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Kinetics of Soybean Oil Epoxidation in a Semibatch Reactor

Elio Santacesaria,* Rosa Turco, Vincenzo Russo, Martino Di Serio, and Riccardo Tesser

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ABSTRACT: In this work, the kinetics of soybean oil epoxidation

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with hydrogen peroxide in the presence of formic acid as an oxygen

carrier and phosphoric acid as a catalyst has been studied. A
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biphasic kinetic model developed in a previous work has been

improved considering the evolution of four different reactions with
time: (1) the oxidation of formic acid to performic acid, occurring
in aqueous phase; (2) the epoxidation reaction, occurring in oil
phase; (3) the ring-opening reaction, mainly occurring at the
liquid−liquid interface; and (4) the performic acid decomposition,
occurring in aqueous phase. The kinetics of reactions 1, 3, and 4
have been studied in an independent way, and the best kinetic
parameters found and published elsewhere have been used for
interpreting the experimental results obtained in performing
reaction 2. A kinetic law for this reaction has been proposed, and the related best-fitting parameters have been determined.

1. INTRODUCTION performic acid, for example, decomposes with a radical

Epoxidation of vegetable oil results in products that are widely mechanism10−12 giving place to the main reaction12
employed as plasticizers and stabilizers for PVC resins in
substitution of phthalates that were banned in many countries HCOOOH → CO2 + H 2O (3)
for their negative effects on health.1,2 Moreover, considering the
high reactivity of the epoxy groups, epoxidized vegetable oils are This reaction consumes directly the reactant HCOOH and
also useful as starting raw materials to produce a variety of indirectly the reactant H2O2, and to compensate this negative
chemicals such as polyols3 and lubricants4 or as intermediates effect, an excess of both these reactants is normally employed.
for polyurethanes production. 5 For these reasons, the According to this stoichiometry, both hydrogen peroxide and
production of epoxidized soybean oil (ESBO) by the formic acid are consumed during the epoxidation reaction, and
Prileschajew reaction6 has shown in the recent years a significant the carbon dioxide evolved can be determined indirectly from
growth worldwide. The study of vegetable oil epoxidation is the mass balance of these two components. The epoxidation
currently performed in semibatch reactors using peracids reaction is extremely exothermic. There are some discrepancies
(performic or peracetic) as oxidant species.7−9 For safety in the values of enthalpy published in the literature; hence, we
reasons, the peracids are generated in situ by oxidation of an adopted the value estimated by us in a previous work by
organic acid, such as formic acid or acetic acid, with hydrogen simulating non isothermal runs,13 that is, ΔH = −230 kJ/mol for
peroxide in the presence of a mineral acid (sulfuric or each reacted double bond; this value is the same used by Zheng
phosphoric) promoting the reaction as a catalyst. For this et al.33 and is in agreement with the value of 250 kJ/mol reported
purpose, the main reaction occurring in the aqueous phase is by Ullmann,14 with 215 kJ/mol found by thermochemical
measurements, made at 70 °C, by Rossi15 and in acceptable
H 2O2 + RCOOH V RCOOOH + H 2O (1) agreement with the values published by de Quadros and
This reaction is fast and reaches equilibrium in a short time. Giudici16 and Vianello et al.8 of 197 and 193 kJ/mol,
Performic or peracetic acid, which is more soluble than respectively.
hydrogen peroxide in the oil phase, migrates in that phase and
reacts as it follows Received: September 14, 2020
Revised: October 30, 2020
Accepted: October 30, 2020

