PROSES INDUSTRI KIMIA
PENDAHULUAN
KONTRAK PERKULIAHAN
• Mahasiswa dilarang telat untuk mengikuti perkuliahan
• Pelaksanaan perkuliahan adalah 13 kali pertemuan dan 2 kali ujian
• Presensi kehadiran minimal adalah 80%
Persentase nilai:
1. Tugas : 30%
2. Quiz : 10%
3. UTS : 30%
4. UAS : 30%
NILAI
A ≥ 80
AB 70 – 79.99
B 60 – 69.99
BC 54 – 59.99
C 48 – 53.99
D 42 – 47.99
E ≤ 41.99
Pustaka
1. Richard D. O‟Brien, Walter E. Farr, Peter [Link],
“Introduction to Fats and Oils Technology”
2. D.K. Salunkhe, J.K. Chaven, et al,“World Oilseeds
(Chemistry, Technology, and Utilization)”
3. SBP Consultants and Engineers, “Handbook of Oilseeds,
Oils, Fats & Derivatives”
MATERI
• Pertemuan 1: Pengantar industri oleokimia
• Pertemuan 2: Industri minyak sawit & kelapa, proses fat spliting &
faksionasi asam lemak
• Pertemuan 3: Esterifikasi asam lemak, proses transesterifikasi.
• Pertemuan 4: Produksi sabun dan surfaktan
• Pertemuan 5: Produksi dan pemanfaatan alkohol lemak, produk-
produk aminasi dan oksigenasi oleokimia.
Fats and Oils: An Overview
Pertemuan 1
Introduction
• For centuries, humans have used fats and oils for food and a
variety of other uses, as: food, medicine, cosmetics, sources of
illumination, paints, lubricants, soaps, and other uses.
• The use of fats and oils for some foods was probably
instinctive; however, most likely resulted from observations of
the properties and behavior of fats and oils under different
environmental.
• Today’s uses stem largely from a knowledge of composition,
structure, properties, and reactions of the component fatty
acids obtained through the application of scientific research.
Sources of Fats and Oils
• The combined largest source of vegetable oils are the
seeds of annual plants grown in relatively temperate
climates.
• A second source of vegetable oil is the oil-bearing trees,
i.e., olive, coconut, and palm oils.
• Edible meat fats are supplied almost entirely by three
kinds of domesticated animals, i.e., lard from pigs, tallow
from cattle and sheep, and milk fat or butter from cows.
Vegetable Oil Yields
Industrial Fats and Oils Applications (1)
Fats and oils are added to various types of feeds at different levels from
0.5 to 10% for a number of reasons including the following:
1. for caloric or energy value,
2. as a growth factor,
3. to increase feed efficiency,
4. to increase palatability,
5. to reduce dustiness,
6. to allow easier handling,
7. to reduce wear on machinery for handling, mixing, pelleting, and
other processes,
8. to aid in homogenizing and stabilizing the mixture of fine-particled
feed additives, and
9. to give feed a better appearance.
Industrial Fats and Oils Applications (2)
Fat splitting, fatty acid distillation, and glycerine water evaporation are
production techniques used to produce oleochemicals or fatty acids.
These processes resemble the fat splitting of fatty glycerides or the
hydrolysis process by which fat is metabolized by humans and animals.
• The saturated fatty acids, stearic and palmitic, are used to make
products that include soap, detergents, cosmetics, candles, waxes,
chemical intermediates, and synthetic rubber.
• The unsaturated fatty acids, oleic and linoleic, are used in paints,
printing inks, metallic driers, soaps, detergents, flotation agents,
cutting oils, lubricating oils, linoleum, and chemical intermediates.
• Soap Manufacture
▫ The principal consideration for selecting a mixture of fats and oils for making
soap is that it contain the proper ratio of saturated and unsaturated, and long-,
medium-, and short-chain fatty acids to result in the desired qualities of stability,
solubility, ease of lathering, hardness, and cleaning ability in the finished soap.
• Resins and Plastics
▫ Slip agents used in resins for plastic film allow one surface to slide horizontally across another.
▫ Plasticizers are incorporated into plastics or rubber-like materials to increase flexibility,
workability, distensibility, and toughness.
• Lubricants
• Natural fats and oils were once widely used for lubrication fluids, but petroleum-derived
mineral oils have replaced most of this usage.
• Varnish and Paint
Paints are coatings used to cover surfaces and must dry quickly. Varnishes are
similar, except that no pigment is used to hide the surface.
Other industrial Applications
Cosmetics: Ethylene glycol mono- and diesters are surfactants used in
preparation of cosmetics.
Textiles: Polyamide nylon I I is made from undecenaoic acid obtained from
castor oil.
