Chemistry of Oleochemicals and Surfactants

✓ Oils and fats are tri-esters of glycerol

and fatty acids : tri-acylglycerol.
✓Oleochemicals: chemicals derived
from oils; fatty acids, fatty esters, and
glycerol are primary oleochemicals.
✓fatty alcohols, fatty amines -sec.
oleochemicals Structure of triglyceride

➢Surfactants: Surface active substances or substances

active at interfaces through modification of surface
energy. Soap is the oldest known surfactants.
 Oils & Fats of Vegetable Origin
• By-products, where the crop is grown for purpose other than seed oil :
Cotton (fabric), Corn (grain), Soybean (protein rich meal), ricebran
• Tree crops which are generally slow to mature but then produce crop
regularly for many years : Palm, Palm Kernel, Coconut, Olive
• Crops, which have to be replanted each year to produce an annual harvest :
Rape/ Mustard, Sunflower, Groundnut, linseed, sesame, Castor etc.
• Modified Crops, High/Low erucic rape (plant breeding) and high
monounsaturated sunflower & high lauric canola (Molecular biology)
• Tree borne oils of forest origin (Indian context): Sal, mahua, neem, karanj,
undi, pisa, khakhan etc.
• Oils & Fats of Animal Origin: Milk Fat, Lard, Tallow, Fish
oils
• Microbial oils/ Single Cell Oil
 Oils & Fats production
World vs India
in Mn MT
Oil & Fats World India
Palm Oil 58.46 0.13
Soya Oil 43.78 1.39
Rapeseed Oil 25.69 2.53
Sunflower Oil 15.64 0.18
Cottonseed Oil 4.86 1.08
Groundnut Oil 4.11 0.58
Rice Bran Oil 1.2 0.93
Other Oil & Fats 42.69 2.93
Total 196.43 9.75
Vegetable oil – Import Dependence
 Structures of Important Fatty Acids
Common Name Symbol Unsaturation
Saturated
Lauric 12:0 _
Myristic 14:0 _
Palmitic 16:0 _
Stearic 18:0 _
Arachidic 20:0 _
Behenic 22:0 _
Monounsaturated
Oleic 18:1 9c
Petroselinic 18:1 6c
Erucic 22:1 13c
Polyunsaturated (Non conjugated)
Linoleic 18:2 9c12c
Linolenic (ALA) 18:3 (ω-3) 9c12c15c
Linoleic (GLA) 18:3 (ω-6) 6c9c12c
Arachidonic 20:4 (ω-6) 5c8c11c14c
Eicosapentanoic (EPA) 20:5 (ω-3) 5c8c11c14c17c
Docosahexanoic (DHA) 22:6 (ω-3) 4c7c10c13c16c19c
Polyunsaturated (Conjugated)
Eleostearic 18:3 9c11t13t
Hydroxy
Ricinoleic 18:1 12-OH9c

Typical
triglyceride
molecule (1-
palmitine 2-
linolein 3-olein)
 % Fatty Acid Composition

Sr. Name of
ρ S. V. I. V. C14: C C18:
C18:1 C18:2 C18:3 C20:0
Any special fatty
No. the Oil 16:0
acid
0 0
177-
0.945-0.965/ 187 Ricinoleic:86-90; 9,10
1 Castor 83-86 ---- 2.0 1.0 7.0 5.0 ---- ----
25°C H.V.- dihydroxy stearic: 0.7
160
C6:0: 0-0.8, C8:0: 5.0-
13.0
0.917-0.919/ 251- 7.5- 8.0- 1.0- 9.0, C10:0: 6.0-10.0,
2 Coconut - 5.0-8.0 0-1.0 ---- 0-0.5
25°C 263 10.5 11.0 3.0 C12:0: 44.0-52.0,
19.0
Palmitoleic: tr -2.5
0.915-0.926 191- 103-
3 Cottonseed 0.4 20.0 2.0 35.0 42 ---- ---- ----
/15°C 196 115

0.910-0.915/ 188- 84- 6.0- 3.0- 52.0- 13.0- Lignoceric: 1-3, Behenic
4 Groundnut ---- ---- 2.0-4.0
25°C 195 100 9.0 6.0 60.0 27.0 acid: 1-3

