcetera. The acid reacts with the metal com-
plex of the non-hydratable phospholipids and makes them hydratable so they can be
removed from the crude oil. Normally the gums removed by the acid-process can be
used for making lecithin, but the clarity is sacrificed. It is usually blended into the
animal feed.
The integrated crusher-refiners in the United States found that it is advantageous
to de-gum the fresh soybean and corn oil immediately after extraction. De-gummed
oil produces lower amounts of soap in the refining process. This reduces the load on
the soap acidulation plant. This reduces the BOD (Biological Oxygen Demand) and
COD (Chemical Oxygen Demand) in the plant effluent as compared to that from
the plant processing non-de-gummed crude oil. Cottonseed oil is mostly processed
through the micella refining process. This generates less soap in the oil refinery.

Section 3.4 Methods for De-gumming

Various de-gumming processes are used in the vegetable oil industry. They are:

1. Water De-gumming

2. Acid Conditioning
 Crude Oil De-gumming and Acid Pre-treatment  35

3. Acid De-gumming

4. Super De-gumming (Special De-gumming)

5. Ultra De-gumming (Special De-gumming)

1. Water De-gumming
Hydratable phospholipids absorb water and settle out from the rest of the oil. This
property of the hydratable phospholipids is utilized in the water de-gumming process.
Water de-gumming removes most of the hydratable phospholipids from the
crude oil. The hydratable gum from the crude oil is easily separated from the crude
oil when it is fresh and especially when made from good quality soybean grain with
proper extraction process. Crude oil derived from poor quality soybeans contains a
higher proportion of non-hydratable phospholipids. The oil in this case needs acid
de-gumming or acid pre-treatment for better reduction of phospholipids.
Figure 3.1 shows the Alfa Laval process for water de-gumming. The following
steps are involved in the process:

1. Determine percent phospholipids in the crude oil by checking PPM

phosphorus.

2. Crude oil is heated to 140°–150°F (60°– 65°C).

3. Deionized water, equal to percent phospholipids is added to the oil through

an in-line mixer.

Reactor Vacuum
Water De-gumming
MX Mixer Vacuum
Disc Stack Dryer
Centrifuge

Water Heater

Heater
Steam
Crude Oil

Steam
Gums To Storage

FIG 3.1. Schematic Diagram for Alfa Laval Water De-gumming Process
36  M. Gupta

4. The oil and water are gently mixed in a hydration tank for 30 – 40 minutes.
The hydrated gum separates and agglomerates.

5. The oil is then gently pumped out of the tank and separated in a centrifuge.

6. The heavy phase contains hydrated gum.

7. The temperature of the oil leaving the centrifuge is 140°–150°F

(60°– 65°C).

8. Water de-gummed oil contains 0.4 – 0.8% moisture. The oil is heated

to 185°–190°F (85°– 90°C) in a heater and then pumped into a vacuum
dryer, maintained at a maximum absolute pressure of 50 mm of mercury.
Heating of the oil is necessary because the temperature of the oil leaving the
centrifuge is too low for vacuum drying at this level of vacuum.

9. Vacuum-dried oil should have a moisture content of 0.05% or less.

10. The oil is cooled to <130°F (55°C) before storage.

11. Hydrated gum is dried in a wiped-film vacuum dryer if the gum is to be used
to make lecithin. The vacuum dryer is equipped with a specially designed
mist eliminator in order to prevent any product loss due to excessive foaming
in the vessel.

12. The vacuum system must be designed with non-contacting condensers in

order to prevent any mixing of the phospholipids into the condenser water
and forming an emulsion in the water tower basin.

Critical Control Points in Water De-gumming

The critical control points in water de-gumming are:

• Oil temperature

• Amount of deionized water

• Residence time in the hydration tank

• Agitation in the hydration tank

• Vacuum drying of oil

• Vacuum drying of the gums

 Crude Oil De-gumming and Acid Pre-treatment  37

Oil Temperature
Temperature of oil at hydration is critical. At temperature <130°F (55°C) the degree
of hydration is better but the viscosity of the oil is higher which makes the separation
of oil and gum difficult. Less hydration of the phospholipids occurs at temperature
above 149°F (65°C). This reduces the efficiency of gum removal and higher phospho-
rus is found in the de-gummed oil.

Amount of Deionized Water

The amount of water is normally equal to that of the phospholipids content of the
crude oil. At lower water addition, the hydration of the phospholipids is incomplete,
causing a reduction in the removal of the phospholipids. At higher water addition, the
difference of density between the oil and the gum is reduced, causing poor separation
in the centrifuge. This may leave more phospholipids in the oil and also increased oil
loss in the gum phase.

