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Epoxidation of Vegetable Oils, Unsaturated Fatty Acids and Fatty Acid Esters: A
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DOI: 10.2174/1570193X16666190430154319

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Kornelia Malarczyk-Matusiak Łukasz Sałaciński

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Mini-Reviews in Organic Chemistry, 2019, 16, 1-11 1

REVIEW ARTICLE

Epoxidation of Vegetable Oils, Unsaturated Fatty Acids and Fatty Acid

Esters: A Review

Grzegorz Lewandowski*, Marlena Musik, Kornelia Malarczyk-Matusiak, Łukasz Sałaciński and

Eugeniusz Milchert

West Pomeranian University of Technology, Szczecin, Faculty of Chemical Technology and Engineering, Institute of
Organic Chemical Technology, Piastów Ave. 42, PL 71-065 Szczecin, Poland

Abstract: A comprehensive review of recent existing methods of epoxidation of vegetable oils, un-
saturated fatty acids and alkyl esters of unsaturated fatty acids has been presented. The importance of
ARTICLE HISTORY epoxidized vegetable oils and their applications in the production of polyols and polyurethanes was
discussed. Interests of researchers have been mainly focused on the development of advantageous
Received: January 04, 2019
Revised: March 20, 2019
technological parameters of vegetable oils epoxidation. The epoxidations with peracetic acid or per-
Accepted: April 08, 2019 formic acid generated in situ were mainly performed in the presence of strongly acidic catalysts. The
DOI: influence of process variables such as temperature, stirring speed, the molar ratio of carboxylic acid
10.2174/1570193X16666190430154319 and hydrogen peroxide to the amount of ethylenic unsaturation, amount of catalyst and reaction time
on the course of epoxidation has been investigated.

Keywords: Epoxidation, technological parameters, unsaturated fatty acids alkyl esters, unsaturated fatty acids, vegetable oils,

1. INTRODUCTION is, in fact, greater than the rate of peracid formation what
enhances the safety of the process.
Epoxidized vegetable oils are of great importance as
readily biodegradable, renewable intermediates of the chem- However, there are well-known methods in which the
ical industry and the commercial products [1]. They are used peracetic acid or performic acid is obtained separately as
as plasticizers and stabilizers of polyvinyl chloride and its well as perbenzoic, m-chloroperbenzoic, monoperphthalic
copolymers as well as biodegradable lubricants. Many works and pertrifluoroacetic acid.
have been devoted to their hydration to glycols and pro- The most common oils used for the epoxidation include:
cessing into more reactive polyols, which are subsequently soybean, rapeseed oil with various erucic acid content (cano-
utilized in the production of polyurethanes and surfactants. la), linseed, corn, sunflower, palm, castor and cotton seeds.
The hydrolysis was carried out in the presence of acetic, The epoxidation of inedible vegetable oils such as mahua,
formic, sulfuric(VI), phosphoric(V) and hydrochloric acids Karanja, jatropha, unsaturated fatty acids and their alkyl es-
as catalysts. Similar importance has the aminolysis with eth- ters also has a commercial importance.
ylenediamine which allows to obtain polyols with the sec-
ondary hydroxyl and amine groups [2, 4]. 2. THE IMPORTANCE OF VEGETABLE OILS EPOX-
The epoxidation of oils based on the use of peracids has IDATION
an industrial importance. Industrially carried out epoxida-
Epoxidized oils are intermediates in the production of
tions of oils are based on the reaction of peracetic acid or
polyols, both as products of direct hydration of the oxirane
performic acid, generated in situ during the mixing of hydro-
rings and as oligomers (oligoethers, oligoesters), formed as a
gen peroxide with a carboxylic acid in the presence of acidic
result of further transformations. The most common trans-
catalysts (acid ion-exchange resin, H2SO4, H3PO4, HNO3,
formations are based on the ethoxylation or propoxylation of
HCl, alkane sulfonic acids). In the in situ methods, the perac-
the hydration products of epoxidized oils (glycols and poly-
ids are consumed immediately after their formation. The
glycols). As a result, the primary hydroxyl groups are intro-
peracids have limited durability and at higher concentrations, duced, which are more active in the reaction with isocya-
they can pose fire or explosion hazard. The rate of epoxidation nates than the secondary groups. Moreover, the number of -
OH groups is increased and the polyol structure is changed.
*Address correspondence to this author at the West Pomeranian University Alternatively, the -OH groups of the primary polyglycols are
of Technology, Szczecin, Faculty of Chemical Technology and Engineering, esterified with an anhydride or phthalic acid or adipic acid.
Institute of Organic Chemical Technology, Piastów Ave. 42, PL 71-065
Szczecin, Poland; Tel: +4891 4494891; Fax: +4891 449 4365; In general, the opening of oxirane groups in the epox-
E-mail: grzegorz.lewandowski@zut.edu.pl idized oils involves the reaction with low molecular weight
1570-193X/19 $58.00+.00 © 2019 Bentham Science Publishers
2 Mini-Reviews in Organic Chemistry, 2019, Vol. 16, No. 00 Lewandowski et al.