Then, formic or acetic acid migrates back to the aqueous phase

and a new oxidation cycle restarts. Peracids are not stable,

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c04530

A Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

This aspect gives rise to serious problems of safety in starting from a completely epoxidized soybean oil by evaluating
performing the reaction.17−21 To avoid an excessive increase of along the time the disappearance of the oxirane rings in the
the temperature in the industrial reactors, limited amounts of presence of different concentrations of all of the possible
hydrogen peroxide and formic or acetic acid are added as pulses nucleophilic agents.24 Therefore, in the present work, the
to a mixture of oil and acid catalyst. Alternatively, by adopting a kinetics of the soybean oil epoxidation by performic acid (PFA),
slow feed flow rate of hydrogen peroxide and formic or acetic generated in situ, by reacting highly concentrated H2O2 (60 wt
acid, a semibatch operation is also possible. %) with formic acid, in the presence of phosphoric acid as a
The reaction normally requires 8−10 h for completion, catalyst, has been studied in a fed-batch reactor. In this kinetic
keeping the temperature between 60 and 75°C. It must be study, we have considered:
pointed out that, initially, epoxidation is a relatively fast reaction, (i) the partition between the reacting phases of the reagents
giving rise to a steep rise of temperature; then, the reaction (data and parameters achieved in an independent way);
becomes slower and slower and, as a consequence of the long (ii) the rates of both performic acid formation and
reaction time, the epoxide groups are subjected to a ring- decomposition occurring in aqueous phase (data and
opening side reaction.22−27 This unwanted reaction has the parameters achieved in an independent way);
effect of decreasing the selectivity and, according to different (iii) the rate of the epoxidation occurring in oil phase for
researchers,22−27 occurs at the water−oil interface. Recently, we determining the kinetic law and related kinetic parame-
have shown24 that this is true only in the presence of a strong ters;
Bronsted acid.
(iv) the rate of degradation of oxirane rings (data and
By concluding, during epoxidation, four different reactions
parameters achieved in an independent way);
occur: (1) oxidation of an organic acid to the corresponding
peracid, (2) decomposition of the peracid, (3) epoxidation (v) the effect of mass transfer in limiting the reaction rates;
reaction, and (4) epoxide ring-opening side reaction. The first (vi) the occurring thermal contributions related, respectively,
two reactions occur in the aqueous phase, epoxidation occurs to the heat released by all of the reactions, the heat
inside the oil phase, while the ring-opening reaction, in the removed by exchange with the thermostatting fluid and
presence of strong Bronsted acids, occurs mainly at the water− the heat dispersed with the external environment.
oil interface. The present work is devoted to the study of the kinetics of the
Process optimization requires a detailed knowledge of both epoxidation reaction performed in the presence of phosphoric
the kinetics of all of the occurring reactions and the effects of acid, adopting all of the kinetic laws and the parameters
heat and mass transfers on those reactions. Different papers have estimated independently in our previous publications, on both
been published in the past on the kinetics of the epoxidation of performic acid decomposition and ring-opening reaction.
vegetable oil.27,28 All of these papers considered the occurrence In conclusion, the main scopes of this work are: (i) to develop
of the reaction as a pseudo-monophasic system. Rangarajan et an improved reliable biphasic kinetic model useful as a base for
al.29 first proposed a two-phase model, considering a local phase modeling batch, fed-batch, and continuous reactors operating in
concentration to calculate the reaction rate and the mass transfer safe conditions; (ii) to validate kinetic laws and related
effect. The monophasic approach is clearly oversimplified for parameters used in the model; (iii) to evaluate the role of heat
correctly interpreting a very complex reaction system, while few and mass transfer in the reaction under different operative
biphasic studies have been reported in the literature.29−34 In our conditions; and (iv) to have a basis for a process intensification.
previous work,13 we developed a biphasic kinetic model rather
similar to the one presented here, at least for the mathematical 2. EXPERIMENTAL SECTION
aspects. Two different kinds of experiments were conducted and 2.1. Materials, Apparatus, and Methods. 2.1.1. Materi-
interpreted, eight runs containing sulfuric acid and two runs als. The soybean oil, with iodine number 128 (gI2/100 gsample),
containing phosphoric acid as a catalyst. Hydrogen peroxide was purchased from a local food store. Its fatty acid composition,
consumption, not due to the epoxidation reaction, was measured by gas chromatographic analysis, was as follows (wt
erroneously considered as a direct hydrogen peroxide %): palmitic = 11, stearic = 4, oleic = 23, linoleic = 56, linolenic =
decomposition, because, at that time the decomposition was 5, others = 1. Hydrogen peroxide (54.9 wt %) was supplied by
not identified to be due to the performic acid. The Solvay SpA. Formic acid (96 wt %), phosphoric acid (85 wt %),
decomposition of performic acid was studied in a successive and all of the other reagents were provided by Merck at the
work specifically devoted to that subject.12 Moreover, the ring- highest level of purity available and used as received.
opening reaction was considered, in agreement with other 2.1.2. Apparatus. The kinetic runs were carried out in a 500
researchers,22−27 occurring at the interface. This is correct only mL volume jacketed glass reactor with four necks, equipped with
for the experiments performed in the presence of sulfuric acid, a thermocouple, a reflux condenser, and system to follow the
not when phosphoric acid is used as a catalyst, as we evolution of gas.
demonstrated in a recently published work24 specifically The reacting mixture was stirred with a magnetically driven
devoted to the investigation of the kinetics of the ring-opening mechanical stirrer (>750 rpm) well mixing the oil−aqueous
reaction. It is opportune to point out that an adequate biphasic emulsion. This rotating speed was chosen on the basis of the
model requires introduction of correct kinetic laws for each results obtained in a previous study on the kinetics of ring-
considered reaction with the related kinetic parameters. This can opening reaction24 to avoid mass transfer limitation.
be achieved by collecting, for some reactions, experimental data Temperature control was made by recirculating thermo-
with independent experiments. For this purpose, we have statted water inside the reactor jacket. The thermal profiles of
studied separately the kinetics of the reaction of performic acid the reaction mixture and the water in the jacket were
formation and decomposition, in aqueous phase, in the absence continuously monitored, collected by thermocouples, and
of vegetable oil.12 In the same way, the ring-opening reaction has recorded by a data acquisition module purchased from the
been studied with an independent experimental approach National Instruments Co. Before use, the reactor has been
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Table 1. Operative Conditions Adopted for the Epoxidation Runs

run oil (g) H3PO4 (g) HCOOH (g) H2O2 (g) modality addition step Tinitial (°C) Tdigestion (°C) Tdigestion (min)
1 100 1.16 5.38 37.00 1 56 66−68a 180
2 100 1.14 5.8 37.00 2 64 72 240
3 200 2.32 10.76 74.00 3 64 72 240
4 200 2.34 10.76 74,01 3 64 72 240
5 200 2.34 10.76 74.00 4 64 72 240
6 100 1.00 5.38 37.00 see ref 13 64 64 240
a
The digestion was performed at 66 °C for 1 h and at 68 °C for 3 h.

