Food Technology

FDE 405

Sinan Uzunlu, PhD

ALKU Engineering Faculty
Food Engineering Department
Room: 125/120

Lecture 10- Jan 05 of 2024

Plant-based Oil Technology

Reference book: Processing and Nutrition of Fats and Oils. TP248.65 L57 2013.
Importance of fats and oils as a nutrient
• - the most concentrated source of its energy. 1 gram gives 9.1 kcal
energy to the body.
• Contains essential fatty acids.
• Oil-soluble vitamins could be transported in fat-rich sources.
Chemical and physical properties of lipids
• The term lipids describe two groups of compounds containing fatty
acids, neutral lipids (acylglycerols and wax esters) and complex lipids
(phospholipids and glycolipids).
• Lipids are defined as; glycerol-derivates that are insoluble in water,
but soluble in non-polar organic solvents such as hydrocarbons,
chlorinated hydrocarbons, benzenes, ethers, and higher alcohols.
• Later, a number of other molecular species including steroids,
isoprenoids, hydrocarbons, and other minör fat-soluble compounds
were classed as belonging to the lipids.
Chemical and physical properties of lipids
• Lipophilic compounds that do not contain acyl groups and do not form
soaps upon treatment of lipids with sodium or potassium hydroxide are
regarded as unsaponifiable materials.
• These include sterols, prenols, hydrocarbons, phenolic compounds.
• Classification of lipids:
• Acyl- and non-acyl lipids
• Acyl-class contains fatty acids and their combinations with glycerol and
other alcohols including sterols and long-chain alcohols.
• Non-acyl lipids include other lipid-soluble, non-esterified species, such
as free sterols, hydrocarbons, alcohols, etc.
Chemical and physical properties of lipids
• Acyl-lipids are classified acc.to their solubility, into neutral lipids
(mainly fatty acid esters of glycerol) and polar lipids (mainly phosphor-
and glycol-lipids).
• The classification is now forwarded to include the wide variety of
human, animal, microbial and plant lipids.
• 8 lipid classes are thus identified:
• 1. Fatty acyls (FA) 4. Sphingolipids (SP) 7.Saccharolipids (SL)
• 2. Glycerolipids (GL) 5. Sterol lipids (ST) 8. Polyketides (PK)
• 3. Glycerophospholipids (GP) 6. Prenol lipids
Chemical and physical properties of lipids
Fatty acyls (FA) or Fatty acids
• Represent the main component of most biological lipids.
• They consist of a hydrocarbon chain following a carboxylic head
group.
• The hydrocarbon chain can be saturated, unsaturated, branched,
cyclic, oxygenated, halogenated, nitrogenated, or sulfated.
• Saturated and unsaturated fatty acids are the most abundant in
nature and they are vital constituents of animal and plant tissues.
• Fatty acids are products of the polyketide biosynthetic pathway.
Unsaturated Fatty Acids