alcohols (methanol, ethanol), and multifunctional alcohols O

such as ethylene glycol, glycerol, erythritol, glucose, sucrose CH 2OC (CH 2)16 CH3
and xylitol. In addition, the compouds such as amines (di- O
ethylamine), aminoalcohols (di-, triethanolamine), carbox- CHOC (CH 2) 7CH CH(CH 2) 7CH3
ylic acids: acetic, adipic, phthalic and mixtures of fatty acids O
are used. The oxirane ring opening also involves a reaction CH 2OC (CH 2) 7CH CH(CH 2)CH CH(CH 2) 4CH3
with water, hydrogen chloride or bromide, hydrogenation
and polymerization. + H 2O 2, 30-70%
+ RCOOH
The methoxylation of the oxirane groups in vegetable
oils also results in the formation of polyols used in the pro- + cat.
duction of polyurethanes. In this process, the fluoroboric
acid acts as a catalyst [5-8]. The polyols of low molecular CH 2OC (CH 2)16 CH3
weight alcohols have an average molecular weight of 1000 O
g/mol and the hydroxyl number of about 200 mg/g. Howev- CHOC (CH 2) 7CH CH(CH 2) 7CH3
er, the polyurethanes prepared from these polyols have a O O
relatively low glass transition temperature - Tg ≅ 30°C, re- CH 2OC (CH 2) 7CH CH(CH 2)CH CH(CH 2) 4CH3
sulting in considerable brittleness and hardness. Such proper- O O O
ties eliminate these polymers from many applications [9]. Scheme 1. Epoxidation of stearic, oleic and linoleic trigliceryde
However, the obtained polyurethanes exhibit enhanced ther- with percarboxylic acid.
mal and antioxidant resistance compared to the petrochemi-
cal polyols formed during the oligomerization of propylene 3. EPOXIDATION METHODS OF VEGETABLE OILS,
oxide [10]. UNSATURATED FATTY ACIDS AND THEIR ALKYL
A significant increase in the hydroxyl number of polyols ESTERS
used in the production of polyurethanes was obtained by Among various methods used for epoxidation of vegeta-
opening the oxirane ring with lactic acid (2-hydroxypropane ble oils, unsaturated fatty acids and their alkyl esters, the
acid) [11]. The glass transition temperature of the resulting following can be distinguished:
polyurethanes can reach the value Tg ≅ 96°C. This enables to
replace the petrochemical polyols obtained based on propyl- - epoxidation of previously prepared or generated in
ene oxide. The polyurethanes above the glass transition tem- situ carboxylic peracids,
perature behave like highly elastic materials, since the poly- - reactions with the use of organic hydroperoxides or
mer chain segments have the ability to perform the rotational hydrogen peroxide, in the presence of high valence
movements. The aforementioned feature, results from the metal compounds, in particular, Mo, Ti, W, V as cata-
increased molecular weight of the polyols part of polyure- lysts,
thane and the structure of polyols (content of primary hy-
droxyl groups). The increase in the amount of primary hy- - chemoenzymatic epoxidation with hydrogen peroxide
droxyl groups was achieved by the ethoxylation of the -OH in the presence of the Candida antarctica lipase B
groups in glycols and polyols. Most often, previously epox- enzyme, immobilized onto an acrylic resin (Novo-
idized soybean oil was subjected to methoxylation [12]. A zym®435) or onto silica and other lipases as catalysts.
significant increase in the amount of primary hydroxyl
groups and the molecular weights of polyols was also 3.1. Epoxidation with Carboxylic Peracids
achieved by ethoxylation of the secondary -OH groups in the Peracetic acid or performic acid and strong acidic ion ex-
hydrolysis products of epoxidized oils. change resins or strong mineral acids are predominately used
Hydrogenation of the oxirane groups in epoxidized oils as the catalysts for the epoxidation ofthe aforementioned
results in the formation of hydroxyl groups bound to a sec- group of compounds. Generally, the mechanism of vegetable
ondary carbon. This direction is less interesting due to lower oils epoxidation involves several stages. In the conventional
reactivity of -OH group in the reactions with diisocyanates process, the peracetic acid or performic acid were initially
[8, 13, 14]. generated from the corresponding acid and hydrogen perox-
ide in the presence of H2SO4 or another strong mineral acid.
Ethoxylates of diols of such oils as: rapeseed, peanut and The peracid formed was gradually introduced into the epox-
olive were applied for the foaming regulation in the follow-
idized oil. In a novel solution, hydrogen peroxide is gradual-
ing processes: alcoholic fermentation, production of starch,
ly introduced to epoxidized oil, acetic acid or formic acid
sugar, baker's yeast, and cellulose and paper coating [15].
and ion exchange resin as catalyst (in situ method). Strongly
Epoxidized oils due to their biodegradability are also uti- acidic ion exchange resins of the type of sulfonated styrene-
lized as high-temperature lubricants, plasticizers and stabi- divinybenzene copolymers: Amberlite IR 120H, Dowex
lizers for polyvinyl chloride and other polymers, [4, 10]. 50WX2, Amberlyst 15 were used. The technological pa-
The general scheme for epoxidation of stearic, oleic and rameters are established individually for a given type of veg-
linoleic trigliceryde with percarboxylic acid is shown in etable oil, unsaturated fatty acid or its alkyl ester [16-19].
Scheme 1. The parameters of the epoxidation reaction with peracids are
Epoxidation of Vegetable Oils, Unsaturated Fatty Acids and Fatty Acid Esters Mini-Reviews in Organic Chemistry, 2019, Vol. 16, No. 00 3

Table 1. Parameters of vegetable oils epoxidation in the presence of acidic ion exchange resins and H2SO4 as a catalysts.