thermally characterized by heating and cooling the oil with a (38 pulses of 1 cm3 each) of the oxidizing mixture (hydrogen
thermostat fluid. The temperature of the oil, as well as the inlet peroxide 60 wt % + formic acid (95 wt %) added to a fixed
and outlet temperatures of the thermostat fluid remained quite amount of preheated oil (100 g) containing about 1% H3PO4
similar without any significant delay for the oil in reaching the (86 wt %) catalyst. Pulses were added in a very short time (2 s)
imposed temperature. This means that in the reactor the heat that means a flow rate of 30 mL/min. After each addition, a
transfer is very fast and consequently a high value of heat transfer known time passed before a successive pulse to lower the
coefficient can be assumed in the simulation of the temperature temperature. The addition started when the oil temperature
profile of the runs performed. Formic acid and hydrogen reached 57 °C, and the oxidizing mixture was fed at room
peroxide were charged together or separately through a pump temperature (25 °C), while the temperature of the thermo-
system consisting of two pumps: a single syringe infusion pump statting fluid was initially 64 °C. Details on the type of reactor
(KD Scientific, series 100) equipped with a glass syringe employed for performing this run are reported elsewhere.13 In
(Micromate Popper & Sons, 20cc) and an high performance the present work, this experiment was reinterpreted with the aim
liquid chromatography (HPLC) pump (Jasco, series PU2086i). to introduce the new findings in the simulation and gain more
2.1.3. Methods. In this work, five different epoxidation kinetic confidence with the improved model.
runs, using phosphoric acid as a catalyst, have been performed. Samples of the emulsion containing the two phases were
Normally, a weighed amount of preheated soybean oil was withdrawn at different times. Each sample was quenched in a
initially put in contact with a concentrated solution of cold water and ice bath; then, a sodium bicarbonate solution (10
phosphoric acid. Then, hydrogen peroxide and formic acid, wt %) was added to the reaction product to neutralize the acids
taken at room temperature, were slowly added at a constant flow present in the sample. Since the neutralization reaction proceeds
rate, mixed or separately, for about 1 h, following four main with the formation of gaseous carbon dioxide, this step was
procedures. carried out using a separating funnel to safely degas the treated
2.1.3.1. Modality 1. The mixture of formic acid and hydrogen product. Each sample thus treated was centrifuged for 10 min
peroxide at 25 °C was added by a syringe pump, with a flow rate (350 rpm), at the end of which only the organic phase was taken
of 0.73 cm3/min, to oil and catalyst in a reactor set at 56 °C. At and subsequently dried with anhydrous magnesium sulfate. Each
25 °C, the conversion of formic to performic acid and the sample thus treated was further centrifuged, to separate it from
performic acid decomposition are relatively slow and the the solid suspension, and then analyzed to determine the iodine
behavior observed in the experiment performed with this number and the oxirane number. The iodine number is an index
modality is poorly affected by the adopted experimental of the oil unsaturation expressed as grams of iodine fixed by 100
procedure. g of oil. It has been determined by the Wijs method.35 The
2.1.3.2. Modality 2. Hydrogen peroxide and formic acid at 25 oxirane number (grams of oxygen bonded/100 g of oil) defines
°C were added separately. The formic acid was loaded by an the content of epoxy groups in the epoxidized oil and has been
HPLC pump at a flow rate of 0.19 cm3/min, while the hydrogen determined by potentiometric titration with a standard
peroxide was loaded by a syringe pump at a flow rate of 0.54 method.36
cm3/min.
2.1.3.3. Modality 3. Formic acid solution with a flow rate of
3. RESULTS AND DISCUSSION
0.19 cm3/min and H2O2 solution (54.9%) with a flow rate of
0.64 cm3/min were added separately by an HPLC pump and a 3.1. Development of a Complete Biphasic Kinetic
syringe pump, respectively. Model. 3.1.1. Description of the Occurring Reactions and of
2.1.3.4. Modality 4. The oxidizing reactants at 25 °C were the Related Available Kinetics. A kinetic model has been
added separately. Formic acid was added with a flow rate of 0.2 developed considering: (a) the kinetics of performic acid
cm3/min, while H2O2 solution, containing the catalyst H3PO4, formation and decomposition; (b) the rate of CO2 formation;
was added with a flow rate of 0.64 cm3/min. (c) the overall H2O2 consumption; (d) the partition of formic
This reaction phase has been named as an “addition” step. and performic acid in the two phases and the eventual effect of
Afterward, the reaction proceeded for another 3−4 h to mass transfer limitation; (e) the change of pH in the aqueous
complete the reaction (“digestion” step). The adopted phase; (f) the change of volume of the reacting mixture for both
experimental conditions are detailed in Table 1. the reactant feeding and the withdrawing of samples to be
In all of the runs with the exclusion of run 6, the initial analyzed; (g) the evolution with time of both the iodine number
temperature was increased by heating till reaching the value (IN) and oxirane number (ON) by taking into account both the
corresponding to the digestion temperature and remained then kinetics of epoxidation and that of ring-opening side reaction.
approximately constant for the whole duration of the run. Run 6 Moreover, were also simulated the temperature profile inside the
has been taken from a previous work published by Santacesaria reactor along the time by applying an energy balance.
et al.13 This run is characterized by a series of many small pulses 3.1.1.1. Reaction 1. The reactions occurring in the system are
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

H 2O2 + HCOOH V HCOOOH + H 2O (4) the mass and heat transfer exchanges, and the solubilities of both
performic and formic acids in the reacting oil phase. The more
This reaction, occurring in the aqueous phase, has been studied
suitable rate law, in agreement with other authors,29−34 is of first
independently, that is, in the absence of soybean oil, and the
order for both performic acid dissolved in oil and double-bond
kinetic results are reported in detail in a previous work.12 The
concentrations.
reaction is promoted by the acidity of the aqueous phase, and in
3.1.1.4. Reactions 4 and 5. The epoxide ring-opening
the presence of H3PO4, it occurs with a kinetic law of the type12
reaction is an undesired side reaction having the effect of
r1 = k1[H+][HCOOH]w [H 2O2 ] lowering the selectivity. In the presence of a strong mineral acid
ij y
jj1 − 1 [HCOOOH]w [H 2O] zzz (mol/L min)
like sulfuric acid, it mainly occurs at the interface with the
jj Ke1 [HCOOH]w [H 2O2 ] zz{
mechanism reported here.13,24
k
ÄÅ ÉÑ
(5)

ÅÅi −E yij 1 1 yzzÑÑÑÑ

k1 = k1 − 323 K expÅÅÅÅjjj a1 zzzjjj − zÑ = (7.8±0.78)
ÅÅk R {j T
ÅÇ k Tkref zz{ÑÑÑÑÖ
ÄÅ É
ÅÅi −19830 ± 694 yi 1 1 yzÑÑÑÑ
Recently, we demonstrated24 that, in the presence of sulfuric
× 10−2 expÅÅÅjjj zzzjjj − zzÑÑ
ÅÅÇk 323 {ÑÑÖ
acid, the reaction is affected by the concentration of both the
{k T
acid, in particular formic acid, and the nucleophilic agents. To
1.987
explain this behavior, it must be assumed that the nucleophilic

ÄÅ É
(L2/mol2 min) attack to the protonated epoxide is the rate-determining step. By

yzÑÑÑÑ
(6)

ÅÅi −ΔH e yi 1
Å j z j
zjj − zzÑÑ
considering all of the involved equilibria, the rate law becomes of
Ke1 = Ke1 − 298 K expÅÅÅjj
ÅÅk R z{jj T Tkref zz{ÑÑÑÑÖ
1 first order with respect to [H+], [ESBO], and [Nu]. Then, we