H H H H H H H H
-C - C – C – C – -C - C C – C –
H H H H H H
C atoms in a
C atoms in a
saturated fatty acid unsaturated fatty acid
chain chain
Fatty acyls (FA) or Fatty acids
• The structures of fatty acids are generally indicated by the number of
carbon atoms and the number and position of the double bonds
and/or other substituents, for example;
• 18:0 (stearic acid),
• 18:1 9 (oleic acid)
• 18:2 9,12 (linoleic acid) (9Z, 12Z-octadecadienoic acid)
• : the position of the double bond (s) is indicated with reference to
the carboxyl group, for example, 18:2 9,12 or 9cis, 12cis-
octadecadienoic acid for linoleic acid.
Fatty acyls (FA) or Fatty acids
• Another system for nomenclature, the «omega nomenclature»;
• The position of the last double bond is indicated with reference to the
methyl group as ꙍx or n-x (with x being the position of the double
bond to the distal methyl group).
• For example; linoleic acid is 18:2(n-6) or 18:2ꙍ6.
Saturated Fatty acyls (FA) or Fatty acids
• Plants as well as animals are able to synthesize saturated fatty acids
de novo (means; from the beginning).
• Fatty acids with an even number of carbon atoms extending from C4
to C24 are present in higher plants and animals, while odd-chain fatty
acids are abundant in microorganisms and some are present in milk
fats and fish lipids.
• Besides natural saturated fatty acids, these are generated by
hydrogenation of vegetable oils.
• Fig 2.1.
Monounsaturated Fatty acyls (FA) or Fatty
acids
• The main monounsaturated fatty acid in nature is oleic acid (18:1 9).
• All natural monounsaturated fatty acids have a cis configuration.
• In addition, monounsaturated fatty acyls are produced during the
hydrogenation of polyunsaturated fatty acids and some of these have
a trans configuration.
Polyunsaturated Fatty acyls (PUFA) or Fatty
acids
• Include a number of fatty acids with a varying number of carbon
atoms and double bonds and positions.
• Most of the double bonds in PUFA are three carbons apart but
exceptions exist,
• For example, a group of fatty acids with conjugated double bonds.
• PUFA are metabolized in vivo to a large number of oxygenated
derivatives, for example, the prostaglandins (PG).
Chemical properties of lipids
• The ester bonds between the fatty acyl and alcohols (glycerols,
sterols, etc.) are easily hydrolysable in alkaline media.
• As a result the fatty acyl moieties are transformed into soaps, which
are soluble in water,
• While other, water-insoluble, compounds constitute what is known as
the unsaponifiable fraction.
• The main components of this fraction are sterols, alcohols,
terpenoids, hydrocarbons, and other minör components.
• Triacylglycerol lipases and phospholipases are enzymes that are able
to hydrolyze glycerol-fatty acyl ester bonds specifically.
• Triacylglycerol lipases (or triacylglycerol ester hydrolases, EC 3.1.1.3)
are widespread in plants, animals, and microorganisms and are able
to hydrolyze the ester linkages between the fatty acyls and glycerol:
• Triacylglycerol +H2O diacylglycerol + a fatty carboxylate
• Natural lipases, in for example cereal grains, cause lipid hydrolysis
and generation of free fatty acids, which undergo facile oxidation
leading to rancidity in these products.
• In addition to their catalysis of the hydrolysis of ester bonds, lipases
do catalyze other reactions, such as esterifications,
interesterifications, and transesterifications in non-aqueous media.
• These abilities render the lipases versatility in various applications in
the food, detergent, pharmacautical, leather, textile, cosmetic, and
paper industries.
• The presence of double bonds in the fatty acids allows a number of
reactions.
• An important reaction that has been used by the food industry is
hydrogenation.
• Oils high in unsaturated fatty acids can be saturated via reaction with
hydrogen in the presence of a metal catalyst, usually nickel.
• Hydrogenation of unsaturated fatty acids was used historically in the
stabilization of highly unsaturated fish and whale oils and in the
preparation of margarines.
• One disadvantage of partial hydrogenation is the generation of fatty
acids with trans double bonds.
• For example, elaidic acid, the trans isomer of oleic acid are claimed
to be athergenic and are currently undesirable in food products.
• The problem of trans fatty acids is avoided by the use of complete
hydrogenation and interesterification of fats and oils.
• The presence of double bonds in the fatty acids makes them
vulnerable to reactions with oxygen and formation of
hydroperoxides and other oxidation products.
• These alterations lead to loss of the sensory quality (rancidity) as well
as the nutritional value of foods.
• In addition, oxidation products are toxic to the human organism.
• Oxidation reactions are generally autocatalytic reactions involving
free radicals and lipid hydroperoxides.
• Lipid oxidation reactions are inhibited in the presence of antioxidants
and synergists.
• The degree of unsaturation or number of double bonds in the fatty
acids of triglyceride oils will determine the degree of susceptibility to
oxidation.
• The more double bonds means the higher oxidation rate.
• E.g. 1 for stearic, 10 for oleic, 100 for linoleic, 150 for linoleic acid.
Physical properties of lipids
• Lipids consist of carbons and hydrogens, with a relatively small number of
other atoms such as oxygen, nitrogen and sulfur.
• Generally insoluble in water.
• May be partially hyrophilic, but most hydrophobic.
• Solubility in organic solvents varies from complete solubility in hydrocarbon
solvents (e.g., sterol esters and waxes) to complete insolubility in these
solvents (e.g., glycolipids).
• For extraction and solubilization of mixed lipids, especially from animal
tissues, solvents should include some polarity modifications, for example
by using heptane or hexane with isopropanol or chloroform with methanol.
• Lipids can be separated into classes using silica-gel columns or thin-
layer plates with mixtures of hydrocarbon solvents such as diethyl
ether, chloroform, and/or methanol.
• Fatty acids and triacylglycerols exist in solid and liquid forms
depending on the presence of double bonds, which enhance liquidty.
• The lipid components have detrimental effects on the crystallization
behaviour of fats and on such things as the consistency, fluidity, and
melting of the final products.
• Crystalline structure influences the rheological, mechanical, and
sensory aspects of high fat foods.
• The packing of the acyl chains of triacylglycerols into crystals occurs in
three different modifications, mainly the α-, β’-, and β-polymorphic
forms.
• Crystallization behaviour is affected by the nucleation and crystal
growth.
• The length of fatty acids and the degree of unsaturation, causes
bending of the chains. This is the key determinants for crystallization
form and behavior.
• The fatty acid composition and crystal structure determines physical
properties such as the melting behavior, specific gravity, viscosity,
smoke and flash points.
• α- -crystals melt about 5-15°C lower than β’- crystals, which also melt
about 5-10°C lower than the β-crystals.
• For example; for PPP (45, 56.6, 66.1°C)
Biochemical and bioactive properties of fats
and oils
• Humans and animals can synthesize saturated fatty acids as well as
oleic acid but not polyunsaturated fatty acids.
• These fatty acids are called essential fatty acids and there is an
obligate need for their intake through the diet because they are
obligate components of cell membranes and precursors for the
synthesis of eicosanoid hormones.
Composition and properties of edible fats and
oils
• Butter and milk fat (e.g., ghee) provided the first isolated fats used in
cooking.
• This was followed by tallow and lard.
• These fats are also rich in cholesterol.
• Both dietary saturated fatty acids and cholesterol induce atherogenic
effects on humans.
• However, consumption of margarines leads to decreased atherogenicity.
• Indeed, the trans fatty acids in margarine are more comparable to
saturated fatty acids than cis monounsaturated fatty acids in
atherogenicity.
5 main vegetable oils
• Soybean (Glycine max L. Merr.)
• Palm (Elaeis guineensis)
• Sunflower (Helianthus annuus L.)
• Rapeseed (Brassica spp.)
• Peanut (Arachis hypogaea L.)
Obesity and diabetes
• Increased energy intake contributes negatively to the body weight,
metabolic syndrome, and to diabetes in genetically disposed
individiuals.
• The metabolic syndrome, which is a cluster of risk factors for coronary
heart disease caused by deleterious metabolic imbalances, is directly
related to obesity and diabetes.
• Obesity comes not only from the amount of fat we consume and is
also affected by the fatty acid quality.
• High intake of dietary fat, especially saturated fatty acids, adversely
affects insülin sensitivity.
• While consumption of ꙍ-3 PUFAs prevent insülin resistance.
• High serum cholesterol is a major risk factor of coronary heart
disease.
Processing techniques for fats and oils
• The main components of crude edible oils are triacylglycerols, which
consist of 3 fatty acids attached to a glycerol backbone.
• Fatty acids (R-COOH) and gliserol/gliserin [C3H5(OH)3] : trigliserid is
called as esthers.