Acid/C=C H2O2/C=C Stirring Reaction Iodine

Catalyst Temperature Conversion RPC
Oil Name Molar Ratio Molar Ratio Rate o Time Number Literature
wt% C % %
mol/mol mol/mol rpm h g/100g

CH3COOH or 20,
Soybean oil Amberlite IR-120 a 1000 b 80 3.5 80 4.7-6.0 c
HCOOH/C=C 1.5:1 95 21,
INo=135g/100g 25 500-2000 30-80 3.5-14 80-94 2-12
0.5:1 22

CH3COOH or
Amberlite IR-120
Canola oil HCOOH/C=C 1.5:1 65
22 Continuous 7 88 90 10.2 23
INo=112g/100g 0.5:1 0.5-2.0:1 40-75
6-22
0.3-1.0:1

Amberlite IR-120 a CH COOH/C=C

Castor oil 3 18,
15 1.5:1 1500 d 50 8 78 - -
INo=81.5g/100g 0.5:1 24
5-15

Amberlite IR-120 CH3COOH/C=C

Cotton seed oil 1.5:1 1800 70-80
15 0.5:1 6 65 65 20.0 18
INo=105g/100g 1.1-2.5:1 600-2400 30-90
10-25 0.25-0.75

CH3COOH/C=C
Mahua oil Amberlite IR-120 1.1:1 2500 70
0.5:1 3.5 32 85 2.7 25
INo=88g/100g 16 0.8-2.5:1 500-2500 30-70
0.3-1.0:1

CH3COOH/C=C
Karanja oil Amberlite IR-120 1.5:1 1500 70
0.5:1 3.5 - 85 - 26
INo=89g/100g 16 0.8-2.5:1 500-2500 30-85
0.3-1.0:1

CH3COOH or
Jatropha oil Amberlite IR-120 2500 70
HCOOH/C=C 1.5:1 10 73 - 19-35 27
INo=105g/100g 16 500-2500 30-70
0.5:1

Catalyst CH3COOH/C=C
Soybean oil 28,
H2SO4 0.4:1 0.7-1.1:1 Continuous 30-80 0.5-13 80 ≅6 8.5
INo=125g/100g 29
0.5-5.0 e 0.25-1.0:1

Soybean oil mineral acids, CH3COOH/C=C 30,

1.0-1.1:1 Intensive 55-60 6 - - 1.1-58.0
INo=129g/100g 0.5-5.0 e 0.25-1.0:1 31
a
- in relation to the sum (CH3COOH+30 wt% H2O2), in other cases with respect to oil, b - toluene 44 wt% relative to oil, c - with complexing agent for heavy metals
(diethylenetriaminopentaacetic acid), d - benzene 1:1 by weight of oil, e - relative to the sum (CH3COOH+50 wt% H2O2), RPC- relative percentage conversion to oxirane, RPC =
EOe/EOt·100%, EOe - experimentally determined content of oxirane oxygen in 100 g of oil, EOt - theoretical maximum oxirane oxygen in 100 g of oil, IN - iodine number, - tested
range of parameter changes was written in italics.

summarized in Table 1. Both methods are used on an indus- Ti/SiO2 [37] or on the mesoporous materials [38-41]. These
trial scale. epoxidation methods did not find industrial implementation.

3.2. Epoxidation in the Presence of High Valency Metal The epoxidation of soybean oil, methyl esters of unsatu-
Compounds rated fatty acids with organic hydroperoxides: tert-butyl hy-
drogen peroxide (TBHP), cumene hydroperoxide, in the
Special attention should be paid to the epoxidation meth- presence of transition metal ions: Mo, W, V, Cr was carried
ods of the following vegetable oils: castor oil, soybean oil, out on a laboratory scale [41]. Higher selectivities were ob-
sunflower oil, coriander oil and their fatty acid methyl esters tained during the epoxidation of oleic acid with TBHP in the
with H2O2 or tert-butyl hydroperoxide (TBHP) as oxidant in presence of a molybdenum complex: [Mo(O)2(SAP)(EtOH)],
the presence of titanium-silicate catalysts: TS-1, Ti-beta, Ti- SAP - supported aqueous-phase, Et - ethyl group [42].
MCM-41, Ti-MCM-48, Ti-MWW [32-36]. In this group of
catalysts, Si(IV) atoms in the silica structure are partially On a small scale, the epoxidation of castor oil and ricino-
replaced with Ti(IV) atoms. The large molecules of glycer- leic acid derivatives was carried out using the phase transfer
ides do not reach the active sites of tetrahedral titanium Ti+4, catalysts (PTC) and H2O2 as an oxidant. Peroxophospho-
located inside the channels of the catalyst. As a result, the tungstate complexes as the epoxidation catalysts were used:
conversion of ethylenic unsaturation and selectivity to H+/WO4-2/PO4-3/Q+X-, QX - onium salt or crown ether [43,
oxirane oxygen was decreased. Similar results were obtained 44]. The separation and reuse of the catalyst are the main
over the titanium catalysts supported on amorphous silica - problems.
4 Mini-Reviews in Organic Chemistry, 2019, Vol. 16, No. 00 Lewandowski et al.

