INDUSTRIES

ChE 313 Industrial Chemistry Lecture

Engr. May V. Tampus

OILS, FATS, & WAXES

Fats and oils are composed primarily of triglycerides , esters of glycerol and fatty acids. Waxes are esters of fatty acids with long-chain aliphatic alcohols, sterols, tocopherols, or similar materials.

FATS & OILS

World production of fats & oils

5%

vegetable oils
40% 55% land-animal fats marine oils

Ullmanns Encylcopedia of Industrial Chemistry, 6th ed., 1998

Classes of Fats & Oils

Based on the Rate of Drying
Non-drying Oils Coconut oil Butter Tallow Palm oil Lard Semi-drying Oils Olive oil Peanut oil Rapeseed oil Cottonseed oil Corn oil Soybean oil Sunflower oil Sesame oil Iodine no. = 85-130 Drying Oils Fish oil Tung Linseed oil Perilla oil

Iodine no. = 9-65

Iodine no. = 150-200

A process which results in the solidification of the fat or oil upon exposure to air which is caused by oxidation, or chemical combination with oxygen, rather than by evaporation of a solvent Iodine number a measure of the rate of drying of the oil

Common Types of Vegetable Oils

Rapeseed/canola oil Coconut oil Corn oil Cottonseed oil Olive oil Palm oil Safflower oil Soybean oil Sunflower oil Sesame oil Peanut oil

Types of Animal Fats & Oils

Neats foot oil Whale oil Cod liver oil Shark liver oil Fish oils Lard

Composition Natural Fats & Oils

Principal component: Triglycerides which contain at least two different fatty acid groups The chemical, physical, and biological properties of oils and fats are determined by the type of the fatty acid groups and their distribution over the triglyceride molecules. Component of fats & oils triglycerides (triacylglycerides) diglycerides (diacylglycerides) monoglycerides (monoacylglycerides) % 97 Up to 3 Up to 1

Other Components of Fats & Oils

Minor components of Fats & Oils Formed by Found in

Free fatty acids & Partial glycerides (mono- & diglycerides)

Phospholipids Sterols

Enzymatic cleavage of triglycerides Hydrolysis

Esterification of glycerides by fatty acids with phosphoric acid derived biologically from terpenes

Rice bran oil, Palm oil

Coconut oil Palm kernel Lard , Tallow, Butterfat , Milk fat Algae , Coconut oil, Olive oil Wheatgerm oil, Soybean oil Cottonseed oil

condensation of isoprene condensation of isoprene units units Carotenoids & Xanthophylls Chlorophyll

condensation of eight isoprene units hydroxylation of the carotenoid skeleton

Physical Properties of Fats & Oils

Physical property Melting point Description -increases with increasing chain-length of the even-numbered saturated FA, and decreases with increasing degree of unsaturation -wide range of temperature -depends on the polymorphic form of the glycerides -increases with increasing chain length and increasing degree of saturation -Naturally occurring fats generally have a lower heat of fusion than simple glycerides. The specific heat of liquid oils and fats increases with increasing chain length and degree of saturation; it also increases with temperature. -decreases with increasing molecular mass and degree of saturation -A high free fatty acid content tends to decrease the density of a crude oil -Oxidation generally leads to higher densities. -Oils tend to have a relatively high viscosity because of intermolecular attraction between their fatty acid chains. -Generally, viscosity tends to increase slightly with increasing degree of saturation and increasing chain length -approximately linear relationship between log viscosity and temperature -The viscosity of oils tends to increase on prolonged heating due to the formation of dimeric and oligomeric fatty acid groups. -Nearly all fats and fatty acids are easily soluble in common organic solvents such as hydrocarbons, chlorinated hydrocarbons, ether, and acetone. -The water solubility of fats is low and decreases with increasing chain length and with decreasing temperature. -The solubility of gases in oils generally increases with increase in temperature, the reverse holding for carbon dioxide