ÅÇ k
1

ÄÅ É
observed also that the nucleophilic agents show different

ÅÅi 2390 ± 215 yi 1 1 yzÑÑÑÑ

= (1.6 ± 0.1)expÅÅÅjjj zzzjjj −
activities, with formic acid being the most powerful agent. A
zzÑÑ
ÅÅÇk 1.987 {k T 298 {ÑÑÖ
rough estimation of the different nucleophilic contributions was
made,24 in which formic acid is about 40 times more active than
(7)
the others in promoting the ring-opening reaction. In
This reaction is relatively fast and normally can be considered at conclusion, a general kinetic law can be written for the reaction
equilibrium. The subscript “w” stands for aqueous phase occurring with the described mechanism.
concentration.
3.1.1.2. Reaction 2. The kinetics of Reaction 2 was studied r4 = k4[H+][ESBO](α1[FA] + α2[H 2O2 ] + α3[PFA]
independently, too, together with Reaction 1, and the related + α4[H 2O]) (mol/(Loilmin)) (13)
data are reported in the same previous work.12
In the presence of H3PO4, although the reaction is poorly
HCOOOH → CO2 + H 2O (8)
affected by the stirring rate and by the catalyst concentration, we
The kinetic law and related parameters determined in the cannot exclude the intervention of this type of mechanism, and
presence of H3PO4 as a catalyst are the related contribution was estimated from the experimental

ÄÅ ÉÑ
runs performed elsewhere24 as
ÅÅi −E yi 1 1 zyzÑÑÑÑ
ÄÅ ÑÉ Å
Å j a4 zj
j
r2 = k 2[HCOOOH]w (mol/L min)
k4 = k4 − 333 K expÅÅjj zj −
(9)

ÅÅi −E yi 1 1 yzzÑÑÑÑ zÑ
Å
Å j
j a2 zj
zj ÅÅk R z{jj T Tkref zz{ÑÑÑÑÖ
k 2 = k 2 − 323 K expÅÅj j − zÑ = (8.4 ± 0.83) ÅÇ k
ÅÅk R z{jj T Tkref zz{ÑÑÑÑÖ ÅÄÅi −21 000 ± 900 y
ÅÇ k Å
ÄÅ É
1 yzÑÑÑÑ = (5.2 ± 0.2) × 10−6 expÅÅÅjjj zz
z
ÅÅÅij −23180 ± 720 yzij 1 ÅÅÇk {
× 10 expÅÅjj zzjj − zzÑÑ (1/min)
ÅÅÇk {k T 323 {ÑÑÖ ÉÑ
ij 1 1 yzÑÑ Ñ
−3 1.987

jj − zzÑÑ
333 {ÑÑÖ
1.987

kT
(10)
(14)
3.1.1.3. Reaction 3.
where k4 and Ea4 are expressed in L2/(mol2 min) and cal/mol,
respectively. Then, it holds: α1 = 40, α2 = α3 = α4 = 1. This is
justified by the fact that again the nucleophilic power of formic
acid became much greater than the ones of the other
components.
However, in the presence of phosphoric acid, that is, in an acid
environment less strong than sulfuric acid, another mechanism
prevails characterized by a direct nucleophilic attack to one or
both the carbon atoms of the oxirane ring.24 An intermediate
This reaction occurs inside the oil phase. Performic acid, formed
specie is formed with a negative charge on the oxygen followed
in the aqueous phase, migrates in the oil phase, being moderately
by the abstraction of a proton from another nucleophilic
soluble in soybean oil. After the reaction, formic acid that is
molecule, according to the mechanism
formed comes back to the aqueous phase starting a new
oxidation cycle. The evaluation of the kinetic law of this reaction
(r3) and related parameters is the objective of this work, and the
experimental data collected for this purpose will be interpreted,
as it will be seen, by considering all of the reactions occurring,
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We observed in a previous work24 that the kinetic law, in this The dissociation equilibrium constants at 25 °C can be easily
case, is poorly dependent on the proton concentration, but it is found in the current study or in many other studies.
of second order with respect to the nucleophile concentrations, As mentioned above, following a rigorous approach, for
that is determining the correct H+ concentration in the managed
solutions and its evolution along the time, we have to solve three
r5 = k5[ESBO][Nu]2 different sets of algebraic equations that are:
= k5[ESBO](γ1[FA]2 + γ2[H 2O2 ]2 + γ3[PFA]2 + γ4 (1) System equations to evaluate H+ concentration in a formic
acid solution used as a reactant
[H 2O]2 ) (16)
[H+][HCOO−] − KE4[HCOOH] = 0 (24)
This kinetic law is in agreement with the observation made by
some other authors that reported in the literature a kinetic [H+][OH−] − K w = 0 (25)
law20,22 of the type r = k[ESBO][Nu]2. We simply differentiated
the activity contribution of the nucleophilic agents on the basis [HCOOH] + [HCOO−] − [HCOOH]° = 0 (26)
of our experimental observations.24

ÄÅ É
yzÑÑÑÑ
Again it holds approximately: γ1 ≃ 40, γ2 = γ3 = γ4 ≃ 1 and
ÅÅÅji −Ea5 zyij 1
[HCOO−] + [OH−] − [H+] = 0 (27)

k5 = k5 − 333 K expÅÅÅjj zjj − zzÑÑ

ÅÅk R z{jj T Tkref zz{ÑÑÑÑÖ
1 The dependence of the equilibrium constants KE4 and Kw
ÅÇ k
ÄÅ É
1 yzÑÑÑÑ
on the temperature must be considered, and it can be
ÅÅi −10750 yi 1
= (2.5 ± 0.045) × 10−7 expÅÅÅjjj zzzjjj − zzÑÑ
found in the literature. Kw, for example, is strongly