Peroxophosphotungstate immobilized on polymeric sup- O

port as a heterogeneous catalyst was used for the epoxidation R1 C OOH
of unsaturated fatty esters [45]. This solved the problem of
separation and reuse of the heterogeneous catalyst. In the H 2C OCO R1 H 2C OH
most recent solutions, the anion {PO4[WO(O2)2]4}-3 was H 2O 2
supported on the Amberlite IRA-900 and other ion exchange HC OCO R2 HC OCO R2 1
lipase
resins [46, 47].
H 2C OCO R3 H 2C OH
Another method of epoxidation is the reaction of soybean
oil and their methyl esters with hydrogen peroxide in the O
biphasic system CH3ReO3/CH2Cl2/H2O2. The selectivity was R1, R 2, R 3 - fatty acid alkyl R 3C OOH
95% as the total conversion of ethylenic unsaturation was
achieved after 2 h of reaction at room temperature [48]. Me- O O
H 2O 2
thyl linoleate was completely epoxidized by aqueous H2O2 R1 C OR R1 C OOH ROH 2
lipase
within 4 h, in the presence of methyltrioxorhenium -
CH3ReO3 [49]. R - C1-C5 alkyl

The epoxidation of oleic acid with oxygen in the pres- Scheme 2. Perhydrolysis of triglycerols (1) and alkyl esters of fatty
acids (2).
ence of benzaldehyde and cobalt acetate as a homogenous
catalyst proceeded with the conversion of 75% and the selec-
tivity of 88% [50]. The same epoxidation performed with preferably in the form of triglyceride or the mixture of acids.
heterogenized homogeneous Co-type ion-exchange mem- In order to obtain a high conversion of ethylenic unsaturation
brane as a catalyst exhibits a conversion of oleic acid equal within a short period, an excess of hydrogen peroxide com-
to 70% and the selectivity 86% [51]. pared to the amount of double bonds was necessary. At the
same time, the decomposition of hydrogen peroxide is lim-
The alumina produced by sol-gel process possesses a ited by using a temperature below 60°C and the initial con-
good catalytic activity in the epoxidation of unsaturated fatty centration of 30 wt% or lower. Due to inactivation of lipase,
esters (methyl oleate and soybean oil methyl esters) using the H2O2 concentration in the reaction medium usually does
H2O2 as oxidant and ethyl acetate as a solvent [52]. A con- not exceed 1 wt%. The main advantages of chemoenzymatic
version of 95% with selectivity to the epoxide greater than epoxidation are as follows: mild reaction conditions, possi-
97% was obtained after 24 h. bility of operation the process without a solvent, neutral or
Diastereoselective epoxidation of methyl ricinoleate to slightly acidic pH, the use of immobilized lipase as a bio-
(Z)-9,10-epoxy-12-hydroxyoctadecanoate was carried out catalyst, high stereo- and chemoselectivity (small contribu-
using ethylmethyldioxirane [53]. Simultaneously high yields tion of side reactions), high conversion of ethylenic unsatura-
and low enantiometric excess were obtained. The same oxi- tion, high production safety and environmental protection.
dant and PTC method was used for the epoxidation of many Characteristic examples of chemoenzymatic epoxidation of
vegetable oils are presented in Table 2.
mono- and polyunsaturated oils [54]. The best conversion for
polyunsaturated oils was achieved with a molar ratio of In the chemoenzymatic epoxidation of vegetable oils and
ethylmethyldioxirane/oil = 2.5:1 when a two-stage addition their derivatives, the most important for the activity of en-
of the oxidant was used. zyme is the concentration of hydrogen peroxide and tem-
peratures. Controlled addition of hydrogen peroxide is ap-
3.3. Chemoenzymatic Epoxidation plied for enzyme stability, especially at the initial period,
The enzymatic approach for the synthesis is an energy ef- until the formation of water is sufficient to dilute the added
ficient alternative to the chemical process and is much sim- H2O2. The use of a temperature-programmed technique is
pler. At chemoenzymatic epoxidation, the highest selectivity also advantageous [64]. The reaction schemes epoxyglycer-
of transformation to oxirane oxygen in epoxidized vegetable ols leading to the compounds used in polyurethane synthesis
oils was achieved in the presence of Candida antarctica li- are presented in Scheme 3.
pase B, immobilized onto an acrylic resin (Novozym® 435),
or lipase B immobilized onto silica (CALB-silica) and an- 4. INDUSTRIAL METHODS OF VEGETABLE OILS
other lipases as a catalyst [55-57]. Triglycerols and alkyl EPOXIDATION
esters of fatty acids in the presence of enzyme lipase and In the industrial processes, the epoxidizing agent is per-
hydrogen peroxide undergo perhydrolysis with the formation acid, which is generated in situ in the epoxidation reactor by
of the corresponding percarboxylic fatty acids, Scheme 2. reacting acetic acid or formic acid with hydrogen peroxide at
Free fatty acids react in a similar way. The chemoen- a concentration of 30 to 70 wt% or prepared separately. A
zymatic epoxidation exhibits the highest selectivity among resin-type of a sulfonated copolymer of styrene and divi-
the aforementioned methods, moreover, it is also highly ste- nylbenzene (Amberlite IR-120H, Amberlyst 15, Dowex
reoselective. In the epoxidation of vegetable oils, the highest 50WX5) or sulfuric acid are used as the catalyst of peracid
conversion of ethylenic unsaturation and the reaction rate synthesis. In a variant with resin occurs a less intensive in-
were achieved by adding only a small amount of free fatty teraction of the organic phase containing the epoxidized oil
acid (up to 5 wt% relative to the number of C=C bonds), with an aqueous phase containing carboxylic acid and H2O2.
Epoxidation of Vegetable Oils, Unsaturated Fatty Acids and Fatty Acid Esters Mini-Reviews in Organic Chemistry, 2019, Vol. 16, No. 00 5

Table 2. Technological parameters chemoenzymatic epoxidation of vegetable oils, free fatty acids and their alkyl esters

H2O2/C=C Stirring Reaction

Amount of Free Fatty Temperature Catalyst Conversion
Oil Name Molar Ratio Solvent Rate Time Literature
Acid (FFA) °C wt% %
mol/mol rpm h