Latent heat of fusion Specific heat Density

Viscosity

Solubility & miscibility

Fats & Oils

RELEVANT CHEMICAL REACTIONS

Hydrolysis
Hydrolysis of glycerides into glycerol and fatty acids

Alkali hydrolysis (saponification) of glycerides

Hydrolysis Description
Reversible Equilibrium can be shifted to the right via:
Large excess of water High temperature High temperature

Catalysts:
inorganic and organic acids, e.g., sulfonated hydrocarbons Enzymes, e.g., pancreatic lipase

Interesterification
Interesterification occurs when acyl groups of glycerides are exchanged inter- and intramolecularly without addition of acids or alcohols
Transesterification occurs when a carboxylic acid (acidolysis) or alcohol (alcoholysis) reacts with an ester to produce a different ester. Ester-ester interchange is also a form of transesterification. Random interesterification or Randomization

Directed interesterification

Interesterification in LARD
H2 C O Na O + NaK + H2O (trace) O HC O C R2 + KOCR + H2 1 O H2 C O C R3
Intramolecular interesterification

H2 C O C R1 O HC O C R2 O H2 C O C R3 O H2 C O C R4 O HC O C R5 O H2 C O C R6 + O H2 C O C R2 HC O Na O H2 C O C R3

Intermolecular interesterification

Interesterification in LARD
O H2 C O C R4 O HC O C R5 + O H2 C O C R2 O HC O C R6 O H2 C O Na H2 C O C R3 , etc.

In directed interesterification, a molecule crystallizes when its three fatty acids are saturated.

Interesterification Description
Fats must contain only 0.1 % FFA and dried to avoid excessive deactivation of the catalyst Catalyst: 0.1-0.3 %sodium ethoxide, sodium methoxide or Na-K alloy Temperature: 80 100 C Operating mode: batch or continuous

Transesterification

Transesterification: Acidolysis
Example: transesterification of coconut oil with acetic acid and subsequent esterification of excess acetic acid with glycerol Catalysts: base (e.g., NaOH) or acid (HCl) No catalyst is required at temperatures of 260 300 C!

Transesterification: Alcoholysis
Example: transesterification of fats with methanol as the first step in the continuous production of soap Bradshaw process Catalysts: 0.1 0.5 % caustic soda Temperature: ca. 80 C

Hydrogenation
General Scheme:

C17 H 31COO 3 C3 H 5 3H 2

Ni

C17 H 33COO 3 C3 H 5 H

420 .8 kJ / kg

Hydrogenation Description
Also termed as hardening always leads to an increase in melting point Partial hydrogenation can lead to isomerization of cis double bonds to trans double bonds. Catalysts: nickel, platinum, copper, or palladium An exothermic process Neither absolute selectivity nor complete isomerization (or complete suppression of isomerization) can be achieved. Operating mode: batch or continuous

Batch Hydrogenation
Scale of production: normally on a scale of 5 25 t Catalyst: 0.01 0.1 % active nickel Operating temperature: 100-180oC Usual working pressure: 0.15 0.3 MPa (1.5 3 bar)

Production Ni catalyst from Nickel formate

Methods:
1. 2. Liquid-reduced process Wet-reduced process

Operating temperature: 160-240oC (though 160oC is more common) Operating pressure: 200-700 kPa Chemical Reaction:
Ni HCOO
2

2 H 2O

Ni 2CO2

H2

2 H 2O

Isomerization
Naturally occurring fatty acids exist predominantly in the cis form. An equilibrium mixture in which the higher melting trans form predominates can be formed by heating to 100 200 C in the presence of catalysts such as nickel, selenium, sulfur, iodine, nitrogen oxides, or sulfur dioxide. If reaction times and temperatures (above 200oC) are extended, linolenic acid can be converted into cyclohexadiene and benzene derivatives :

Isomerization can occur if oils and fats are heated at temperatures above 100 C in the presence of bleaching earth, kieselguhr, or activated charcoal.