Residence Time (Contact Time) in the Hydration Tank

A certain minimum amount of contact time is necessary for the hydration of the
phospholipids in the crude oil. Lower than 30 minutes of contact time may not allow
sufficient hydration of the phospholipids. This reduces the efficiency of separation of
the oil and the gum. A longer than 40-minute contact time is not harmful but is not
required. Besides, a longer contact time requires a larger hydration tank, which makes
the process more costly.

Agitation in the Hydration Tank

The agitation in the tank must be gentle to prevent any emulsion formation.
Any amount of emulsion in the hydration tank will reduce separation efficiency
of the process.

Vacuum Drying of the Oil

The oil must be dried if it is to be stored. The moisture in the vacuum dried oil should
be <0.05% and not >0.1%. The oil does not have to be dried if it is sent immediately
for chemical refining or bleaching for physical refining.

Storing wet oil can cause the following issues:

• The gum in the oil can hydrate and cause hydrolysis of the neutral oil. This will
increase the FFA in the crude oil in storage.

• The hydration of the gum can increase the refining loss.

Vacuum Drying of the Gum

The gum goes through several steps before it becomes lecithin. It is dried to <1%
moisture. Crude lecithin contains 65 – 70% oil. Higher moisture in the lecithin
38  M. Gupta

makes the lecithin very viscous and unacceptable in most applications. In addition,
high moisture can produce higher FFA in the lecithin during storage.

2. Acid Conditioning
This method is generally used to treat high quality palm oil and coconut oil. This is a
very simple method but it has its limitations. The oil is treated with 400 –1000 PPM
of phosphoric acid using a high shear mixer. The oil is then directly sent to bleaching
for physical refining. The steps of the procedure for acid conditioning are listed be-
low:

1. Good quality palm oil or coconut oil is heated to 130°–140°F (55°– 65°C).

2. 400 –1000 PPM of phosphoric acid is added to the crude oil and the two
liquids are mixed in a high shear mixer. In some cases citric acid works
better and is considered to be preferable over phosphoric acid. For example,
citric acid or maleic acid is preferred for treating canola oil.

3. The oil/acid mixture enters a retention tank called the conditioning tank.
This tank is provided with gentle agitation.

4. The oil stays in the retention tank for 15–30 minutes. This hydrates the
phospholipids and the hydrated phospholipids separate out of the oil
because the metal salts of phosphoric acid are insoluble in oil.

5. The hydrated phospholipids are not separated from the crude oil before it
goes to bleaching or caustic neutralization.

The precipitated salts and the hydrated gums have a tendency to plug up the filter
screens. This is because the metal salts of phosphoric or other acids are insoluble in
the oil and precipitate out. This tends to plug up the filters in bleach. It is always
recommended to pre-coat the filter screens with diatomaceous earth. This procedure
will be described under bleaching (Chapter 5).
Many stand-alone refiners tend use this technique to treat the crude oil in order
to hydrate some of the non-hydratable phospholipids in the crude oil before it is refi-
ned. Although this is a low-cost option for treating seed oils, it is not a very effective
means to achieve good results.
Many stand-alone refiners use this technique to pre-treat the crude oil from poor
quality or hard to refine seed oils. This is inexpensive but not as efficient as the acid
de-gumming process.
Figure 3.2 shows the schematic flow diagram for the acid-conditioning process.

Critical Control Points in Acid Conditioning

Following are the critical control points in the acid-conditioning process:
 Crude Oil De-gumming and Acid Pre-treatment  39

Mixer

Acid Tank

crude Oil
Acid Conditioned Oil to
Flow Meter
Plate Heat Exchangers Caustic Refining or
Prebleaching
FIG 3.2. Schematic Flow Diagram for Alfa Laval Acid-Conditioning Process
1. Oil temperature

2. Amount of acid added

3. Mixing of oil and acid

4. Holding time after acid treatment

5. Agitation in the conditioning tank

Oil Temperature

• At temperatures <55°C (130°F) the reaction between the acid and phospholipids
is slow.

• At temperatures >60°C (140°F), some of the crude oil may get hydrolyzed by the
acid, causing an increased FFA level in the crude oil.

Amount of Acid
As stated earlier, most refiners use 400  –1000 PPM of phosphoric acid based on the
crude oil flow. This may or may not be the right amount depending on the non-
hydratable phospholipids in the crude oil. At low acid dosage, the non-hydratable
phospholipids may not be adequately hydrated. With high acid dosage there may be
some hydrolysis of the neutral oil, resulting in higher refining loss.
A better way to determine the required amount of phosphoric acid is outlined as
follows.
40  M. Gupta

For crude soybean oil:

1. Analyze the PPM of calcium in the crude oil.

2. Estimate the amount of acid needed for treatment using the following
example.

Crude soybean oil with a calcium content of 100 PPM

Atomic weight of calcium = 40

Molecular weight of phosphoric acid = 98
Theoretical ratio of phosphoric acid/calcium = 2 Moles of phosphoric acid/
3 atoms of calcium

Theoretically, 120 parts of calcium will react with 196 parts of phosphoric acid.
Therefore, the amount of phosphoric acid needed if the crude oil contains 100
PPM of calcium:

= 100 {(98 × 2) / 40 × 3} = 163 PPM

In actual practice, the amount of phosphoric needed for this crude oil could be as
much as 5–10 times the calcium content in the crude oil. This is because:
1. In addition to calcium the acid reacts with magnesium and iron present in
the crude oil.