0.931-0.938/ 189- 170- 4.0- 2.0- 12.0- 17.0-

5 Linseed ---- 35.0-60.0 0.3-1.0 ----
15°C 196 180 7.0 5.0 34.0 24.0

0.906-0.910/ 169- 98- Erucic: 47.0,

6 Mustard ---- 1.5 0.4 22.0 14.2 6.8 ----
25°C 176 110 Behenic:2.0

0.921-0.925 196- 0.5- 32.0- 2.0- 38.0- 5.0-

7 Palm 48-58 ---- ---- ----
/15°C 205 2.0 45.0 7.0 52.0 11.0

0.916-0.922/ 189- 128- 7.0- 2.0- 22.0- 43.0-

8 Soyabean tr.0.5 5.0-11.0 ---- ----
25°C 195 143 11.0 6.0 34.0 56.0

0.915-0.919 / 188- 125- 3.0- 1.0- 14.0- 44.0-

9 Sunflower ---- ---- 0.6-4.0 Behenic: 0.8
25°C 194 140 6.0 3.0 35.0 75.0
Fatty Acids
14.0
Production (≈ Demand) Capacity
12.0

Million MTs 10.0

8.0 9
8.1 8.4
6.0
6.2 7 7.5
4.0

2.0

0.0
2011 2012 2013 2014 2015 2016

Global Fatty Acid Capacity by Region

CL 2016 : 12 Mn MTs

Malaysia
17% Indonesia
Europe
31%
13%

China
ROW 16%
North America 7% India
7% 9%
 8
Diverse oleochemicals from oils and fats
Oleochemical Portfolio

Oleochemicals

Fatty Acids Fatty Alcohols Glycerin

➢ Oleic Acid ➢ Lauryl-Myristyl ➢ Entire range of

➢ Stearic Acid (Triple Alcohol Glycerin grades:
pressed and Rubber grade) ➢ Cetyl Alcohol USP/JP/CP/IP
➢ Behenic Acid ➢ Stearyl Alcohol
➢ Erucic Acid ➢ Ceto-Stearyl Alcohol
➢ Palmitic Acid ➢ Behenyl Alcohol
Chemical Reactions and
derivatisations
• Crude level decreasing
• Increasing fines for
pollution
• High Costs for waste
disposal
• Taxation for storage of
hazardous wastes
• Chemical Legislation

http://ngm.nationalgeographic.com/ngm/0406/feature5/
 Applicability of Green Chemistry
• According to the seventh principle of Green Chemistry, a raw
material or feedstock should be renewable rather than
depleting whenever technically and economically practicable.
• The term ‘Renewable Resources’ primarily includes
carbohydrates (starch, cellulose, sugars) and lipids (animal and
vegetable fats and oils, phospholipids etc.).
• The National Research Council of the USA has presented the
forecast on utilizations of renewable feedstock upto 2090. In
2020, 25% of the production of organic chemical products is
expected to come from renewable feedstocks.
• [Ref.: Thayer, A. (2000), “Biobased Industrial Products: Priorities for
Research and Commercialisation (Ed.: National Research Council)”, Chem.
Eng. News, Vol. 78, Issue 22, pp. 40 Washington, DC.]
 Oleochemical Derivatizations
• i) The terminal functional group mostly ester or carboxyl group-
Traditionally, industrial oleochemistry has concentrated predominantly on
exploiting synthetic methods- transesterifications, esterifications
hydrogenolysis, saponifications, acylation etc. applied to the carboxylic
group of FA to synthesize major industrial oleochemicals.
• ii) Single or multiple double bonds- Chemical modification of seed oils at
the unsaturated bond sites results in changes to the physical properties of
the substrate and allows products to be tailored to meet specific
applications. Currently less than 10% of the modifications have involved
the hydrocarbon backbone of the fatty acid.
• iii) Carbon atom α to the functional group- although the most reactive
sites in fatty acids are the carboxyl group and double bonds, methylenes
adjacent to them are activated, increasing their reactivity. Only rarely do
saturated chains show reactivity.
• iv) Secondary OH group- The presence of hydroxyl group on castor oil
makes it vital industrial raw material.
• v) Other special functional groups- e.g. epoxy group in Vernolic acid
present in oil obtained from Euphorbia lagascae.
 Chemistry of Oleochemicals
✓Oleochemicals: chemicals derived from oils; fatty acids,
fatty esters, and glycerol are primary oleochemicals.
➢Secondary Oleochemicals:
saponification and coprecipitation (metallic soaps),
transesterification and esterification (e.g. FAME, sucrose
polyesters, MG), hydrogenation and hydrogenolysis (e.g. fatty
alcohols), ethoxylation (e.g. alcohol ethers), sulphonation and
sulphation (e.g. ester sulphonates, TRO), ammonolysis and
amidation (nitrogen derivatives), ozonolysis (azealic/
pelargonic acids) epoxidation and hydroxylation, dimerization
and polymerisation, pyrolysis, alkali fusion etc.
Chemical reactions related to Chemical reactions related to the
unsaturated centres carboxyl group
❖ Hydrogenation
❖ Hydrolysis
❖ Oxidation
❖ Saponification
❖ Halogenation
❖ Esterification
❖ Epoxidation ❖ Interesterification
❖ Hydroxylation ❖ Hydrogenolysis
❖ Acid chlorides and
❖ Metathesis anhydrides
❖ Dimerisation ❖ Nitrogen derivatives
❖ Double bond migration and ❖ Ethoxylation and
propoxylation
cyclisation ❖ Sulfonation and other
❖ Pyrolysis and alkali fusion reactions at the α-position
CHEMICAL PROPERTIES RELATED TO THE
CARBOXYL GROUP
• Reactions of the carboxyl and ester functions represent a
very significant part of lipid chemistry.
• These may be conducted on a milligram scale for
analytical purposes such as the preparation of methyl
esters for gas chromatography and formation of
oxazolines and picolinyl esters for mass spectrometry, on
a gram scale for laboratory synthesis such as the
preparation of specific triacylglycerols, or on a tonne
scale for commercial manufacture of acids, methyl
esters, other esters such as olestra and
monoacylglycerols.
• The range of reactions is wide and includes hydrolysis,
alcoholysis (especially methanolysis and glycerolysis),
acidolysis, esterification, interesterification, and
synthesis of structured triacylglycerols.
• The starting point for these reactions may be acids or
esters including natural mixed triacylglycerols.
 Fat Splitting- Fatty Acids and Glycerol
• Fat splitting is essentially a homogeneous reaction that
proceeds in stages. The fatty acid radicals are displaced
from the triglyceride one at a time from tri to di to mono.
• The reaction can be catalyzed by acid, base, or lipase, but
it also occurs as an uncatalyzed reaction between fats and
water dissolved in the fat phase at suitable temperatures
and pressures.