Autoxidation
Autoxidation oxidation of olefins with oxygen; involves the formation of a hydroperoxide on a methylene group adjacent to a double bond ; this step proceeds via a free-radical mechanism

Photooxygenation - light-induced oxidation leads to a fast buildup of radicals

The intermediate hydroperoxides are labile compounds that decompose into a number of different products : epoxides, alcohols, diols, keto compounds, dicarboxylic acids, aldehydes, and isomerization and polymerization products. The volatile carbonyl compounds formed in this process are responsible for the taste and odor of oxidized oils and fats. When the radical concentration has reached a certain limit, the chain reaction is gradually stopped by mutual combination of radicals.

Industrial Uses of Fats & Oils

Fats & Oils Animal Fats Coconut oil Linseed oil Soybean oil Castor oil Tung oil Uses Soaps, greases, paints, varnishes, syndets, fatty acids, & plasticizers Fatty alcohols, soaps, & detergents Paints, varnishes, floor coverings, lubricants, & greases Paints, varnishes, floor coverings, lubricants, & greases Protective coatings, plastics, plasticizers, lubricants, hydraulic fluids Paints & varnishes

Tall oil

Soaps, leather, paint, emulsifiers, adhesives, ink

WAXES

What are WAXES?

According to German Association for Fat Science waxes must have : 1. A drop point (mp) >40 C 2. Their melt viscosity must not exceed 10 000 mPa s at 10 C above the drop point 3. They should be polishable under slight pressure and have a strongly temperature-dependent consistency and solubility 4. At 20 C they must be kneadable or hard to brittle, coarse to finely crystalline, transparent to opaque, but not glassy, or highly viscous or liquid 5. Above 40 C they should melt without decomposition 6. Above the mp the viscosity should exhibit a strongly negative temperature dependence and the liquid should not tend to stringiness 7. Waxes should normally melt between ca. 50 and 90 C (in exceptional cases up to 200 C) 8. Waxes generally burn with a sooting flame after ignition 9. Waxes can form pastes or gels and are poor conductors of heat and electricity (i.e., they are thermal and electrical insulators).

Waxes are characterized by the following:

1. 2. Composition: Complex mixtures of compounds Melting point: may vary over a wide range, usually above of the harder fats & fatty acids. 3. Phase: Solid at ambient temperature while liquid at 38o C to 93o C. 4. Solubility: Insoluble in water 5. Combustibility: combustible 6. Thermoplastic in nature 7. Some waxes have very good wetting or penetrating qualities 8. Most waxes exhibit low surface tensions 9. Most waxes are non-adhesive and slippery 10. Certain waxes are incompatible with other waxes, resins and other materials 11. Admixtures of higher melting materials does not necessarily raise the melting pint of waxes proportionally

Classes of Waxes
Partially Synthetic Fully Synthetic Waxes Waxes Fossil waxes Esterified waxes C1 Building Blocks Nonfossil or recent Amide waxes Polyolefin waxes natural waxes Alcohol (lanette) waxes Modified natural waxes Wool wax (Lanolin) Natural Waxes

Waxes can also be classified as:

a. Vegetable waxes b. Animal waxes c. Insect waxes

d. Mineral waxes e. Synthetic waxes

Vegetable Waxes
Vegetable Wax Source Carnauba wax fronds of palm tree almost exclusively grown in the semiarid region of Brazil Candelilla wax stalks and leaf stems of plants, which grow as bushes or shrubs: Japan wax berries of a small tree native to Japan and China cultivated for its wax Jojoba oil seeds of the jojoba plant grown in semiarid regions of Costa Rica, Israel, Mexico, and the United States ca 80 wt % of esters of eicos11-enoic and docos-13-enoic acids, and eicos-11-en-1-ol, and docos-13-en-1-ol, ca 17 wt % of other liquid esters, with the balance being free alcohols, free acids, and steroids virtually colorless to golden yellow, odorless, unsaturated oil Melting point of 6.8 7.0 C; saponification number of 92 and acid number of 2

