EDIBLE AND

Edible
ESSENTIAL OILS 285

Liquid oil
Vanaspati (Hydrogenated oil) 57%
19
Soaps and detergents
Cosmetics 10
Paints and varnishes 9
2
Miscellaneous
1

Shemical Composition and Physical Properties of

Vegetable Oils
1.1. Fats and oils--mixtures of glycerides of fatty acids where Ri,
necessarily the same R, and R, are Ot
RCO"0CH,
R,"CO"0"CH

R,"CO"0CH,
By terminology of the industry, oils are all liquid and fats are solid at normal
temperatures.
1.2. Waxes-mixed esters of polyhydric alcohols other than glycerin. Usually solid at
room temperature.
1.3. Effect of Degree of Saturation--number of double bonds in the fatty acid radical (R)
controls the melting point and chemical reactivity as shown in the following table:

R Number of Melting Reactivity to

Name Composition Double Bonds Point, °C Oxygen
Stearic C,Hs 69 Nil
Oleic 1 14 Fair
-S Rapid
Linoleic C,,H
Linolenic C,Hy 3 -11 Extremely rapid
forming
The ability to react with oxygen enhances the use of unsaturated fatty acids as film
Vehicles for paints. It also is the cause of rancidity in edible fat products which can be avoided
by use of:
Hydrogenation-removes reactive double bonds
Antioxidants--compounds which oxidize preferentially to fats without much increase in
color or odor

Methods of Extracting Vegetable Oils

L.l, Reference Flow Sheet: Figure IllA-l
2.2. Mechanical
15-20 minutes, then pressed in
Seeds cleaned and huled, steam cooked at 220-250°F for
either:
 286 NATURAL PRoDUCT INDUSTRIES
Extracted
Finished
Solvent

uwno Buddus wnn Steam Finished

Recycle
Sovent Open
FlashEvap.) Oil
Film SOLVENT
EXTRACTION
Stean Steam 1 Fullers
Earth
L

Aid Carbon|Waste
Filter
Solven
Removal Mfg. methods.

Soap
Wes Mea Meal extraction
Extroctor| PURIFICAT
to
Clear
Oil Foots
oil
Vegetable

cÓRolis
Cracking JAkali
MECHANICAL IIIA-1
Flaked
Seeds ScrewConveyed
partsEXPELLER
100 PROCESS Fig.

---Altern
Routes
Miscella
Cleaning
and
Mechanical
Dehulling
Seeds '546Par's) Expeller
(Steanf Animal
HoO Feed
 EDIBLE AND
Continuous screw extruder or expeller
ESSENTIAL OILS 287

Batch hydraulic press

2.3. Solvent Extraction
2.3.1. Characteristics
May be used alone or in
preferred for most seeds combination with mechanical methods. The latter S
" high except soyabean since solvent extraction gives
" poor yields98-99% of available oil
qualitydark
Combination color,
of expeller and odoriferous, and high free fatty acid content
solvent extraction methods yields over 80% as prime
quality oil and only 18-19% as the poorer
2.3.2. Types of solvents used grades.
Petroleum cuts in the hexane range-flammable
" Trichlorethylene--toxic
Despite fire hazards, petroleum solvents are preferred.
Purification
2.4.
Alkali such as NaOH or Na,CO, is added to remove free fatty acids as foots" by
centrifugation. Bleaching is done with adsorbent clays such as Fuller's carth and with
adsorption carbon. Filtration is done on pre-coat rotary vacuum filters (or plate and frame
presses for small capacity plants).
An alternate route is to solvent extract by use of propane. This solvent is miscible
the
with all of the oil below 80°C but is immiscible with fatty acids and color bodies near
in an extraction column are
critical temperature of propane (96°C). Temperature gradients
used to effect a two-phase separation.
Oíls
3. Hydrogenation of process which is used in the fat and oil
industry to remove double
Hydrogenation is a unit resistance to rancid oxidation. The major
point of the fat, and improve its
bonds, raise the melting household oil for cooking. Other products are
Vanaspati, a solidified
end-product in India is hydrogenated liquid oil.
oils, and partially
vegetable ghee, hardened industrial Figure IIIA-2
3.1. Reference Flow Sheet: indicates activated catalyticstate)
3.2. Chemical Reactions (* Ni* catalyst

= C), R, + (-y) H ’ R, (C= C), R,

(a) R, (C
Example: Ni*
(C,H,CO0), "CH,
(C,,H,,CO0), C,H, + 3H, ’
decomposition)
(nickel formate
(b) Nickel catalyst preparation

+
190°C
2C0, + H, + 2H,0
Ni(HCOO), " 2H,0’Ni*
(oil base)
preferred for well-stirred
is
divided catalyst which
This produces a finely
hydrogenation reactors.
288
Oil
Hydrogenated
Partialy

|Fullers
Earth
Pradxto
orVanaspati
Waste
Solids
Filter
Aid Carbon
Barornetric
Leg

oils.
Decolorization
vegetable

Steam
Steam of
Hydrogenation

Steam
or
Water
Hydrogenator Recycle
Catalyst
IIA-2.