ÅÅÇk 1.987 {k T 333 {ÑÑÖ

dependent on the temperature, and several studies have
been devoted to the subject.37,38 The following relation-
(17) ship, although has no physical mean, well interpolates the
Kw values at different temperatures
where r5 is expressed in mol/(Loil min) and k5‑333 in L /(mol2 2

min). The kinetics of this reaction has been studied separately by K w = 8.754 × 10−10 · exp( −1.01 × 106 /T 2) (28)
us in a previous work24 by putting already epoxidized soybean oil
(ON > 6) directly in contact with different concentrations of all Different works have also been published on the
of the possible nucleophilic agents, hydrogen peroxide, water, dissociation constant of formic acid,39,40 and the depend-
and formic and performic acids and in the presence of ence of Ke4 on the temperature can be calculated with the
phosphoric acid. The described behavior agrees with some relation
results reported in the literature by different authors.22,23,27
According to these authors, for a given pH, a second order with KE4 = 10−{(−57.528) + (2773.9/ T ) + 9.1232·ln(T )} (29)
respect to [Nu] was found. Moreover, these works show also
that, at a given pH, both formic and performic acids and (2) System equations to evaluate H+ concentration in a
hydrogen peroxide influence the reaction rate. phosphoric acid solution. As seen, phosphoric acid gives
In conclusion, in the presence of phosphoric acid, both the rise to three different dissociation steps; therefore, the
described mechanisms are operative and the rate of oxirane ring- system to be solved, in this case, becomes
opening reaction (ROR) can be expressed as rror = r4 +r5.
3.1.1.5. Reactions 6 and 7. As we have seen, reaction 1 and [H+][H 2PO4 −] − KE1[H3PO4 ] = 0 (30)
reaction 4 are promoted by the acid environment. A rigorous
approach would be to calculate how the H+ concentration [H+][HPO4 =] − KE2[H 2PO4 −] = 0 (31)
changes with time in the aqueous reactants by adding a solution
of hydrogen peroxide and formic acid to the catalyst. For this [H+][PO4 3 −] − KE3[HPO4 =] = 0 (32)
purpose, we have developed different programs code for solving
the set of algebraic equations for determining, respectively, the [H+][OH−] − K w = 0 (33)
H+ concentration in a solution of formic acid (the solution to be
added), in a solution of concentrated phosphoric acid (solution [H3PO4 ] + [H 2PO4 −] + [HPO4 =] + [PO4 3 −]
in contact with oil), and in a solution containing both formic and
phosphoric acids (solution formed by adding the oxidant − [H3PO4 ]° = 0 (34)
mixture). The reactions occurring are
(3) System equations to evaluate H+ concentration in a
H3PO4 V H+ + H 2PO4 − KE1 = 7.11 × 10−3 (18) phosphoric acid + formic acid solution. When the solution
of formic acid is added to the catalyst, the following
H 2PO4 − V H+ + HPO4 = KE2 = 6.31 × 10−8 (19)
equations must be solved to evaluate the corresponding
HPO4 = V H+ + PO4 3 − KE3 = 4.8 × 10−13 H+ concentration
(20)
[H+][H 2PO4 −] − KE1[H3PO4 ] = 0 (35)
HCOOH V H+ + HCOO− KE4 = 1.77 × 10−4
(21) [H+][HPO4 =] − KE2[H 2PO4 −] = 0 (36)
HCOOOH V H+ + HCOOO− KE5 = 7.90 × 10−8
(22)
[H+][PO4 3 −] − KE3[HPO4 =] = 0 (37)

H 2O V H+ + OH− K w = [H+][OH−] = 10−14 (23) [H+][OH−] − K w = 0 (38)

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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

[H3PO4 ] + [H 2PO4 −] + [HPO4 =] + [PO4 3 −] The numerical values of k6 and k7 must be taken arbitrarily high
to allow the achievement of the equilibrium in a very short time
− [H3PO4 ]° = 0 (39) without determining instability in the solution of the system of
differential equations representing the model. It is important, on
[H 2PO4 −] + 2[HPO4 =] + 3[PO4 3 −] + [OH−] the contrary, to define the dependence on the temperature of
KE1 that, according to the data reported in the literature,41 can be
+ [HCOO−] − [H+] = 0 (40) written as
[H+][HCOO−] − KE4[HCOOH] = 0 (41) KE1 = 10−{(799.31/ T ) − 4.5535 + (0.013486·T )} (47)
−
[HCOO ] + [HCOOH] − [HCOOH]° = 0 (42) The dependence of Ke4 was already given (see relationship 29)).
The first two equations system must be solved only one time for 3.1.2. Description of the Physical Occurring Phenomena,
determining the initial conditions of pH of the reactants, while Partition of Formic and Performic between the Two Phases,
the third equations system must be solved many times, that is, at and Mass Transfer Rates of These Components. The
any instant of the occurring reactions, because the pH changes epoxidation reaction occurs because a certain amount of
by feeding the aqueous reactants into the reactor containing performic acid, obtained by oxidizing formic acid with hydrogen
soybean oil and catalyst. These algebraic equations would be peroxide, migrates toward the oil phase in which it is moderately
coupled with the differential ones, and the overall problem is soluble, reacting there with the double bonds to give the oxirane
represented by a DAE system (differential algebraic equations); rings. Formic acid, obtained in this reaction, accumulates in the
the algebraic part is solved at the integration step in time. In this oil phase until reaching saturation and then counterdiffuses
way, the calculation time becomes very long. However, some toward the aqueous solution for initiating a new oxidizing cycle.
reasonable approximations can be introduced, for example, the Two physical phenomena occur that must be kept under control
contribution of the second and third dissociations of phosphoric in the kinetic model: the partition of both formic and performic
acid in determining the H+ concentration, considering the very acids between the aqueous and oil phases and the mass transfer
low values of the corresponding equilibrium constants, can be rates of these two components from one phase to another. The
neglected. Then, the contribution of the performic acid partition of FA and PFA and the absolute value of their
dissociation can be neglected, too, for the same reason. Despite solubilities are the most uncertain data that are very difficult to
these approximations, the calculation time remains very long. evaluate also by experimental measurements. The data reported
Another possibility is to consider all of the ionization reactions in the literature on this aspect are rare and uncertain. UNIFAC
occurring as a set of reactions with their kinetic laws to be added and UNIQUAC cannot be used because there are no group
to the four reactions occurring together with the epoxidation. contributions for peracids. For this reason, we adopted for this
This can be done by assuming a very high kinetic constant that evaluation, as explained in a previous work, the SPARC online
brings promptly all of the ionization reactions to the equilibrium. calculator to have a reproducible way for determining the
In this case, the number of differential equations to be integrated solubilities. The solubilities, at different temperatures, of formic
in the model simply increases, but this occurs by highly reducing and performic acids, water, and hydrogen peroxide in soybean
the calculation time. Obviously, the mass balance must consider oil were estimated in this way in a previous work.13 We observed
the evolution with time of all of the ionic and undissociated that the solubilities of water and hydrogen peroxide were
species. Moreover, by introducing the already mentioned negligible and only formic and performic acids were moderately
approximations, only two equilibria can be considered in the soluble.13 As the epoxidized oil has a chemical structure similar
calculations that are to the soybean oil, we assumed that the solubilities remain
relatively constant during the reaction, changing only with
H3PO4 V H+ + H 2PO4 − (43) temperature. It is clear that when more reliable solubilities data
will be available, it would be easy to recalculate the
HCOOH V H+ + HCOO− (44) corresponding kinetic constants. However, all of these aspects
Hence, it is necessary to follow along the time just the evolution were better explained in the already mentioned previous work.13
with time of the concentrations of undissociated H3PO4, The obtained values, for different temperatures, have been
H2PO4−, undissociated HCOOH, HCOO−, and obviously H+, interpolated with the following equations
that is, five further differential equations. The ODE system has
HFA = 9.0 × 10−7 ·T 2 − 5.0 × 10−5·T + 0.0046 (48)
been solved with a MATLAB program using the ODE solver
“ode15s” suitable for solving stiff differential equations and
DAEs. HPFA = 4.0 × 10−6 ·T 2 − 4.0 × 10−5·T + 0.04022 (49)
The rates that must be added to the kinetic model are
Hi = [i]aq */[i]org *
l − |
therefore where:
o jij 1 zyzjij [H ][H 2PO4 ] zyzo
(50)