Lipase B/ acrylic
Soybean oil (SO) Oleic acid 8 wt%/SO 2:1 50 Toluene − 4 95-99 58
resin

Soybean oil methyl FFA/SME = 0.001:1

1.4 g H2O2/1g 3 wt% Lipase B/ 5:1 g/g tolu-
esters (SME) mol/g stearic, behenic 55 800 10-12 98 59
SME acrylic resin ene/esters
IN=133.0 g/100g oil acid

Lipase B
Sunflower oil methyl Octanoic acid/esters = CH2Cl2 or
− 30 10 times was − 16 99 60
esters 10 mmol/g CH2Cl2-H2O
reused

Oleic acid or ethyl 0.2 wt% H2O2 10 wt% Amano

a 55 Ethyl acetate 150 3 88 61
oleate lipase c

Safindus mukorossi
2 wt% Lipase B/
seed oil Stearic acid 4:1 50 − − 7 90.2 62
oil
IN=84.8 g/100g oil

FFA are formed by 3 wt% Lipase

Rapeseed methyl esters 15 M H2O2 b 40 − 450 14 83 63
partial ester hydrolysis B/RME
a
- concentration in solution, b - concentration in water phase, c - by weight of oleic acid, IN - iodine number, FFA - free fatty acids, SME - soybean oil methyl ester, RME - rapeseed
methyl esters.

O O OH OH
O CH 2OC (CH 2) 7CH CH(CH 2) 7CH3 + H 2O CH 2OC (CH 2) 7CH CH(CH 2) 7CH3
R1 COHC O
O
HBF 4 O OH OCH3
CH 2OC R 2
+ CH3OH CH 2OC (CH 2) 7CH CH(CH 2) 7CH3

O OH NHR
+ RNH 2 CH 2OC (CH 2) 7CH CH(CH 2) 7CH3

O OH
CH 2OC (CH 2) 7CH CH(CH 2) 7CH3
NR
CH 2OC (CH 2) 7CH CH(CH 2) 7CH3
O OH
O OCOR
+ RCOOH CH 2OC (CH 2) 7CH CH(CH 2) 7CH3
OH
H 2O O OCOR
+ (RCO) 2O CH 2OC (CH 2) 7CH CH(CH 2) 7CH3
OCOR
O OH N(CH 2CH 2OH) 2
+ HN(CH 2CH 2OH) 2 CH 2OC (CH 2) 7CH CH(CH 2) 7CH3

O OH OCH 2CH 2OH

+ CH 2OHCH 2OH CH 2OC (CH 2) 7CH CH(CH 2) 7CH3

Scheme 3. The reaction schemes epoxyglycerols leading to the compounds used in polyurethane synthesis.

The heterogeneity of catalyst decreases the rate of side reac- rosion of the apparatus are noteworthy. The industrial epoxi-
tions of the oxirane ring opening. dations of vegetable oils are carried out in periodic reactors.
The selectivity to the oxirane oxygen in relation to the re- On a laboratory scale, the influence of technological pa-
acted ethylenic unsaturation is increased. The other ad- rameters: stirring speed (400-2500 rpm), temperature (30-
vantages of the heterogeneous catalyst such as the ease of 90°C), molar ratio of hydrogen peroxide to unsaturated
separation, regeneration and recirculation, and reduced cor- bonds (H2O2/C=C = 1.0-2.0:1), molar ratio of carboxylic
6 Mini-Reviews in Organic Chemistry, 2019, Vol. 16, No. 00 Lewandowski et al.

O
H+
RCOOH H 2O 2 R C H 2O
1
O –OH

O R1 H R1 O H
R C RCOOH 2
O –OH H (CH 2)nOCOR 2 H (CH 2)nOCOR 2

OH OH OH OCOR O R1 (CH 2)nOCOR 2

R1 CH–CH(CH 2)nOCOR 2 R1 CH–CH(CH 2)nOCOR 2 R1 C –CH 2(CH 2)nOCOR 2 [ CH–CHO ]x 3

Scheme 4. The main reactions (1, 2) and by-products (3) of oxirane ring transformation: glycols, hydroxyesters, carbonyl compounds, and
polyethers.
R, R1, R2 - alkyl groups