Fig.
Çatalyst
Make-up
Nickel
00000000

oil
Surry
Catalyst
H2
Oil

Oil
 EDIBLE AND ESSENTIAL OILS 289
i Nickel catalyst preparation (reduced Nion
inert catalyst support)
Ni(OH) H, ’ Ni* +H,0
t
NiCO, + H, ’ Ni* + H,0 + CO,
Nickel salts are precipitated on
inert porous kieselguhr or diatomaceous
earthand reduced at high temperature in a carrier such as
hydrogen atmosphere.
A Nickel catalyst preparation (Raney or
spongy nickel method)
2AI " Ni + 6NaOH ’ Ni* 4
alloy
2NaAlO, + 3H,
(Raney nickel)

Produces spongy, high-surface area catalyst when the sodium aluminate is washed out
with water.
3.3. Raw Materials
Major raw materials are oils to be hardened, and purified hydrogenwhich can be obtained
from several sources such as:
Electrolytic H,0 or chlor-alkali
Steam-iron: reaction of steam on Fe followed by regeneration with water gaS
Synthesis gas processes discussed in IIB
poisons for the hydrogenation
Sulfur containing compounds (SO,, H,S) are extreme by cryogenic distillation or a
processes
catal yst. These are removed from the last two H,
reactive metal guard converter.
3.4. Quantitative Requirements using
depends on the type of oil and extent of saturation desired. A typical example
This
cottonseed oil is as follows:
(a) Basis: 1ton hardened oil 50 Nm
Hydrogen 0.6 kg
Nickel catalyst losses
0.5 ton
Steam 4.5 tons
Cooling water operating on 1-3 hr cycle
5-30 ton batch reactors
(b) Plant capacities: vary from 2 to 10, depending on
plant size.
Number of reactors will
in
3.5. Process Description large residence times_(1-3 hours) and variation
Batch operationis used
because of
day. Batch hydrogenators can treat 5-30 tons
properties from day to turbine agitators to
Olinput and product equipped with coils for heating and cooling, and
of oil per batch; are controis
disperse the injected hydrogen. relationships are complicatedinthat1the combinationexample,
The
pressure-temperature
certain types of double--bond saturation. For
for
the selectivity of hydrogenationat low pressures (1-2 atms. gage) and high temperatures (135-
shortening is produced
ghee-base oil is hydrogenated similarto butter. Vanaspati
with melting point gage) and lower temperatures (120-160°C)
180° C) to yield a higher pressures (2-3.5 atms. stability for cooking purposes.
fat
by hydrogenating at melting point fats of maximum charged to the
to maintain higher process operates as follows: Oil is
hydrogenation batch off air and water.. Acatalyst-oil slurry is pumped in;
Atypical evacuated to drive
Teactor, heated and
 NATURAL PRODUCT INDUSTRIES
290
Hydrogen is introduced and the
oil.
kg per ton of After the desired hydrogenation has steam
the catalyst concentration is 5to 15 exothermic.
cooled and
filtered to ensuedthe
is turned off since reaction is mildly e the batch is recover
as checked by an iodine number iteration,
catalyst for reuse.
deodorized in
heated,
a Dowtherm next steeam Sparging
The hydrogenated oil is next continuous basis. The oil is vitamins.
vacuum tower which operates on a filtered, mixed with
decolorized
and sent
with
to
Fuller's earth, carbon or similar absorbent, then refrigerated slow-cooling in
the packaging-storage operations. This involves packaged
tins
For non-granular products used for
to reproduce the granular structure of ghee. jacketed cylinder equipped with fast.
confectionery and bakery purposes, rapid chilling in a
revolving internal scraper blades is employed.
3.6. Major Engineering Problems
3.6.1. Thermodynamics and kinetics
(a) Heat of reaction
shown
The heat of reaction for hydrogenation of oils is mildly exothermic as
by the following generalized diagram:

-AH=1 Kcal lg.atom

Heat of
Formation
(K cal./g.atom C)
React ants ((CnH2n)
Products
(CnHen2)
carbon

@100-200C o
Range for
Vegetabe
Oils

3 6 9 12 15
No of Carbon Atoms

The energy liberation during

cooling via cooling coils. hydrogenation requires a nominal amount of water
(b) Temperature
This variable is kept below
to prevent sintering of the 200°C to avoid side reactions such as
(c) Kinetic rate factors porous catalyst. pyrolysis and
For a gas-liquid reaction of the
H, (g) + Oil (1) ’ Fat (1),
research has shown that a series of
hydrogenation type:
pictured by this analog diagram: rate processes exist ywith 8 kinetic
resistance
 EDIBLE AND
H2
ESSENTIAL OILS 291

Oil

Soution of
H2 1
Diffusion Catalyst

Diffusion to
Catalyst 2
Chernisorption on
Catalyst

Chemisorption 3
on Catalyst

6 Surface Reaction
on Catalyst

Desorption of Fat Products

from Catalyst
Diffusion of Fat Products from
Catalyst to Liquid Phase

catalytic reactions, the rate behavior

As typically found for many heterogeneous
was characterized as:
reaction and adsorption controls reaction rate in the vicinity of 100°C
Surface
increased by increasing H, pressure (maximum pressure of 7 atms. gage
Rates are
used commercially) are
transfer for solution of H, and diffiusion to and from catalyst
At 180°C,mass
the rate-controlling steps
3.6.2. H, handling problemswide explosive limit range (4.1-74.2%). All equipment
Hydrogen gas has a before operating. While
freon or helium detectors as
should be leak-tested with problem at high temperatures and pressures such
is a
hydrogen embrittlementsynthesis carbon steel can be used throughout for oil
plants,
found in the ammonia
hydrogenatioh.
4. Economics possible
4.1, Raw Materials the principal oil stock for India. Although it isVanaspati,
furnish such as cottonseed for better
quality
Groundnuts (peanuts)
source, other
oils
have increased support.
The cottonseed
of should of reasons,
to expand this type coconut for soap
attractive economic venture for a number
linseed for paints, and presentlyan cattle feed usage, (2) low
is not
crushingindustry of whole seed because of competition for
price
e.g., (1) high market for oil cake.
oil yield, (3) no