o o
r6 = k6 [H3PO4 ]m j z j z}
o
o j KE1 zj [H3PO4 ] zzo
j z j
{o
+
As the mass transfer of, respectively, the formic and performic
n k {k ~
1 − acids, under certain conditions, can limit the reaction rate, it is
necessary to include also mass transfer rates in the biphasic
(mol/(L min)) model. Assuming Whitman’s two films theory valid, the

l ij 1 yzij [H+][HCOO−] yz|

(45)

o o
o jj zzjj zzo
following equations for the mass transfer rates can be written

r7 = k 7 [HCOOH]m
o j z j z}
o
o j z
n k KE4 {k [HCOOH] {o ~
1 − JFA aq = βFA aq ·([FA]aq − HFA ·[FA]*org ) (51)

(mol/(L min)) (46) JFA org = βFA org ·([FA]*org − [FA]org ) (52)

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JPFA aq = βPFA aq ·([PFA]aq − HPFA ·[PFA]*org ) (53) (3)

dn H +
= (FTOT·yHCOOH ·X Z2) + (r6 + r7) ·VL
dt w (61)
JPFA org = βPFA org ·([PFA]*org − [PFA]org ) (54) dnHCOOH
(4) = (FTOT· yHCOOH · X Z1) + ( − r1 − Jfaq − r7) · VL
where βJ are the product of the mass transfer coefficients and the
i
dt w

interfacial surface area for the component J in the phase i. We (62)

assumed this parameter constant for the aqueous phase (βJaq), dnHCOO−
while for the organic phase, the interfacial area increases with the (5) = (FTOT·yHCOOH ·X Z2) + r7·VL
dt (63)
aqueous volume and βJorg can be determined from the following
w

expression dn H2O2
aq aq (6) = (FTOT·yH O ) − r1·VL
V V dt (64)
βi org = kL·aorg = kL·aaq · = βi aq · org
2 2

V org V (55)
dn H 2 O
We assumed the same value of βJaq for both formic and (7) = (FTOT·yH O ) + (r1 + r2) ·VL
dt 2 (65)
performic acids. It is then possible to calculate the concen-
trations of both formic and performic acids at the interface dnHCOOH w
assuming steady-state conditions and hence (8) = (FTOT·yHCOOH ) + ( −r1 − Jfaq ) ·VL
dt w
aq org
Ji ·Vaq = Ji ·Vorg (56) (66)

It results dnHCOOOH w
(9) = (FTOT· yHCOOOH ) + (r1 − r2 − Jpaq ) · VL
dt w
Vaq ·βFA aq ·[FA]aq + Vorg ·βFA org ·[FA]org (67)
[FA]*org =
Vorg ·βFA org + Vaq ·βFA aq ·HFA (57) XZ1 and XZ2 are the fractions of, respectively, non dissociated
HCOOH and HCOO− with respect to the total amount of
Vaq ·βPFA aq ·[PFA]aq + Vorg ·βPFA org ·[PFA]org HCOOH in the aqueous phase. FTOT is the molar flow rate in
[PFA]*org = mol/min. When the flow rate of the oxidizing mixture is stopped
Vorg ·βPFA org + Vaq ·βPFA aq ·HPFA
between a pulse and the successive pulse, integration continues,
(58) but FTOT =0.
3.1.3. Description of the Biphasic Kinetic Model Employed 3.1.4.2. Oil Phase.
for Interpreting the Experimental Data. The biphasic kinetic
dnHCOOHoil
model, developed for simulating all of the experimental (10) = (r3 + Jforg ) ·Vorg
performed runs, is characterized by 17 differential equations dt (68)
describing the evolution with time of 17 variables that are:
dnHCOOOHoil
(a) The number of moles in the aqueous phase: (1) nH3PO4 (11) = ( −r3 + Jporg ) ·Vorg
(69)
(not dissociated); (2) nH2PO4−; (3) nH+; (4) nHCOOH dt
(not dissociated); (5) nHCOO−; (6) nH2O; (7) nH2O2; dnDB
(8) nHCOOH (overall in aqueous phase); (9) (12) = ( −r3) ·Vorg
dt (70)
nHCOOOH (in aqueous phase);
(b) The number of moles in the oil phase: (10) nHCOOHoil dnDEGESBO
(dissolved in oil); (11) nHCOOOHoil (dissolved in oil); (13) = (r4 + r5) ·Vorg
dt (71)
(12) nDB (double bonds amount); (13) nDEGESBO
(opened oxirane rings); (14) nESBO (moles of oxirane dnESBO
ring formed) (14) = (r3 − r4 − r5) ·Vorg
dt (72)
(c) Other variables: (15) VL (overall liquid volume in the
reactor); (16) nCO2 (moles of CO2 formed for the The epoxidation rate r3, in agreement with the findings of other
decomposition of HCOOOH); (17) T (reaction temper- authors,29−34 can be expressed as
ature); r3 = k 3[HCOOOH]oil [DB] (mol/(Loil min)) (73)
To consider the change of mass and volume determined as a
where [DB] is the concentration of double bonds and
consequence of the samples withdrawn, other two variables have
[HCOOOH] is the concentration of performic acid in oil,