acid (HCOOH or CH3COOH) to unsaturated bonds The technological parameters influence the content of ethyl-
(RCOOH/C=C = 0.2-0.75:1), the amount of catalyst relative enic unsaturation in the epoxidized oil. Moreover, the tech-
to the epoxidizing agent or relative to the oil −H2SO4/ nological parameters that ensure the highest selectivity are
(CH3COOH + H2O2) = 0.1-5.0 wt%, (5-25 wt% for acidic not always identical with the parameters at which the highest
ion exchange resins) have been studied. conversion of ethylenic unsaturation or process yield is
achieved. Therefore, it is often necessary to choose between
The course of changes in the concentration of oxirane
the parameters determining the highest conversion or selec-
oxygen reveals that the fastest epoxidation that occurs at the
tivity. However, knowledge about the course of the function:
initial stage process, within 30-40 min after the introduction
of hydrogen peroxide. When the highest selectivity to the selectivity, conversion and yield is required. The achievable
oxirane oxygen was achieved, the rate of opening of the yield of the synthesis of epoxidized oil does not always con-
stitute a process variable that determines the choice of tech-
oxirane groups is significantly increased. Among the unde-
nological parameters. The intermediate parameters can be
sired side, reactions prevail the hydration to glycols. Moreo-
also used. In the current studies, the optimal technological
ver, the oxirane groups react with a carboxylic acid to form
parameters of epoxidation of particular oil were presented
monohydroxyesters at a lesser extent. Simultaneously, the
and their influence on the course of the process was dis-
isomerization of the oxirane groups to carbonyl groups and
cussed.
polymerization of oxirane and ethylenic unsaturation may
proceed − Scheme 4. The obtained technological parameters are affected, to a
significant degree, by the content of unsaturated acids: oleic,
The opening of the oxirane rings by hydrogen peroxide
and a peracid is also possible. The amount of side reaction linoleic, linolenic, α-eleostearic (C18:3 in the conjugated
products during the epoxidation of vegetable oils can be lim- system of bonds: 9c, 11t, 13c), in the molecule of glycerides.
ited by optimization of the process parameters. The process The obtained technological parameters are affected, to a
variables, which characterize the course of the reaction and significant degree, by the content of unsaturated acids: oleic,
are used to develop the optimal parameters, are as follows: linoleic, linolenic, α-eleostearic (C18:3 in the conjugated
conversion of ethylenic unsaturation, relative percentage system of bonds: 9c, 11t, 13c), in the molecule of glycerides.
conversion to oxirane - RPC, iodine number, the selectivity The oils, which do not undergo the epoxidation using the
of transformation to oxirane oxygen, and other magnitudes peracid method because they readily undergo polymeriza-
presented below. The optimization of the technological pa- tion, are also known (tung oil with ≅ 80 wt% of α-eleostearic
rameters of the following oils: soybean [65, 66], rapeseed acid, polyunsaturated fish oils).
[67], canola [68, 69], castor [70], mahua [25, 71], jatropha
In many studies, the measure of the selectivity of trans-
[27], karanja [72, 73] has been performed.
formation to oxirane oxygen (S) was the molar ratio of the
determined amount of oxirane oxygen to the number of re-
5. METHODS FOR THE EVALUATION OF EFFECT
acted ethylenic unsaturation:
OF TECHNOLOGICAL PARAMETERS
In order to determine the influence of technological pa- ⎛ EOe IN 0 ⎞
S=⎜ ⋅ ⋅100% (1)
rameters on the course of the epoxidation process and to de- ⎝ EOt IN 0 − IN ⎟⎠
velop the optimal parameters, the method of one variable or
mathematical methods of experiential planning were applied. where: EOe (wt%) - is the experimentally determined content
The most important objective of the optimization is to devel- of oxirane oxygen in 100 g of oil:
op the technological parameters allowing the preparation of EOe = EN ⋅ AO (2)
epoxidized oil with the highest oxygen oxirane content and
with the highest selectivity of transformation. Such obtained where: EN - is the epoxy number of oil after epoxidation
oils are particularly valued due to numerous applications. (mol/100 g), A0 = 16.0 is the atomic weight of oxygen
Epoxidation of Vegetable Oils, Unsaturated Fatty Acids and Fatty Acid Esters Mini-Reviews in Organic Chemistry, 2019, Vol. 16, No. 00 7

