The foundamental concept of

OleochemistryBK 3523

CHAPTER 2

Content

• Fats and oils as oleochemical raw materials

- feedstock from animal fats

- feedstock from plant oils

- other feedstock• Fats and oils compositions, properties

and specifications

Feedstock for Oleochemical

• Animal fats (renewable raw materials)• Vegetable oils (renewable raw materials)• Their use avoids the upstream pollution

associated with petroleum extraction and refining

• They are readily biodegradable, low in toxicity and do not harm aquatic organisms compare with petrochemicals

Vegetable and Animal Oils and Fats

Basic Oleochemicals Fatty acids, Glycerine, Fatty Alcohols, Methyl ester & Fatty amines

ApplicationsDetergent, Soaps, Softners, Cosmetics, Pharmaceuticals

Candles, lubricating oils, greases, paint, plastics, printing inkCoating etc

Palm Oil

Coconut Oil

Inedibile Animal Fats

Soybean oil

Corn Oil

CottonseedOil

Sunflower oil

Soybean Oil

Fatty Acid

Cutting oils, special lubrucants, rolling oils

Fatty Amines

-sulfo fatty acid

Polymer

Fatty Ester

Nonamethylene diamine,Undecy acid

Fatty Alcohol

Soap

Diagram of source and use of fatty acid in oleochemistry overview (1)

Salt formation

Hydrogenolysis

Oxidation

Esterification

Polymerization

-sulfonylation

Reaction with

Cl- & NH3

Reaction with Sulfur

& Sulfur chlorides

Oleochemial Raw Material & Their Derivatives Overview (2)

Fats and Oils

• Fats and oil are water insoluble, hydrophobic substances.

• Mainly derived from of vegetables & fruits, land or marine animal

• Predominant composition = triacylglycerols.• Also contain other minor glyceride fractions =

diacylglycerols, monoacylglycerols & free fatty acids.

• Other non-glyceride fractions = phosphatides, sterols, carotenoids, & other types of fatty alcohols.

Fats and Oils (cont.)

• Different temperatures can change a fat to different states from solid to liquid.

• Thus, FATS are defined as those that are solid at room temperature while OILS are those that are liquid at room temperature.

10

Triglycerides

1. GLICERIDES– Triglycerides 90 – 98 %– Diglycerides 0.2 – 8 %– Monoglycerides 0.2 – 0.3 %– Fatty acids 0.2 – 10% ( Saturated / Monosaturated/

Polysaturated)

2. WATER 0 – 0.3 %

3. IMPURITIES 0.1%4. POLAR LIPIDS - Phospholipids 0.1 – 3% - Glycolipids 0.1 – 3%5. UNSAPONIFIABLE - Sterols 0.3 – 0.7% - Tocopherols 0 – 0.1% - Pigments

Carotena 0 - 0.1%ChlorophylleGossypol 0.1%

- Hydrocarbons - Waxes - Metals - Toxic compounds - Oxidation products - -Flavours

Fats and Oils Composition

Triglycerides

• The different placement of FA and FA types attached to the glycerol molecule leads to a number of different TAG

• Affect phycisal properties, the stability of the oils and fats

13

Types of Triglycerides (TAG)

1. Saturated TAG • Cheese• Beef• Whole milk• Fats in baked goods• Butter• Margarine

14

Types of Triglycerides

Monounsaturated TAG – Olive oil– Canola oil– Peanut oil– Margarine made with

canola oil or other highly monounsaturated fat

Olive Oil Canola Oil

Peanut Oil

15

Types of Triglycerides

Polyunsaturated TAG– Safflower oil– Corn oil– Soybean oil– Sesame oil– Sunflower oil– Nuts and seeds

• Saturated fatty acids- Short (C2:0- C4:0) medium (C6:0- C12:0) and long chain fatty acids (C14:0- C22:0)

• Unsaturated fatty acids- monounsaturated and polyunsaturated

Fatty Acids

Feedstock from Animal Fat

• Derived both from terrestrial and marine animals

• Marine fats include liver oils, blubber oils, and fish oils

Feedstock from Animal Fat

• terrestrial animals include pig fat (lard), sheep/beef fat (tallow, suet), butter (clarified butter, ghee), poultry fat (chicken, duck,

goose)

Feedstock from Plant Oils

• found abundance in fruits and seeds

• also found in the roots, stalks, branches, and leaves of plants

• Vegetable fats and oils may or may not be edible. 