Euphorbia (E. cerifera, E. antisyphilitica) and Pedilanthus (P. pavonis, P. aphyllus) species
hydrocarbons, esters of long-chain alcohols and acids, long-chain alcohols, sterols, and neutral resins, and long-chain acids

Composition

aliphatic and aromatic esters of long-chain alcohols and acids, with smaller amounts of free fatty acids (FFAs) and alcohols, and resins

triglycerides, tripalmitin

primarily

Important properties

one of the hardest and highestmelting natural waxes readily soluble in most nonpolar solvents on warming but partially soluble in polar solvents has a weakly aromatic odor and a characteristic haylike scent (similar to coumarin) in the molten state acid number of 8, and a saponification number of 80 Pigments, inks, gels, polishes, solvent and oil paste formulation, cosmetics, castings and food

hard, brittle wax that is very similar to carnaba wax with regard to solubility in polar and nonpolar organic solvents melting point of 70C, a penetration of 3 dmm at 25C, an acid number of 14, and a saponification number of 55

melting point of 53C, an acid number of 18, and a saponification number of 217

Uss & applicatios

cosmetics, foods, pharmaceuticals

and

candles, polishes, lubricants, and as an additive to thermoplastic resins & foodrelated applications

Cosmetics, candles and low volume specialty applications

Insect & Animal Waxes

Insect/animal wax Source Beeswax end product of the metabolism of a honeybee class (Apis mellifica, A. Spermaceti head oil & parts of the blubber of the sperm whale Shellac wax resinous exudate of the scale insect Laccifer lacca (formerly Wool wax Raw wool from sheep

carnica), which belongs to the Apis genus

Tachardia lacca) of the Coccidae family

secreted by bees and is used to construct the combs in which bees store their honey Composition major components are esters of C30 and C32 alcohols with C16 acids, free C25 to C31 carboxylic acids, and C25 to C31 hydrocarbons Largely cetyl palmitate Total acid: essentially of a mixture of even-numbered fatty acids (C12 C18 , 21 26 % of the total acid) and waxy acids (C28 C34 , mainly C32 and C34) Alcohols: (C28 C32) the C28 component predominates (62 65 % of the total alcohol). Hydrocarbon: paraffins with 27, 29, and 31 carbon atoms. hard, yellow to brown ca. 48 % wax esters, 33 % sterol esters, 6 % free sterols, 3.5 % free acids, 6 % lactones, and 1 2 % hydrocarbons

Important properties

can have a yellow, orange, or dark brown color melting point of 64C, a penetration (hardness) of 20 dmm at 25C and 76 dmm at 43.3C (ASTM D1321), a viscosity of 1470 mm2/s at 98.9C, an acid number of 20, and a saponification number of 84 moderately hard

Translucent, odorless, & tasteless

Crude wool wax is a greasy, glutinuous, brown-yellow to brown-black substance with a penetrating goatlike odor (mp 34 38 C). Neutral wool wax is yellow to light brown in color (mp 38 42 C), with a milder odor, whereas Adeps lanae is a pale yellow, almost odorless substance (mp 40 42 C).

Uses & applications

Cosmetics, pharmaceuticals, candle production

Base for ointments

Surface coating

leather polishes, cosmetics (e.g., creams, baby-care products, and toilet soap), pharmaceuticals (e.g., plasters, ointments, and suppositories), and lubricants; purified form known as lanolin

Mineral Waxes
Mineral wax
Source/derivation

Montan wax
solvent extraction of lignite forms part of the extractable, bituminous components of lignite and peat

Paraffin wax
From petroleum (macrocrystalline wax) obtained from light and middle lubricating oil cuts of vacuum distillation; also include waxes from heavy lubricating oil distillates composed of 40-90 wt % normal alkanes, with the remainder C18C36 isoalkanes and cycloalkanes

Microcrystalline wax
from the residual fraction of crude oil distillation or from crude oil tank bottoms