18
• Fat splitting is a reversible reaction. At the point of
equilibrium, the rates of hydrolysis and re-
esterification are equal. The glycerine byproduct must
be withdrawn continuously to force the reaction to
completion.
• An increase in temperature from 1500C to 2200C
increases water solubility by two to three times.
• The industrial production of fatty acids uses the direct
reaction between water and fats, which proceeds
rapidly at 2500C and 2–6 MPa (20–60 bar).
• Under these conditions, water is moderately soluble in
the oil phase, and stepwise hydrolysis of the
triacylglycerols proceeds without the aid of a catalyst.
• The reaction is carried out with a countercurrent
contact of water that removes the glycerol formed,
resulting in 99% conversion to fatty acids. Glycerol is
recovered from the aqueous phase.
19
 Acid Value
❖free fatty acid present in a fat
❖ Number of mg of KOH required to neutralize
the free acid present in 1g of fat or oil.
❖ It can be expressed as the % of oleic acid.
SAPONIFICATION
21
 Saponification Value (SV)
❖It is the number of mg of potassium hydroxide
required to saponify 1 gm of fat or oil sample and
indicates the average chain length of FAs
❖Saponification - hydrolysis of ester under alkaline
condition.
 Saponification -Toilet and Washing Soaps
• Soap is one example of a broader class of materials known as surface-
active agents, or surfactants.
• The hydrophilic portion of a soap molecule is the carboxylate head group
and the hydrophobic portion is the aliphatic chain. This class of materials is
simultaneously soluble in both aqueous and organic phases or preferential
aggregate at air–water interfaces.
• It is this special chemical structure that leads to the ability of surfactants
to clean dirt and oil from surfaces and produce lather.
• Carboxylate soaps are most commonly formed through either direct or
indirect reaction of aqueous caustic soda, i.e., alkali metal hydroxides such
as NaOH, with fats and oils from natural sources, i.e., triglycerides. Overall,
the reaction of caustic with triglyceride yields glycerol and soap in a
reaction known as saponification.
 Saponification Reaction
• Although saponification may occur in successive
stages, there is no detectable accumulation of
mono- or diglycerides in the reaction mass at any
stage of the process.
• The reaction is markedly autocatalytic.
• If the amount of fat saponified is plotted against
reaction time ,a sigmoid curve results; the reaction,
at first slow, accelerates rapidly as increased
quantities of soap are formed, and slows again only
toward the end as the concentration of fat
becomes low and considerable proportions of fat
tend to become occluded among alkali-
impoverished soap micelles.
• Since free fatty acids react more readily with alkali than do
glycerides, a fat charge containing some proportion of free
fatty acids is saponified more rapidly than one that is
substantially neutral.
• Fats of a relatively low degree of unsaturation saponify
more readily than more highly unsaturated fats, but there
appears to be no relation between saponification rate and
molecular weight of the acids.
• In technical practice, soap is often boiled on a niger of
preformed soap left from a previous boil. Fresh fat and
alkali slowly added to the boiling soap mass saponify very
rapidly. Considerable heat (about 65 cal/kg of fat
saponified) is evolved in the reaction and the addition of fat
and lye must be carefully controlled to avoid boiling the
batch out of the kettle.
INTERESTERIFICATION/
TRANSESTERIFICATION
 Interesterification
• The term ‘‘interesterification’’ is often used to
describe reactions that involve the exchange of acyl
residues
✓ between an ester and an acid (acidolysis),
✓ an ester and an alcohol (alcoholysis),

or
✓ between an ester with another ester (trans-
esterification).
 Routes for the preparation of Fatty Estersa