Printing: Biodegradable printing inks produced with soybean oil provide
superior print qualities, brighter colors, less rub-off, more print mileage, and
cleaner press runs than petroleum-based inks.
Building Industry: Sealing, caulking, or glazing compounds utilize vegetable oils
to produce rubber-like properties.
Pharmaceuticals: Vegetable oils act as antifoaming agents in production of
penicillin, streptomycin, tetracycline and other aerated fermentation-based
pharmaceuticals.
Food Emulsifiers: Natural glycerine derived from soap making and fatty acid
industries is utilized to produce mono- and diglycerides, the most dominant
food emulsifier.
Properties of Fats and Oils
Introduction
• The most obvious difference is that fats and oils are hydrophobic
and immiscible with water. In addition, their caloric value (9 kcal/g)
is twice as high as that of proteins and carbohydrates.
• The molecular weights of fats and oils, from several hundred to
>1000, are generally smaller than those of proteins and
carbohydrates.
• Their reversible solid-to-liquid phase transition properties allow
them to function as pastry fats, frying shortenings, and
confectionery applications.
• Their ability to dissolve color and flavor, and to provide lubricity
plays an important role in making food palatable and desirable.
• Much research have been devoted to the development of fat
substitutes for targeted performances, such as cocoa butter
substitutes, frying shortening to replace tallow for French fries, fat
substitutes using microcrystalline cellulose and sucrose polyesters.
Nomenclature and Structure
• Lipid Classes
• Aliphatic acids/fatty acids
• have various carbon chain lengths terminated with a carboxylic acid (-
COOH), which is the ∆-terminal, and amethyl group (-CH3), which is
often given the symbol η or ω
• are either saturated or unsaturated
• also exist as hydroxy acids; for example, 12-hydroxy oleic acid (or
ricinoleic acid) is found in castor seed, and cyclic acids, e.g.,
cyclopropanoic acids
• Saturated Fatty Acids
• the most common and the most important fatty acids fall in the range
from C12 to C22
• Unsaturated Fatty Acids
• Fatty acids with trans-double bonds melt at a higher temperature than
their cis counterparts.
• Glycerol-Containing Lipids
• Fatty acids majority of the combined forms are esters with glycerol
(propane- 1,2,3-triol), called triacylglycerols or triglycerides.
• Each triglyceride molecule can release three fatty acids and one glycerol.
• Other common glycerol-containing lipids are monoacylglycerols
(monoglycerides) and diacylglycerols (diglycerides). Mono-acylglycerols
exist as 1 -acyl or 2-acyl isomers which may also be designated as α- and
β-monoglycerides.
• The 1- and 3-acyl, sn isomers are enan-tiomers, which together comprise
the racemic mixture of α-monoglycerides.
Composition of Fats and Oils
• Most of the refined oils contain at least 98% triglycerides. The remainder is
composed of ~0.5% diglycerides, 0.1 % free fatty acids, 0.3% sterols, 0.1 %
tocopherols and ppm levels of phospholipids and various pigments.
• Tocopherols are known by their properties as oil-soluble antioxidants and
vitamin E. The effectiveness of the four isomers of tocopherols as vitamin E
and antioxidants are α >> β, γ, and δ; and δ >> β > γ > α, respectively.
• Sterols are crystalline, neutral, unsaponifiable alcohols; they have high
melting points with properties resembling those of cholesterol.
• They are useful by-products derived from the deodorizer distillate and are
used for the synthesis of sex hormones and vitamin D.
Free Fatty Acids
• FFA are generated by hydrolysis in the oil-bearing materials
throughout harvesting, handling and processing.
• FFA in extracted crude oils are usually removed as soap by caustic
refining. A high FFA concentration in crude oil means higher
refining loss. After refining, any residual FFA can be removed by
deodorization.
• Undeodorized meat fat should contain <1 % FFA.
• The FFA content in oil can be determined conveniently by titrating
the oil in isopropanol and hexane (85: 15) against NaOH (AOCS
Method Ca 5a-40).
• Acidity of oil is sometimes measured as acid value or neutralization
number, which is defined as the milligrams of potassium hydroxide
(KOH) required to neutralize the FFA in l g of fat.
• Each unit of acid value is equivalent to 0.503% FFA, i.e., the acid
value or acid number of a fat is normally about twice its FFA
concentration.
Chemical Properties and Reactions
• Hydrolysis and FFA
▫ Hydrolysis of glycerides with water is catalyzed by enzyme, acid, or
metals to yield FFA and glycerol products.
▫ In practice, fat is hydrolyzed or split under high temperature and
pressure. More complete hydrolysis can be accomplished with a large
amount of excess water and periodic removal of the glycerol-rich water
phase.
▫ Hydrolysis is normally catalyzed by acids.
• Lipolytic enzymes or lipases, which have received much attention in
recent years, can catalyze the hydrolysis at near ambient
temperatures (40-50°C).