2. There is also the lack of intimate mixing oil and acid even with a high shear
mixer.

The exact amount of acid must be estimated by the actual analysis of the oil for PPM
calcium. This amount will vary from lot to lot of the crude oil and also between dif-
ferent types of crude oil.

Mixing of Oil and Acid

Oil and acid must be intimately mixed. Phosphoric acid and oil are not miscible
liquids. Therefore, a high shear mixer is needed to disperse the acid into the oil in
micro size droplets to maximize the interfacial area between the oil and the acid. The
importance of mixing is listed below:

• Hydration of the non-hydratable phospholipids is incomplete if the dispersion of

the acid in the oil is poor, resulting in high phosphorus in the refined oil.

• Inadequate dispersion of the acid in crude oil may cause the acid to settle out
causing eventual corrosion in the tank, piping, etcetera, even if they are made
 Crude Oil De-gumming and Acid Pre-treatment  41

of 304 stainless-steel.

Conditioning Time (Retention Time)

• A minimum retention time of 30 minutes is needed for the reaction between the
acid and the non-hydratable phospholipids in the crude oil when a high-shear
mixer is used.

• A longer retention time does not improve the hydration process.

• A very long retention time may allow some of the acid and the separated hydrated
material to settle at the bottom of the tank, making it difficult to filter the
bleached oil.

Agitation in the Conditioning Tank

The agitation of the acid/oil mixture must be gentle to prevent emulsification in the
oil.

3. Acid De-gumming
Acid de-gumming provides more complete removal of phospholipids from the crude
oil. This method is especially used to treat seed oils and oils that are difficult to refine.
Figure 3.3 shows the schematic flow diagram for the acid de-gumming process by
Alfa Laval.
This is essentially an extension of the acid-conditioning process. The following
are the procedure steps involved in this process:

• Deionized water (approximately 2% of the oil flow) is added to the acid/oil

mixture leaving the high-shear mixer.
Hydration Tank

LC
Mixer

FIC Degummed Oil

to Bleaching
Water

TIC
Mixer

FIC

Crude Oil Heater

Gum
Separator
Acid

FIG 3.3. Schematic Flow Diagram for AlfaLaval Acid De-gumming Process
42  M. Gupta

• The composite liquid stream passes through a static mixer before it enters the
hydration tank.

• The hydration tank is very similar to that in the water de-gumming process in
terms of construction.
• The oil/acid/water mixture is gently agitated in the hydration tank for 20 –30
minutes.

• The oil is then gently pumped out of the hydration tank and centrifuged.

• The heavy phase (acid treated gums) and the light phase (treated oil) are
separated.

• For high quality palm oil or coconut oil, the water can be added just before the
acid/oil mixture enters the centrifuge.

One can see that the acid de-gumming process contains several aspects of water de-
gumming and acid conditioning processes.

Critical Control Points

The critical control points for this process are the same described under the water de-
gumming and acid-conditioning processes.

4. Special De-gumming (Super De-gumming)

This process was developed by Unilever to process soybean crude oil for physical
refining and also treating other seed oils that are hard to refine. This is also known as
the “super de-gumming” process. This process works better on crude oil as compared
to water de-gummed oil. It is believed that the hydratable phospholipids help the se-
paration of the non-hydratable phospholipids by agglomerating them, making it easy
to remove them in a centrifuge. Figure 3.4 shows the schematic flow diagram for the
super de-gumming process.
The process is carried out through the following steps:

• The oil is heated to 35°– 40°C (95°–104°F) and mixed with 0.1% citric acid in
a knife mixer.

• The acid-treated oil is held in a conditioning tank for 30 minutes with gentle
agitation.

• The conditioned oil is pumped out of the conditioning tank and mixed with 2%
deionized water in a second knife mixer. So far the process looks very similar to
a combination of acid conditioning and water de-gumming.

• Along with the water a small amount of caustic is added (as flocculent) before the
 Crude Oil De-gumming and Acid Pre-treatment  43

mixture enters the second knife mixer.