(g/mol), IN0 - is the iodine number of oil before epoxidation A further increase in the molar ratio does not increase the
(g/100g), IN - is the iodine number of oil at a given moment oxirane oxygen [27, 73] and even cause lowering [71, 77].
of epoxidation (g/100g), EOt (wt%) - is the theoretical max-
The amount of by-product formed due to the opening of
imum oxirane oxygen in 100 g of oil calculated as follows:
the oxirane rings can be most effectively decreased by the
⎧⎪⎛ IN ⎞ ⎡ ⎛ IN 0 ⎞ ⎤ ⎫⎪ application of low molar ratios of carboxylic acid to the
EOt = ⎨⎜ 0 ⎟ ⎢100 + ⎜ ⎟ ⋅ AO ⎥ ⎬ ⋅ AO ⋅100 (3) amount of ethylenic unsaturation, i.e. RCOOH/C=C < 1.0:1.
⎩⎪⎝ 2AI ⎠ ⎣ ⎝ 2AI ⎠ ⎦ ⎭⎪ In the case of epoxidation of soybean oil, it was advanta-
geous to use the molar ratio of HCOOH or CH3COOH/C=C
where AI = 126.9 is the atomic weight of iodine (g/mol).
= 0.25-0.5:1.
In the description of the course and results of epoxida-
tion, the conversion of ethylenic unsaturation and a relative 7. PROCEDURES USED IN THE INDUSTRIAL PRO-
percentage conversion to oxirane (RPC) was also calculated. CESSES
The relative percentage conversion to oxirane was calculated
from the equation: In a one-stage process of soybean oil epoxidation with 50
wt% hydrogen peroxide and CH3COOH, the aqueous layer
EOe remains about 5-6 wt% of unused active oxygen (H2O2,
RPC = ⋅100% (4) peracetic acid, traces of acetyl peroxide), CH3COOH 25-30
EO t
wt%, and sulfuric acid (VI) 1-2 wt%. The total utilization of
In other works [1, 67], the conversion (C) was calculated peroxide oxygen can be achieved in a two-stage process
from the ratio of the amount of reacted ethylenic unsatura- [28]. The remaining active oxygen is then consumed in the
tion to the amount of ethylenic unsaturation in the oil before first stage for the epoxidation of fresh oil whereas the prod-
epoxidation: uct of partial epoxidation is subjected to the reaction in the
second stage. Hence, the major amount of hydrogen peroxide
IN 0 − IN is introduced into a product of partial epoxidation. The addi-
C= ⋅100% (5)
IN 0 tion of new amounts of concentrated peroxide (40-90 wt%)
to the aqueous layer after the second epoxidation is possible.
In this method of calculation, the yield (Y) was the ratio The utilization of such peroxide in the epoxidation of the
of the epoxy number of oil to the iodine number of oil before successive portion of oil is also possible. Such procedure is
the epoxidation. ecologically justified because smaller amounts of wastewater
EN are then discharged. In both procedures, acetic acid is recov-
Y= ⋅100% (6) ered from the stream after the final epoxidation. For this pur-
IN 0
pose, the active oxygen (mainly H2O2) is removed from the
aqueous layer after epoxidation. Owing to this, the safe sepa-
6. TECHNOLOGICAL PARAMETERS OF EPOXIDA- ration of acetic acid by distillation can be performed. The
TION
removal proceeds after the introduction of the ions of iron,
During the epoxidation with peracids, the restoration of copper, cobalt and manganese. The decomposition is carried
initial carboxylic acid proceeds. The acid may react with the out in the presence of Ag, Pt, or MnO2. An aqueous solution
oxirane to form a glycol monoester: -CH(OH)-CH(OCOR). of sodium hydroxide or other alkaline agent neutralizes sul-
The course of such reaction and other side reactions (mainly furic acid or other mineral acid. During distillation, the acetic
hydration of oxirane) is favoured by the presence of mineral acid concentrate is collected under reduced pressure. The
acid, necessary at the stage of peracid generation [26]. The recovered acetic acid condensate is recycled to the process.
hydration reactions significantly reduce the selectivity of A large excess of H2O2 in relation to the ethylenic unsat-
transformation to oxirane oxygen. Therefore, in the epoxida- uration (H2O2/C=C > 1.5:1) is also disadvantageous due to
tion process, it is preferable to use a lower molar ratio of the ecological reasons, because the amount of wastewater is
carboxylic acid to the amount of ethylenic unsaturation that increased. The presented method of regeneration of formic
results from the stoichiometry of the reaction (RCOOH/C=C acid cannot be used in the epoxidation with performic acid
<1). In the epoxidation with peracetic acid generated in situ, since the boiling point of formic acid and water is almost the
the molar ratio of acetic acid to the ethylenic unsaturation same.
was generally equal to CH3COOH/C=C = 0.5:1 [26, 65-71,
73-77]. The H2O2 molar excess in relation to the acetic acid In the original technical solutions, the side reactions of
is (H2O2/CH3COOH > 1.0:1), whereas in relation to the eth- oxirane ring and polymerization of the oil were limited by
ylenic unsaturation is (H2O2/C=C = 1.5:1). When a 50 wt% introducing into the reaction medium an inert solvent such
H2O2 was used, the molar ratio was equal to H2O2/RCOOH = as: benzene, toluene, xylene, hexane or heptane [29, 78]. The
2.0:1. As a result, the rate of formation of peracetic acid in- solvent was used in the amount up to 20 wt% in relation to
creases, along with the rate of epoxidation. The study oil. In the place of the mineral acid, an acidic ion exchange
demonstrates that increasing the H2O2 molar ratio to the resin is used as a catalyst. Here, the influence of the catalyst
amount of ethylenic unsaturation in the range of H2O2/C=C = on the opening of the oxirane ring is significantly smaller
0.5-1.5:1 increases the yield (the amount of oxirane oxygen than in the presence of the most commonly used sulfuric
in relation to the ethylenic unsaturation before epoxidation). acid(VI).
8 Mini-Reviews in Organic Chemistry, 2019, Vol. 16, No. 00 Lewandowski et al.

Scheme 5. Technological scheme of vegetable oil epoxidation.

1 - epoxidation reactor, 2 - filter, 3 - separator and tank of rinsing water, 4 - tank for drying of epoxidised oil, 5 - storage tank of epoxidised
oil, 6 -tank of aqueous layer, 7 - dehydration column, 8 - reflux condenser, 9 - separator, 10 - stripper, 11 -recirculated acetic acid tank, 12 -
reflux condenser, 13 - vacuum pomp