ÅÄÅ ÑÉ
been considered: Moil (18) and Vorg (19) that are, respectively,

1 zyzÑÑÑÑ
both expressed in mol/L. Then, we can write
ÅÅij −Ea3 yzji 1
the mass and volume of oil remaining in the reaction vessel.

k 3 = k 3 − 333 K expÅÅjjÅ j
zj − zÑ (L/(mol min))
ÅÅk R z{jj T Tkref zz{ÑÑÑÑÖ
3.1.4. Mass and Energy Balances. When the flow rate is

ÅÇ k
operative, the following differential equations must be integrated
simultaneously:
3.1.4.1. Aqueous Phase. (74)
dn H3PO4 The kinetic parameters k3‑333K and Ea3 (calories/mol) must be
(1) = −r6·VL determined by mathematical regression analysis of the data
dt (59) collected.
dn H2PO−4 3.1.4.3. Other Variables to Be Integrated. The volume of the
(2) = r6·VL aqueous phase initially is the volume of the catalyst, when this is
dt (60) not fed together with the aqueous reagents and increases by
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adding the oxidizing mixture. Obviously, the volume increases Q col = (wH2O2 ·C pH O + wH2O·C pH O + wHCOOH·
only when the flow rate is operative. Therefore, we have 2 2 2

dVL C pHCOOH) ·(TR − Tfeed) (84)

(15) = Q vol
dt (75) where wi are the mass flow rates in g/min corresponding to
where Qvol is the volumetric flow rate (L/min). Between a pulse wH2O2 = FTOT·yH O ·PM H2O2
2 2 (85)
and the successive pulse, Qvol = 0.
The number of moles of CO2 produced is calculated by the wHCOOH = FTOT·yHCOOH ·PMHCOOH (86)
equation
wH2O = FTOT·yH O ·PM H2O (87)
dnCO2 2
(16) = r2·VL
dt (76) Obviously, after each pulse, F TOT becomes zero, and
The last equation to be integrated is related to the energy consequently, wH2O2 = wHCOOH = wH2O = 0.
balance and take into account both the heat released by the When different samples are withdrawn from the reactor, at
reactions occurring and the heat dissipated from the reactor different times, the mass and volume, remaining in the reactor,
walls. become variables and must be opportunely calculated during the
integration. We have, therefore, to add two further variables that
dT are (18) Moil (mass of oil) and (19) Vorg (volume of organic
(17) = (Q r − Q sc − Q col)/(C P − average·wTOT)
dt (77) phase).
where Qr is the heat released by the occurring reaction (cal/ To execute the simulations, the initial conditions (t = 0) were
min). For this purpose, we have: set for all of the components. In detail, the initial values of the
ΔH3 = −55 000 cal/mol, ΔH4 = ΔH5 = −21 000 cal/mol, variables nHCOOH, nHCOO−, nH2O2w, nH2Ow, nCFAw, nCPFAw, nCFAoil,
ΔH2 = −23 000 cal/mol and can write nCPFAoil, nDEGESBO, nESBO, and nCO2 are always zero, because, at
zero time in the reactor, there is only oil in contact with the
Q r = ΔH3·( −r3) ·Vorg + ΔH4 − 5·( −r4 − r5) ·Vorg
catalysts (a concentrated solution of H3PO4). For run 5 also,
+ ΔH2·( −r2) ·VL (78) nH3PO4, nH2PO4−, and nH+ are zero, because the catalyst was
dissolved in H2O2 and fed with this reactant into the reactor.
Cp‑average (cal/(g °C)) is calculated as an average between Cp of The evaluation of some of the initial conditions requires, as
the oil phase and of the aqueous phase seen, the solution of a system of algebraic equations. The ODE
Cp − average = wfORG·Cp − oil + wf aq ·Cp − aq (79) system, as mentioned above, was solved with a MATLAB
program using the ODE solver ode15s.
where wfORG is the weight fraction of oil in the reaction mixture The kinetic parameters of the epoxidation reaction have been
and wfaq is the weight fraction of the aqueous solution according determined from the experimental data collected. For this

ÄÅ
ÅÅi −(24 890 ± 1540) yz
to the following relationships purpose, we can write

k 3 = (0.12 ± 0.007)expÅÅÅÅjjjj zz
z
ÅÅÇk {
wfORG = Moil /wtot(oil mass fraction) with Moil

ÉÑ
1 yzÑÑÑ
1.987
ij 1
= mass of oil and wtot = Moil + Maq = total mass

jj − zzÑÑ
kT 323 {ÑÑÑÖ
(80)
wf aq = Maq /wtot(aqueous mass fraction) (81) (88)
Some examples of the agreements between the experimental and
Maq = n H2O·PM H2O + n H2O2 ·PM H2O2 + nHCOOH calculated data obtained are shown in Figures 1 and 3 related,
respectively, to runs 2 and 4 of Table 1.
·PMHCOOH + nHCOOOH ·PMHCOOOH (82) The model allows us to evaluate also:
Qsc is the heat exchanged with the reactor (cal/min) and is (a) The evolution with time of the moles of, respectively,
calculated with the relation formic and performic acids and their distribution inside
Q sc = UA·(TR − TJ) the two phases at any instant of the run;
(83) (b) The evolution with time of the volume of CO2 developed
where TR is the reactor temperature, TJ is the temperature of the as a consequence of the performic acid decomposition.
jacket, and UA is the heat transfer coefficient. UA has been (c) The evolution of the temperature inside the reactor that,
estimated by independent runs of heating and cooling a known in this case, is well controlled by the thermostatic fluid and
amount of soybean oil put in the reactor and registering the is, therefore, approximately that imposed by the thermo-
change of temperature of the oil and of the thermostatting fluid, stat.
respectively, and at the inlet and outlet of the stream, the (d) The evolution with time of the volumes of the aqueous
estimated value was 300 cal/(min °C). phase considering both the addition of the oxidizing
Qcol (cal/min) is the heat exchanged between oil and aqueous mixture with a predetermined flow rate and the volume
phases during the addition of the oxidizing mixture. The subtracted for the withdrawn samples to be analyzed.
oxidizing mixture is normally added at room temperature (20− (e) The evolution with time of the pH of the aqueous phase
25 °C), while the oil is preheated at the reaction temperature solution.
(60−65°C). (f) The evolution with time of the oil residual in the reactor as
Qcol can be calculated with the following relation a consequence of the withdrawn samples to be analyzed.
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Figure 1. Evolution with time of the iodine number and epoxide Figure 3. Evolution with time of the iodine number and epoxide
number for run 2 of Table 1. The lines correspond to simulation number for run 4 of Table 1. The lines correspond to simulation
profiles, and the symbols correspond to experimental data. profiles, and the symbols correspond to experimental data.