• E.g. of inedible vegetable fats and oils = processed linseed oil (flaxseed oil), tung oil, castor oil

• commonly used in lubricants, paints, cosmetics, pharmaceuticals, etc.

Feedstock from plant oils-edible vegetable fats and oils

1. Palm oil2. Palm Kernel oil3. Coconut oil4. Soybean oil5. Rapeseed (Canola oil)6. Sunflower oil 7. Corn (maize) oil8. Olive oil 9. Cottonseed10. Peanut oil10. Sesame oil11. Grapeseed oil12. Rice bran oil

13. Safflower oil

21

MAJOR SOURCES OF OILS AND FATS IN OLEOCHEMISTRY

PRODUCTION WORLDWIDE

• About 80% is of plant origin• 53 X 106 t in 1980, 110 x 106 t

in 2002• Average growth 3.3% per year

in 1990’s• Out of 110 x 106 t: 15.6 x 106 t

transformed into chemical products out of which 10 x 106 t are soap

WORLDWIDE PRODUCTION

ANIMAL OILS & FATS

VEGETABLE OILS

WORLDWIDE CONSUMPTION

ANIMAL FOOD

CHEMICALS

NUTRITION

22

PRODUCERS OF OILS AND FATS

ASIA

(mostly Malaysia, Indonesia, Phillipines)

Lauric acid (C12:0) from palm kernel and Coconut oil

US & EUROPE

Animal fats

Palm Oil

Extracted from flesh/mesocarp of palm fruit.

Consists of ~ 44% palmitic acid

Can be divided into the solid (stearin) and liquid (olein) fraction by fractionation at controlled temperatures

Contain 50% unsaturates and 50% saturated FA

Fatty Acid Composition of Palm Oil

• Unsaturated fatty acids oleic acid (C18:1): 38.7% linoleic acid (C18:2): 10.5%

• Saturated fatty acids palmitic acid (C16:0): 44% stearic acid (C18:0): 4.6% myristic -saturated (C14:0):1.0%

Soybean oil• extracted from the seeds of the soybean

• Second largest edible oil produced worldwide

• polyunsaturated oil rich in linoleic (typically 54%) & linolenic acids (typically 8%)

• when subject to light hydrogenation process to increase its content of solid triglycerides may lead to formation of trans fatty acids

• trans fatty acids = worse than saturated fatty acid in cholesterol-raising activity

Fatty Acid Composition of Soybean Oil

• Unsaturated fatty acids

linoleic acid (C18:2): 54%

oleic acid (C-18:1): 22%

Linolenic acid (C-18:3): 8%

• Saturated fatty acids

palmitic acid (C-16:0): 11%

stearic acid (C-18:0): 4%

Rapeseed (Canola) Oil

• seed oil of Brassica napus or B. campestris

• typically rich in erucic acid (C 22:1)

• high erucic acid content can cause cardiac muscle damage

• Canola is a genetic variation of rapeseed developed by Canadian plant breeders

• Canola is an acronym for "Canada oil low acid“.

• Canola is the registered name for rapeseed containing - < 2% of erucic acid in the total fatty acids in the oil - < 30 umols of alkenyl glucosinolates per gram of oil-free dry matter of the seed (Thacker, 1990; Bell, 1993).

Fatty Acid Composition of Rapeseed Oil

• Unsaturated fatty acids oleic acid (C18:1): 62% linoleic acid (C18:2): 22% linolenic acid (C18:3): 10%

• Saturated fatty acids palmitic acid (C16:0): 4% stearic acid (C18:0): 2% •  

Sunflower oil

• obtained from Helianthus annuus

• contains 60-75% of linoleic acid 

• Sunola (Highsun) comes from a high-oleic variety and has about 85% oleic acid 

• NuSun with ~ 60% oleic acid has been

developed in the USA

Fatty Acid Composition of Sunflower Oil

• Unsaturated fatty acids linoleic acid (C18:2): 48 - 74% oleic acid (C18:1): 14 - 40%

• Saturated fatty acids palmitic acid (C16:0): 4 - 9% stearic acid (C18:0): 1 - 7%

Other oils

• Evening primrose oil

- rich in gamma linolenic acid (helpful in the production of prostaglandin).