• The mixture is allowed at least 30 minutes of retention time in the hydration

tank. The flocculation step is a distinct step that differentiates it from the other
de-gumming methods.
• The oil from the hydration tank is gently pumped out and sent to a self-cleaning
type centrifuge to separate the oil from the gum. It is important to use a self-
cleaning centrifuge for this process. With a standard type of centrifuge, the
bowl will get dirty too soon, requiring frequent shut downs for cleaning of the
bowl.

This process separates more gums compared to acid de-gumming. The gum separated
is also very sticky. Therefore, in addition to the use of a self-cleaning centrifuge, it
requires the hydrated oil flow to be about 60% of what is used in acid de-gumming.
Thus, in order to obtain the same oil flow, a larger centrifuge and the corresponding
pumps are needed.
Even with the special care mentioned above, the crude oil loss in this process is
higher than that in the acid de-gumming process. This is because of the lower opera-
ting temperature, which increases the viscosity of the fluid and causes the separation
of the two phases to be more difficult.
The gum produced by this method contains a higher percentage of neutral oil
compared to the acid de-gumming or water de-gumming process. This produces
lower acetone insoluble in the gum.
Like in the acid de-gumming process, the gum produced by the super de-gum-

Conditioning
Tank Hydration Tank
Degummed Oil
to Bleaching

Mixer Mixer

Water

Crude Oil Heater

Separator Gums
Acid Focculant

FIG 3.4. Flow Schematic Diagram for Super De-gumming Process (Unilever)
44  M. Gupta

ming process is not suitable for human consumption. Therefore, its outlet is limited
to animal feed.
This process is used to make super de-gummed canola oil. Some processors claim
that maleic acid produces better results in canola oil de-gumming than citric or phos-
phoric acid.

Critical Control Points in Super De-gumming Process

The critical control points for the super de-gumming process are:

1. Oil temperature

2. Retention time in the conditioning tank

3. Retention time in the hydration tank

4. Addition of flocculent

5. Self-cleaning centrifuge

6. Oil flow rate (reduced)

Items # 1– 3 are similar to those in the acid-conditioning process.

Addition of Flocculent
A small amount of caustic is added to form soap with the FFA in the crude oil. The
soap reduces the interfacial tension between the oil and the aqueous phase of the acid
solution. This improves the reaction between the acid and the non-hydratable phos-
pholipids. Thus, a little amount of soap acts as an aid to hydrate the phospholipids
and precipitate them. Addition of large amounts of caustic would produce more soap,
causing emulsion formation. This will reduce the efficiency of de-gumming.

Self-Cleaning Centrifuge
A self-cleaning centrifuge maintains the bowl clean of the sticky gum and provides for
a longer operation cycle, thus improving productivity.

Oil Flow Rate

At increased flow rates the centrifuge bowl gets clogged too soon. This requires more
frequent shut downs to clean the centrifuge bowl and, thus, reduces productivity of
the process.

Combined Special De-gumming and Neutralization

Figure 3.5 shows the schematic flow diagram for combined super-de-gumming and
neutralization. The system offers the flexibility of both:

1. Straight neutralization of high quality crude oil.

 Crude Oil De-gumming and Acid Pre-treatment  45

2. Use a combination of super de-gumming and neutralization capability for

poor quality or hard to refine crude oil.

3. This is basically a parallel system to provide flexibility to plants that do not

strictly process palm or coconut oil (or other lauric oils), but also seed oils
that may be of poor quality.

4. The centrifuge placed in parallel can be used for water washing neutralized
oil or can be used for de-gumming oils as needed.

5. Ultra De-gumming
Walter E. Farr developed this process and the first commercial application was made
by him in 1995. The name ultra de-gumming evolved from the newer technique
of mixing, which was termed by him as ultra-shear mixing. With the help of these
mixers, one can attain a shear force of 100,000 sec -1.
In this process, the acid treatment dose is the same as that is used in acid de-
gumming or less, but the crude oil and the acid (citric acid or phosphoric acid) are
brought in extremely intimate contact with the help of an ultra shear mixer. A very
percentage of the non-hydratable phospholipids reacts with the acid and is converted
to hydratable phospholipids. The treated oil has a phosphorus content of 5 PPM or
less. This allows one to apply physical refining to the oils that are normally difficult to
refine via the physical refining process.
This method cannot reduce the phosphorus content as low as mentioned above
when the crude oil is of very poor quality. In those cases, one can use this ultra shear
technique and combine with chemical refining that uses a fraction of the caustic that
would otherwise be required to refine such crude oil. Walter Farr calls this process the
Semi-Physical Refining Process.

Reactor To drying/stor-
MX Mixer age or bleaching
MX Mixers
Disc stack
Disc stack
centrifuge
centrifuge

Crude Heater Waste

Oil water

Steam Steam
Heater

Gums or
soapstock

Acid Lye
Water

FIG 3.5. Alfa Laval Combined Special De-gumming and Neutralization (Combi Pricess)