• Hydrolysis of oils in oilseed can take place in the preharvest and
postharvest handling and storage, during oil extraction, crude oil
storage, and shipping.
• The result is an elevation of the concentration of FFA in the crude
oil.
• High FFA in finished oil will cause smoke and shorter shelf life.
• Esterification
▫ Esterification can be considered by combining fatty acids with alcohols,
glycols, and polyfunctional materials such as propylene glycol, sugar, and
polyglycerol.
▫ Esterification and interesterification are practiced to produce
emulsifiers, such as monoglycerides, propylene glycol mono- and
diesters, and sucrose esters.
• Interesterification
▫ Interesterification use of an alkaline catalys:
1. the reaction between fat and alcohols is called alcoholysis and produces
simple esters of fatty acids or wax esters of long-chain alcohol and fatty acid
2. the reaction between fat and glycerol is termed glycerolysis and is often
used to produce mono- and diglycerides
3. the interchange of fatty acids between two triglycerides is called either
interesterification and yields a fat with different melting characteristics
than those of its original component fats
Saponification Value
• The saponification value (AOCS Method Cd 3-25) is determined by
reacting a known amount of fat with a known quantity of excess
ethanolic KOH.
• Unreacted KOH is determined by titration with standard HCl in the
presence of an indicator.
• The saponification value is calculated as the milligrams of KOH
required to saponify 1 g of fat.
Iodine Value
• Iodine value (AOCS Method Cd 1-
25 or Wijs Method) is obtained by
reacting fat with a known amount
of excess halogen, iodine, or iodine
chloride.
• The reduction of the excess
halogen with KOH and titration
with standard sodium thiosulfate
using starch solution as an
indicator of free iodine determines
the amount of iodine consumed by
the fat.
• The final iodine value is expressed
as the centigrams of iodine per
gram of fat (or % iodine absorbed).
Oxidative Stability
• The oxidation of oil releases undesirable oxidized odor, it is considered
as oxidative rancidity.
• Quality control professionals often rely on the measurement of
hydroperoxides and conjugated dienes or the amount of carbonyls
(aldehydes and ketones).
• Peroxide Value (PV)
▫ The extent of oxidation is measured by the amount of free iodine the
oxidized fat can liberate from potassium iodide (KI).
▫ The results are expressed as peroxide value (PV) in milliequivalents of
iodine formed per kilogram of fat (AOCS Method Cd 8-53).
Anisidine Value (AV)
• Peroxides are unstable. They tend to decompose and form aldehydes
and ketones. The content of aldehyde, principally 2-alkenal, in the
oil can be measured to further assess its degree of oxidation.
• Determining the absorbance of the sample in isooctane at 350 nm.
Physical Properties
• Crystal Structure of Fats
▫ Fats can crystallize in different forms in a phenomenon called
polymorphism, affects the consistency, plasticity, graininess and
other physical properties of many products such as butter, lard,
margarine, hydrogenated vegetable shortenings, and cocoa
butter.
▫ fats in the α-form are characterized as waxy;
▫ fats in the β’-form are characterized as fine-grained with smooth
texture;
▫ the β-form crystals are termed coarse and grainy.
Thermal Properties
• Melting Point
▫ Fats and fatty acids can solidify in several crystal forms.
▫ The melting points of fatty acids increase with increasing chain
length and decrease as the acids become more unsaturated.
Specific Heat and Heat of Fusion
• Specific heat, cp, is defined as the amount of heat required to raise
the temperature of 1 g of material by 1°C.
• The heat of fusion (Hf) of a fatty material includes the amount of
energy required to melt a gram of material and the heat of crystal
transition.
• Vapor Pressure and Boiling Point
▫ Triglycerides of long-chain fatty acids have extremely low vapor
pressures and can be distilled satisfactorily only by molecular or
short-path distillation.
▫ Their boiling points can be observed only under very high
vacuum condition.
• However, high-vacuum, short-path distillation is preferred to keep
the temperature as low as possible to avoid any undesirable
reactions including interesterification.
• Smoke, Flash, and Fire Points
▫ The smoke, flash, and fire points of fatty materials are measures
of thermal stabilities of fats and oils when heated in the presence
of air.
▫ Lower than normal smoke, flash, or fire points indicate the
presence of an excess of residual nontriglyceride impurities, such
as FFA, monoglycerides, and other volatiles, which should be
largely removed during steam deodorization.
• Density
▫ Liquid oils have a density between 0.91 and 0.92 g/mL at room
temperature. Oil density generally increases with lower molecular
weight and higher unsaturation of the fatty acids.
Surface and Interfacial Tension
• Surface tension at the air and oil surface is defined as the force
(dyne) required to pull the oil film with a known width (cm).