Exchange reactions at the carboxyl group (1) hydrolysis, (2) esterification, (3)
acidolysis, (4) alcoholysis, and (5) glycerolysis. The starting ester RCOOR' will often be
a triacylglycerol. MAG—monoacylglycerol; DAG—diacylglycerol; TAG—triacylglycerol.
 Fatty Acid Methyl Ester and Glycerol
Fat Splitting and esterification
• Hydrolyze the fat, Separate the glycerol, distill the fatty
acids and esterify the fatty acid using acid catalysts.
Hydrolysis route involves use of high temperature and
pressure while esterification may be performed under
vacuum, reflux at atmospheric pressure or supercritical
conditions
Transesterification
• Transesterify the fat with suitable alcohol in
homogeneously alkaline catalyzed media accompanied
with recovery of glycerol.
• Transesterify the fat with suitable alcohol in
homogeneously acid catalyzed media accompanied with
recovery of glycerol.
• Heterogeneously catalyzed transesterification
• Enzyme catalysed Fat Splitting and Transesterification 30
Methanolysis reaction with acidic and basic catalysts
31
 Feedstock Pretreatment for base catalysed methanolysis

• The fat needs to be de-gummed to remove both gums and other

extraneous matter.
• If the colour of the fat is poor, it is then treated with an acid
activated earth and filtered.
• Free fatty acid in the oil must be reduced to less than 0.4 acid value
as the presence of the fatty acids will react with and impair the
performance of the catalyst.
• The free fatty acid reduction can be achieved by alkali refining
using a caustic wash or steam distillation under vacuum.
• Alternative method : pre-esterification of the ffa with methanol
using H2SO4 or PTSA as catalyst thus transforming the ffa into
methyl esters prior to the transesterification process.
• Methanol for esterification of fatty acids needs not to be
completely anhydrous, as for the transesterification process, and a
simple rectification may be carried out independently from the
recirculation system in the transesterification unit.
32
 Quantitative correlations
CH2OCOR’ CH2OH R'COOCH3
| 3 CH3OH Catalyst | +
CHOCOR” CHOH R''COOCH3
| | +
CH2OCOR”’ CH2OH R'''COOCH3
60 Kg 6.78 Kg 0.60Kg 6.5 Kg 58 Kg
Oil Alcohol NaOH Glycerine FAME

•In order to obtain maximum conversion into methyl esters, the following conditions
has to be maintained: the fat and oil must be degummed and deacidified to reduce
the acid value below 0.4 and should be substantially anhydrous; moisture content <
0.065%. Methanol must be anhydrous (max 0.3 water).
•The catalyst of choice is sodium methylate. Sodium methylate powder should
however immediately be dissolved in methanol as a stock solution, otherwise it very
quickly absorbs water and even CO2 from the air, thereby reducing its efficiency as a
catalyst. 33
 The Base catalysed Methanolysis Process
• Commonly the base is dissolved in the alcohol to make a
convenient method of dispersing the otherwise solid catalyst into
the oil.
• The fats and oils (filtered through 53 micron sieve), sodium
methylate stock solution in methanol, and methanol are
introduced by automatic batching, into the reactor. The reaction
mixture is kept boiling under reflux at about 70o C for about two
hours when conversion of triglyceride into methyl ester reaches to
95 –97 %.
• Two alternatives exist to separate the glycerine layer set free after
completion of the interchange reaction.
• Lipase catalyzed methanolysis is less sensitive to fatty acid and
water in the oil and has been tested in batch and fixed-bed reactor
conversion of waste oil and grease to biodiesel.
• Esters based on other primary alcohols such as ethanol, propanol
or butanol are made by reactions of glycerol esters with the
appropriate potassium alkoxide (ROK).
34
 Advantages of Methyl Esters as basic
oleochemical over fatty acids
1. Lower energy consumption
2. Less expensive equipment for production.
3. More concentrated glycerine byproduct.
4. Easier to distill–fractionate.
5. Superior to fatty acids as chemical intermediates in
some applications e.g. alkanolamides.
6. Easier to transport.

35