Ozoc(or k)erite or Ceresin wax

Earth wax mined in Europe (Poland) but now a petroleum-derived paraffin wax

Composition

a mixture of long-chain (C24-C30) esters (62-68 wt %), long-chain acids (22-26 wt %), and long-chain alcohols, ketones, and hydrocarbons (7-15 wt %)

a mixture of saturated hydrocarbons that are predominantly solid at room temperature, such as n- and

isoalkanes, naphthenes, and alkyland naphthene-substituted aromatics

araffin wax of very narrow molecular weight distribution or blend of petroleum waxes

Important properties

black-brown, hard, brittle product with a conchoidal fracture pattern A melting point of 80C, an acid number of 32, and a saponification number of 92

insoluble in water and sparingly soluble in low molar mass aliphatic alcohols and ethers extremely unreactive under normal conditions.

insoluble in water and most organic solvents at room temperature more reactive than paraffin waxes because of the higher concentration of complex branched hydrocarbons with tertiary and quaternary carbon atoms Has a great affinity for oil Petroleum jelly, polishes, adhesives, cheese wax, chewing gum base, cosmetic preparations, sealing & cable compounds, plastics & paper, candles, casting and dental compounds, foam regulator, explosives & propellants

Insoluble in water

Uses & applications

component in one-time hot-melt carbonpaper inks, polishes , plastic lubricants Building industries, wood & metal processing Cosmetics, pharmaceuticals, adhesives, resins & office equipment

Chewing gums, protective coatings for fruits, vegetables & cheeses Food & paper packaging Rubber industries, lubricants , adhesives, candles Cosmetics & pharmaceuticals

Electrical insulations, waterproofing, & impregnating

Synthetic Waxes
Synthetic wax
Source /derivation

Polyethylene waxes
made either by high pressure (free-radical) polymerization or low pressure (Zeigler-type catalysts) polymerization HP-PE wax: consist mainly of branched molecular chains in which shorter side chains, such as ethyl and butyl, predominate; generally have low densities (low-density polyethylene waxes, LDPE waxes) For waxes, an upper limit to the melt viscosity of ca. 20 000 mm2/s at 120 C is defined, which corresponds to an average molar mass (weight-average molar mass Mw) of

Fischer-Tropsch waxes
Derived from liquefaction of coal via Fischer-Tropsch synthesis by polymerization of carbon monoxide under high pressure and over special catalysts essentially n-paraffins with chain lengths between 20 and

Composition

50 carbon atoms

Important properties

ca. 37 000 g/mol

HP-PE wax: colorless, white to transparent and form clear melts; dissolve in nonpolar solvents (e.g., aliphatic, aromatic, and chlorinated hydrocarbons) on heating and generally crystallize as very fine particles on cooling; form mobile dispersions or paste-like gels, which frequently exhibit thixotropic properties Uses & applications additives for inks and coatings, pigment dispersions, plastics, rubbers, polishes, cosmetics, toners, adhesives, and corrosion protection: Wash and wear finishes for textiles Release agents in building industries, plastic processing and rubber industries Surface finishing agents in paper products Protective coating of citrus fruits

have a fine crystalline structure and, because of the narrow molar mass distribution, a small melting range and very low melt viscosities fully compatible with refined waxes, polyolefin waxes, and most vegetable waxes soluble at elevated temperature in the usual wax solvents (e.g., naphtha, turpentine, and toluene) to give clear solutions

Used in plastics processing as lubricants for poly(vinyl chloride) and polystyrene, as well as mold-release agents ; as melting point improvers, hardeners, and viscosity reducers in hot melts and candles ; and, because of their good polishability, for the production of cleaning agents and polishes; improve the abrasion resistance of paints and printing inks

WAXES

RELEVANT CHEMICAL REACTIONS

Chemical Reactions in

POLETHYLENE WAXES PRODUCTION

Free-Radical Polymerization (High-pressure Polymerization)