Fatty Acid Content of Palm Kernel Oil (PKO)

• Saturated fatty acids

Lauric (C12:0):  48.2%

Myristic (C14:0):  16.2%

Palmitic (C16:0):  8.4%

Stearic (C18:0):  2.5%

• Unsaturated fatty acids

Oleic (C18:1):  15.3%

Linoleic (C18:2):  2.3%

Fatty Acid Content of Olive Oil

Saturated fats: Palmitic acid: 7.5–20.0%

Stearic acid: 0.5–5.0%Arachidic acid: <0.8%

Unsaturated fats Oleic acid: 55.0–83.0%

Palmitoleic acid: 0.3–3.5%    Linoleic acid: 3.5–21.0 %

Linolenic acid: <1.5%

Fatty Acid Content of Coconut Oil

• Saturated fatty acids

Lauric :  47.5%

Myristic :  18.1%

Palmitic :  8.8%

Stearic :  2.6%

• Unsaturated fatty acids

Oleic :  6.2%

Linoleic :  1.6%

Other Plant Oils

• Jatropha Oil• Castor Oil• Linseed Oil• Tung Oil• Tall Oil

Castor oil

• Native to the Ethiopian region of tropical east Africa .- Other tropical and warm temperature regions

• Seeds or beans are extremely poisonous. Contain ricin a very deadly protein called a lectin

• Known as ricinus oil, yellowish or almost colourless. Has been used medicinally in the US

• When dehydrated, it converted into a quick-drying oil . Used extensively in paints and varnishes

• Its water resistant qualities make it ideal for coating fabrics

Jatropha Oil• Oil used as a diesel substitute during the 2nd World war.• Also can be used for productions of candles, soap,

biofuel, insecticides• The major fatty acids are oleic, linoleic, palmitic and

stearic acids• The seed is highly poisonous and the oil cannot be used

without detoxifications

Chemical and Physical Properties of Jatropha Oil

Parameter

• FFA (%)• Iodine Value• Saponification value (mg

KOH/g)• Peroxide value (Meq/kg)• Density at 20ºC• Viscosity at room

temperature

Value

• 2. .23 ±0.02• 103.62 ± 0.07• 193.55± 0.61

• 1.93 ± 0.012• 0.90317• 42.88

Tung oil

• Known as China Wood Oil• Seed rich in unsaturated oils. When drying it

absorb oxygen from the air to form plastic, elastic, resin-like substancesIt is a drying oil which has wide applications in the manufacture of paints, varnishes, waterproof coatings and artificial rubber.

• Composed primarily of eleostearic acid

Tall Oil• Know as liquid odorous obtained as by-product of

pulp and paper industry from pine wood rosin, is a dark yellow

• It is composed of a mixture of rosins, fatty acids, sterol, alcohols and other non acid materials

• Use as a component of soap, adhesives, rubbers, inks and as emulsifier, linoleic and palmitic acids

• Main fatty acid oleic

Linseed oil

• known as flaxseed oil, is a clear to yellowish oil obtained from the dried ripe seeds of the flax plant

• Obtained by cold pressing, sometimes followed by solvent extraction-its high levels of α-Linolenic acid (a particular form of Omega-3 fatty acid), it is used as a nutritional supplementI but, because of its strong flavor and odor, is only a minor constituent of human nutrition in the U.S.,

• Use as paint, wood finish• Food-grade flaxseed oil is cold-pressed, obtained without

solvent extraction, and marketed as edible flaxseed oil

A typical linseed oil are of the following types:[3]

The triply unsaturated α-linolenic acid (51.9-55.2%), The saturated acids palmitic acid (about 7%) and stearic acid (3.4-4.6%), The monounsaturated oleic acid (18.5-22.6%), The doubly unsaturated linoleic acid (14.2-17%).

Representative triglyceride found in a linseed oil, a triester derived (from the top) of linoleic acid, alpha-linolenic acid, and oleic acid.

Characteristics of Malaysian Palm Fatty Acid Distillate

• Iodine value• Unsaponifiable matter (%)• Saponification value (mg KOH/g)• Water (%)• FFA (%)• C12:0

• C14:0

• C16:0

• C18:0

• C18:1

• C18:2

• C18:3

• 46.3-57.6• 1-2.5• 200.3 -215.4• 0.03- 0.24• 72.7-92.6• 0.1 -2.4• 0.9-1.6• 43.0-49.1• 4.0-4.5• 34.7 -37.2• 8.5 -9.7• 0.3-0.5

The Chemical and Physical properties Commonly Used as Specifications for Oleochemical

Feedstock

• Fatty acid composition (FA)• Free fatty acid content (FFA)• Iodine value (IV)• Moisture (%)• Impurities• Unsaponifiable matter• Colour• Viscosity• Peroxide value (PV)

End of Lecture 2