• Ester bond: - C – O – C -
Production of edible oils
1. Solvent extraction
• Involves solvent extraction and mechanical pressing.
• Hot water and steam infusion are used as a method of oil extraction.
(e.g. Extraction of fat in animal rendering operations)
• The most efficient method from the oil seed is using solvent (usually
hexane) extraction.
• Fig. 5.1.
• The hexane used for oil extraction is not «pure» hexane, but a mixture
of hexanes with a typical composition of: n-hexane (up to 62%),
isohexane (24%), cyclopentane (13%), and dimethylbutane (1%) with
a boiling point of 65°C.
• Fig. 5.2
Different types of extractors used in the
industry
• 1. Deep-bed stationary extractors consist of non-moving cells filled
with the raw material.
• 2. Deep-bed rotary extractor consists of a series of concentrically
placed cells that rotate under stationary solvent sprays.
• 3. The continious loop, shallow bed, extractor consists of a vertical
conveyor that rotates through several extraction stages.
• 4. Horizontal bed extractor consists of a simple belt conveyor carrying
the solid materials counter currently with a series of spray nozzles.
2. Pressing
• The oldest method of extraction.
• Have lower extraction capacity, has higher power reqirements and
leaves higher residual oil in the press cake.
• Oilseeds are usually heated before pressing.
• For oils that are commonly sold as cold pressed, such as olive oil,
sesame or safflower, the oil is simply filtered or clarified to remove
any remaining suspended solids.
• The cake is ground into meal for further solvent extraction or
processed into products for human consumtion or feed.
Chemical reactions in triglycerides
• 1. Hydrolysis
• 2. Oxidation
• 3. Saponification
• 4. Hydrogenation
• 5. Interesterification
• 6. Polymerization
• 7. Isomerization
Processing of vegetable oils
• Refining of edible oils is also the term used for the entire process that
generates a final product from a crude oil.
• This processing step can be done with or without prior degumming of
the crude.
• Most edible oils undergo three basic processing steps:
refining/neutralization, bleaching, and deodorizing.
• Fig. 5.4.
Degumming
• Usually done by adding soft water to the crude in proportion to the
measured amounts of phosphatides in this crude.
• The amount of water is 75% of the amount of phosphatides.
• For a continious degumming process the oil is heated to 70-80°C.
Caustic refining
• To remove free fatty acids from the crude oil.
• The free fatty acids deteriorate easily and can also impart off-flavor to
the oil.
• They are removed from the crude oil by neutralizing with a caustic
agent and then removal of the saponified material by centrifugation.
• Sodium hydroxide is usually the refining agent mostly used.
Bleaching of edible oils
• To remove colour, impurities such as soaps, metals, phosphatide
residues, and environmental contaminants, and to decompose
peroxides.
• The main colour components to be removed are carotenoid
compounds and chlorophyll.
• The used clays are basically composed of aluminium slicates, such as
bentonites and attapulgites.
Deodorization of vegetable oils
• Undesirable flavor and odor components from crude vegetable and
animal fats.
• Peroxides, carboxylic compounds, free fatty acids, environmental
contaminats are all removed.
• Also have a bleaching effect in the oil.
• Is basically a distillation process that uses steam as a stripping
medium and operates at elevated temperatures and high vacuums in
order to distill volatile and odoriferous materials.
Physical refining
• Removal of polar compounds, mostly free fatty acids, by distillation
under high vacuum and elevated temperatures.
• Because of overall yields, uses less chemicals, produces lesser
amounts of waste effluents such as soapstock.
• The contaminants are removed by physical refining;
• Metals (Fe, Ca, Mg, Cu, S, P, Pb, Ni)
• Excessive peroxides, colour, lecithin, air, residual solvents.
• The equipment used for deodorization can be used for physical
refining.
Fractionation
• Oils with a higher content of saturated fatty acids tend to crystallize
more readily.
• A process of crystallization through cooling is commonly used in oils
such as palm, cottonseed, and sunflower to remove a fraction of the
oil that solidifies more readily.
• This allows for the production of 2 fractions: a clear fraction or olein
and a solid fraction or stearin.
• The level of saturation, crystallization of the higher melting
tryglycerides may take place.
Fractionation
• This makes it necessary to chill fractionate the oil to prevent clouding
during storage in the manufacture of salad oils.
• The solid fraction separated in the winterization of oils such as
sunflower and corn oils are usual true epiticular waxes, that is, long
chain alcohols, which end up in the oil during extraction.
• In oils such as sunflower where the materials that crystallize are
natural waxes, the process of crystallization or dewaxing is used make
the oil crystal clear and improve appearance for the supermarket
shelf.
Fractionation
• The key pieces of equipment for fractionation or dewaxing are an
efficient refrigeration system, a crystallizing tank, and filters.
• There are currently 4 types of filters:
• * press filter
• * leaf filter
• * vacuum filter
• * centrifugal separators
Hydrogenation
• In the US in 1910 Procter and Gamble introduced the product
«Crisco» as a shortening.
• This shortening was marketed as a replacement for lard.
• Before WW II, substitutes for butter consisted mostly of coconout oil,
animal tallow, or lard.
Hydrogenation
• The main objectives of hydrogenation are:
• 1. to convert liquid vegetable oils into plastic fats for use in a variety
of cooking and baking applications
• 2. to improve the oxidative stability and therefore the flavor and shelf
life of liquid vegetable oils.
• The catalyst used in hydrogenation of most vegetable oils is nickel.
• The catalyst is suspended in the oil during hydrogenation and is
afterward removed by filtration.
When formulating a food product the following factors are
taken into account