MECHANISMS: In initiating (start) reactions (Eq. 2), radicals R formed from the decomposition (Eq. 1) of initiator molecules I react with monomer molecules M. The resulting "monomer radicals" R M add further monomer molecules in the propagation reaction (Eq. 3) until the growing polymer radicals R~~~M are terminated by recombination (Eq. 4) or disproportionation (Eq. 5) with other polymer radicals or by addition of initiator radicals (Eq. 6) : I 2 R (1) R + M R M (2) R M + M R M M, etc. R Mn1 M (3) R Mn1 M + M Mm1 R R Mn+m R (4) R Mn1 M + M Mm1 R R Mn2 M=M + X Mm R (5) R Mn1 M + R R Mn R (6)

Where: X = an atom or a group that is transferred from the ultimate monomeric unit of one polymer radical to another polymer radical

Free-Radical Polymerization (High-pressure Polymerization)

Termination of chain growth in PE waxes by reaction with a regulator molecule such as propene RCH2CH2 + CH2 = CHCH3 RCH=CH2 + CH3CHCH3 Termination of polymerization in PE waxes by recombination or disproportionation of two macroradicals

Long-chain branching occurs by intermolecular chain-transfer reactions

Free-Radical Polymerization (High-pressure Polymerization)

UNIQUE FEATURE:
increased formation of short ethyl and butyl side chains that are formed by intramolecular radical transfer

Side reaction: Depolymerization of chain radicals at high reaction temperature

High-pressure Polymerization Process Description

Monomer: ethylene is in a supercritical state Polymerization takes place in a one-phase system. The wax remains as a melt and the unreacted ethylene vapor is recycled. Reaction pressure:
Homo- & copolymerization usually 150 320 MPa; 70 MPa (max.) with isopropanol as the molar mass regulator

Reactors: autoclaves & tubular reactors Reaction temperature:

Homopoymerization - 200 350 C Copolymerization - 200 300 C

Initiators: Organic peroxides and molecular oxygen (the latter exclusively in tubular reactors) Molar mass regulators: Hydrogen, lower alkanes (e.g., propane), lower alkenes (e.g., propene or butene), alkyl aromatics, lower aldehydes (e.g., propionaldehyde), and lower alcohols (e.g., isopropanol) or mixtures of these substances are mainly employed.

Ziegler-Natta Polymerization for PE Waxes

Same chemistry as in polymerization of polyolefins Modified catalysts:
Supported catalysts, which contain titanium atoms as the active species and magnesium compounds as the carrier material Catalysts derived from titanium tetrachloride and magnesium chloride, oxide, hydroxide, or alkoxide

Chemical Reactions in

FISCHER-TROPSCH WAXES PRODUCTION

Fischer-Tropsch Synthesis Mechanisms

Reaction scheme 1
Carbon monoxide dissociates at the catalyst surface (M) to carbon and oxygen atoms. Chemisorbed hydrogen reacts with the carbon to form CHx entities, which combine into hydrocarbon chains. Chain termination produces aolefins or alkanes. To account for the formation of oxygen compounds, a parallel mechanism postulates their production on oxide components of the catalyst surface.

Fischer-Tropsch Synthesis Mechanisms

Reaction scheme 2
Carbon monoxide does not dissociate, but is hydrogenated to form oxymethylene species, which condense on the catalyst surface to propagate the hydrocarbon chain.

Fischer-Tropsch Synthesis Mechanisms

Reaction scheme 3
Carbon monoxide CO molecule does not dissociate, but inserts in an M H or an M C bond . This is observed in homogeneous catalysts.

Fischer-Tropsch Process Description

Catalysts: iron-based catalysts promoted with potassium and copper (SASOL) alkali-promoted catalyst prepared by sodium carbonate precipitation of a solution of iron and copper nitrate ARGE (Arbeitsgemeinschaft) fused-iron catalyst(Synthol) Catalyst lifetime: ca. 6 months Reaction temperature: 220 C - 225C (ARGE) 320 340o C (Synthol) Reaction pressure: 2.5 MPa (ARGE) 2.3 MPa (Synthol) H2 : CO feed ratio: 1.7 (ARGE) and 2.54 (Synthol) CO + H2 conversion, %: 60-66 (ARGE) and 85 (Synthol) Extremely exothermic