Another option of the process [28] relies on the initial acetate at temperature 59°C and at pressure 67 kPa. Dry ace-
epoxidation of soybean oil using 1/5 of the predicted amount tic acid is collected from the bottom of the column and is
of H2O2 and gradual addition of acetic acid containing the recycled to the epoxidation reactor. A residue of acetic acid
catalyst (H2SO4). Subsequently, the remaining amount of and ethyl acetate are removed from the aqueous layer by
H2O2 is introduced at a time and the process is carried out for stripping method with water vapor.
several hours (13 h).
Higher values of process parameters (conversion, RPC, 8. REGULARITIIES OF EPOXIDATION
selectivity) in comparison to sulfuric acid as a catalyst occur The amount of ion exchange resin was usually deter-
in the presence of strongly acidic ion exchange resins (Am- mined in relation to the epoxidizing agent (RCOOH+H2O2),
berlite IR-120H, Dowex 50WX3, Amberlyst 15) − Table 1. or based on the weight of the oil. A noticeable decrease in
In this case, the amount of wet resin with an exchangeability the yield was observed after the time of 13 h and longer, with
2.5 to 4.5 mval/g should be about 20 wt% in relation to a simultaneous increase of the amount of wet resin above 20
epoxidized oil. wt%. A too small amount of catalyst (less than 10 wt% in
The course of the batch industrial process of vegetable relation to the epoxidizing agent (CH3COOH + 30 wt%
oils epoxidation is shown on a simplified technological H2O2) and too short reaction time (less than 6 h) significantly
scheme - Scheme 5. decrease the yield of epoxidation, due to a lower conversion.
A comparison of the epoxidation with peracetic and perfor-
The reactor was successively charged by oil, the catalyst mic acid in the presence of sulfuric acid as a catalyst allows
of type of sulfonated styrene-divinylbenzene copolymers and to notice a higher efficiency of peracetic acid [79]. A lower
acetic acid. After heating to the reaction temperature (50- acidity of acetic acid in comparison with formic acid (pKa
70°C) a 30% hydrogen peroxide was added in such intensity, CH3COOH = 4.77, pKa HCOOH = 3.77) causes a slower course of
so the temperature will not be exceeded, while the reactor the side reactions of the opening of oxirane rings. The use of
was simultaneously cooled with water. After the reaction formic acid generates more proton than acetic which catalyz-
time from 5 to 8 h, a solution of epoxidized oil in acetic acid es the perhydrolysis reaction. Hence, a high acidity of formic
flows through a filter in order to separate the catalyst. The acid increases the rate of formation of peracids, epoxidation
organic phase was separated from an aqueous layer in the and the side reaction. Sulfuric acid is used in the amount of
separating funnel. The epoxidized oil was washed several about 1-2 wt% in relation to the epoxidizing agent
times with water until the neutral reaction of washing water (CH3COOH + 30 wt% H2O2). Lower durability of formic
was obtained. The aqueous solutions of acetic acid (aqueous acid and a simpler way of separation of acetic acid from the
layer) are collected in an intermediate storage tank. The aqueous phase after epoxidation is also important. A differ-
epoxidized oil is dried in a consecutive tank with mixer at a ence in the boiling point of acetic acid and water enables the
temperature of about 70°C at pressure 13.3-20.0 kPa and is separation of acetic acid by distillation.
then transferred to a product tank. A diluted acetic acid from
the tank for water rinsing is directed to a dehydration col- There are well-known studies [20] in which only 2 wt%
umn. The water is removed in the form azeotrope with ethyl of dry resin was used in relation to the epoxidizing agent
Epoxidation of Vegetable Oils, Unsaturated Fatty Acids and Fatty Acid Esters Mini-Reviews in Organic Chemistry, 2019, Vol. 16, No. 00 9

(CH3COOH+H2O2). However, in this epoxidation method, it CONCLUSION

was necessary to increase the temperature to 85°C and to
The most important in the production of epoxidized
prolong the reaction time over a period of 20 h.
vegetable oils are the processes requiring the use of in situ
The investigations on the effect of the amount of strongly peracetic acid or performic acid, carried out in the presence
acidic ion exchange resins indicate a smaller significance of of strongly acidic resins, such as sulphonated polymers of
this parameter. However, in the upper-temperature range styrene or copolymers of styrene and divinylbenzene, as cat-
(70-85°C), the selectivity of transformation to oxirane oxy- alysts formation of peracids. The peracid is formed by the
gen decreases. The reason is the increase in the rate of side reaction of 30-70 wt% hydrogen peroxide with acetic or
reactions involving the opening of oxirane rings [26, 71]. In formic acid. Alternative solutions are based on preformed
order to shorten the reaction time to about 6-8 h, tempera- peracid, which is subsequently introduced into the epoxida-
tures of about 80°C should be used. In general, lower tem- tion reactor.
peratures (50-60°C) require to prolong the reaction time to
Independently of the type of epoxidized oil, the most ad-
about 14-16 h. In this case, the type of epoxidized oil and ion
vantageous technological parameters and safe operation con-
exchange resin becomes more important.
ditions are identical or have similar values in the majority of
In the processes carried out in the batch and semi-batch cases. It was found that the molar ratio of acetic acid or for-
reactors with a mineral acid catalyst, it is necessary to main- mic acid to ethylenic unsaturation RCOOH/C=C = 0.5:1, the
tain the homogeneity of the oil-water reaction mixture. In the molar ratio of hydrogen peroxide to the amount of ethylenic
majority of processes, the stirrer rate was at least 1500 rpm unsaturation H2O2/C=C = 1.5:1, and temperature in the range
[20, 21]. However, the methods are known in which the stir- of 50-80°C should be used. The ion exchange resin catalyst
ring rate is 500-2500 rpm even in the presence of heteroge- is used in the amount of 15-25 wt% in relation to the epox-
neous catalysts (resins). The rate of agitation for commercial idizing agent (CH3COOH+30 wt% H2O2) and 0.5-2.0 wt% in
epoxidation is determined experimentally and depends on the the case of H2SO4. The stirring rate should be at least 1500
size and shape of the reactor and the type of used stirrer. The rpm and the reaction time 4-10 h.
optimum rate is that in which the oil is broken into smaller
globules and layering is eliminated. CONSENT FOR PUBLICATION
The investigations of the simultaneous influence of tem- Not applicable.
perature and the reaction time on the selectivity of transfor-
mation to oxirane oxygen and on the yield indicate that low- FUNDING
er temperatures and longer reaction times lead to higher se-
lectivities and yields [29]. However, the type of epoxidized None.
oil (the degree of unsaturation and position of the unsaturat-
ed bonds) is of great importance. Oils with a high content of CONFLICT OF INTEREST
unsaturated bonds (linseed oil IN = 160-204 g/100g, perilla The authors declare no conflict of interest, financial or
oil IN = 190-206 g/100g) are more preferably epoxidized otherwise.
after longer reaction times. Tung oil does not undergo the
epoxidation due to its high content of α-eleostearic acid (80 ACKNOWLEDGEMENTS
wt%), wherein the three double bonds are in the conjugated
system. For this reason, tung oil readily undergoes polymeri- Declared none.
zation.
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