• 1. Organoleptic properties: The oil ingredients should basically be

bland in flavour and provide and acceptable or desirable mouth feel
for the particular food product ultimately being manufactured.

• 2. Stability: The oil or fat must be stable, with respect to oxidation

and texture, in order to provide an acceptable shelf life and
wholesomeness of the final product.
• 3. Functionality: The oil product should fulfill the functional
requirements for a particular application, that is, good consistency,
plasticity, emulsification, creaming properties, flavor release,
spreadability. It is important to know the crystal characteristics of the
specific oils in order to design acceptable oil and fat blends for the
particular food products; specifically, whether the fat generates beta or
beta prime crystals when solidified.
• 4. Nutritional factors: Fats and oils are an important source of nutrients and
energy in the human diet, that is, essential fatty acids and fat soluble vitamins.

• However, it is also important to recognize that excessive amounts of some fats

can be harmful and this should also be taken into consideration when
designing fat and oil blends for foods. There is interest in nutritional oil blends
containing essential fatty acids such as ꙍ-3, higher content of tocopherols
(vitamin E), and sterols.
Interesterification
• Known as the exchange of acyl groups among triglycerides and
phospholipids.
• Acyl groups may exchange positions within a triglyceride or among
triglyceride molecules.
• This process has a found a wide variety of applications; to change the
melting-point of solid fats, to improve the compatibility of different
triglycerides, to manipulate the plasticity of certain fats, to change the
emulsifying properties of some oils, and to change the nutritional
properties of some edible oils.