In Figure 2, for example, it can be seen how the amount of ously monitored, and in Figure 4, we can appreciate the
oil in the reactor diminished for the withdrawn sample simulation of the temperature profile obtained with the model
and how the volume of the aqueous solution changed described in this paper (run 6 of Table 1). Obviously, for this
during the run time. different reactor, both the thermal parameter UA and the mass
(g) The thermal profile of the reactor. transfer coefficient were different, respectively, equal to 40 (cal/
(h) The heat exchanged with the thermostatting fluid. (min °C)) and 50 (1/min).
As mentioned above, in Figure 3 is reported, as example, the As already mentioned, all of the runs of Table 1 have been
simulation of the kinetic data of run 4 of Table 1. In this case simulated, and in Figure 5, reporting a parity plot for both the
also, the obtained agreement is quite satisfactory considering the iodine and the oxirane number, it is possible to appreciate the
large number of parameters imposed and not adjusted by fitting, obtained agreement that is quite satisfactory considering the
because they are derived by independent sources, as previously large number of parameters employed in the model. The two
explained. The kinetic parameters employed for the simulations runs, described in our previous work,13 have also been simulated
are collected in Table 2. The imposed parameters derived from and reported in the parity plot.
an independent way are reported in the same table in bold font,
and the remaining are determined by fitting. 4. CONCLUSIONS
The improved biphasic kinetic model has also been tested The kinetics of soybean oil epoxidation was studied considering
with satisfactory results on two kinetic runs performed in a all of the occurring reactions and the existence of two phases,
previous work,13 in the presence of H3PO4 as a catalyst. In these polar and apolar. An improved biphasic model has been
runs, a few samples were withdrawn, but as the reactor was developed. The kinetics of performic acid formation and
poorly stirred with a magnetic bar, the efficiency of heat removal decomposition and the kinetics of epoxide ring-opening reaction
was low and the temperature inside the reactor significantly were determined independently, and their kinetic laws and
increased during the reaction. The temperature was continu- related parameters are taken from works12,24 previously

Figure 2. Evolution with time of residual oil volume and mass, in the first plot, and of the volume of the aqueous phase in the second plot (run 2 of
Table 1).

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Table 2. Kinetic Parameters Used in the Simulation of the Runs of Table 1a

constants dimension value Ea (cal/mol) ΔH (cal/mol)
k1‑323 L2/(mol2 min) 0.078 19 830
K1‑298 1.6 −2390
k2‑323 (1/min) 0.0084 23 180
k3‑323 L/(mol min) 0.120 ± 0.007 24 890 ± 1540
k4‑333 L2/(mol2 min) 5.2 × 10−6 21 000
k5‑333 L2/(mol2 min) 2.5× 10−7 10 750
UA cal/(min °C) 300
βiaq 1/min 400 ± 34
a
The Parameters in Bold Font Are Imposed, and the Others Have Been Obtained by Mathematical Regression Analysis.

■ AUTHOR INFORMATION
Corresponding Author
Elio Santacesaria − CEO of Eurochem Engineering LtD, 20139
Milan, Italy; orcid.org/0000-0002-3310-8734;
Email: [email protected]
Authors
Rosa Turco − NICLDepartment of Chemical Science,
University of Naples Federico II Italy, Complesso Universitario
di Monte Sant’Angelo, 80126 Naples, Italy
Vincenzo Russo − NICLDepartment of Chemical Science,
University of Naples Federico II Italy, Complesso Universitario
di Monte Sant’Angelo, 80126 Naples, Italy; orcid.org/
0000-0002-1867-739X
Martino Di Serio − NICLDepartment of Chemical Science,
University of Naples Federico II Italy, Complesso Universitario
di Monte Sant’Angelo, 80126 Naples, Italy; orcid.org/
Figure 4. Temperature profiles of run 6 of Table 1; data from
0000-0003-4489-7115
Santacesaria et al.13 published with the permission of Elsevier Riccardo Tesser − NICLDepartment of Chemical Science,
Copyright 2011. The red line is experimental, the blue line is simulated, University of Naples Federico II Italy, Complesso Universitario
and the green line is the temperature profile of the thermostatting fluid. di Monte Sant’Angelo, 80126 Naples, Italy; orcid.org/
0000-0001-7002-7194
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.0c04530

Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
Thanks are due to Desmet Ballestra Co. and Eurochem
Engineering for the financial support.

■
am
LIST OF SYMBOLS
specific surface area [m2/m3]
Cp specific heat [cal/(°C g)]
E aj activation energy of reaction j [cal/mol]
Ftot total molar feed rate [mol/min]
Hi partition coefficient
[i] concentration of component i [mol/L]
Figure 5. Parity plot related to the comparison of the experimental and [i]* concentration of component i at liquid−liquid inter-
calculated values of, respectively, oxirane number and iodine number. face [mol/L]
Ji mass transfer rate [mol/(L min)]
kj kinetic constant of reaction j [units dependent on the
rate]
published by us on the specific subject. The kinetic law of the kj(Tkref) kinetic constant of reaction j at Tref [units dependent
epoxidation reaction and related parameters were determined on the rate]
and successfully employed for simulating all of the experimental Kj equilibrium constant of reaction j
runs of soybean oil epoxidation performed under different Kj(Tkref) equilibrium constant of reaction j at Tref [units
operative conditions. dependent on the rate]
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

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