ISSN 0023-1584, Kinetics and Catalysis, 2018, Vol. 59, No. 4, pp. 504–508. © Pleiades Publishing, Ltd., 2018.

Original Russian Text © G.S. Dmitriev, A.V. Terekhov, L.N. Zanaveskin, A.L. Maksimov, S.N. Khadzhiev, 2018, published in Kinetika i Kataliz, 2018, Vol. 59, No. 4, pp. 488–492.

Kinetics of the Formation of Solketal in the Presence of Sulfuric Acid

G. S. Dmitrieva, *, A. V. Terekhova, L. N. Zanaveskina, A. L. Maksimova, and S. N. Khadzhieva, †
aTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
*e-mail: dmitriev.gs@mail.ru
Received September 5, 2017

Abstract—The kinetics of reversible solketal synthesis in the presence of sulfuric acid as a catalyst is studied.
The parameters of kinetic equations describing direct and reverse reactions are found.

Keywords: solketal, glycerol, acetone, sulfuric acid, kinetics

DOI: 10.1134/S002315841804002X

INTRODUCTION automotive fuels produced from natural renewable raw

2,2-Dimethyl-4-hydroxymethyl-1,3-dioxolane materials [1]. Solketal is formed from a reaction of
(solketal) belongs to a new type of component for glycerin with acetone:

O OH + H2O
O (I)

H+
2,2-Dimethyl-4-hydroxymethyl-1,3-dioxolane
HO OH + H+
OH
OH O
glycerol acetone + H2 O (II)
(GL) (AC) O O
2,2-Dimethyl-1,3-dioxan-5-ol

Simultaneously, a zolketal isomer, 2,2-dimethyl-
1,3-dioxan-5-ol, is formed.
In the presence of acid catalysts the reaction pro-
ceeds fairly quickly even at room temperature. Zeolites
[2–8] or ion-exchange resins [2, 4–9] can be used as
heterogeneous catalysts. Acids, for example, H2SO4,
are used as homogeneous catalysts [8, 10]. Sulfuric
acid is the most active catalyst and hence the techno-
logical scheme for the production of solketal in the
presence of H2SO4 is considered to be the most ratio-
nal scheme [8].
The optimization of the reaction unit is an import-
ant stage in the development of this processing
scheme. For the solution of this problem, a kinetic
model of the reaction should be considered. However,
no information on this model was found in the litera-
ture. Thus, this paper aims to determine the kinetic
† Deceased.
parameters for the synthesis of solketal in the presence
of sulfuric acid.
EXPERIMENTAL
Glycerol (analytically pure), acetone (chemically
pure), sulfuric acid (chemically pure), and a 0.1 M
solution of NaOH were used as the reagents in the
experiments.
The experiments were carried out in batch and
continuous mixing reactors at the initial molar ratio of
glycerol : acetone = 1 : 5. Previously, this component
ratio was shown to be optimal [8], as a relatively high
conversion of glycerol (~80%) can be achieved at this
ratio with reasonable costs for the separation of reac-
tion products by rectification.
In the batchwise experiments, 25 g of glycerol (GL)
and 80 g of acetone (AC) were introduced into a 200-mL
glass reactor, equipped with a jacket, a reflux con-

504
 KINETICS OF THE FORMATION OF SOLKETAL
denser, and a thermocouple sleeve. The reaction mix-
ture was stirred with a magnetic stirrer. The tempera-
ture in the reactor was regulated by feeding a heat car-
rier to the jacket. After the predetermined temperature
was reached, 0.0036–0.1215 g of the catalyst (sulfuric
acid) was introduced to the reactor under continuous
stirring of the reaction mixture. The catalyst concen-
tration in the reaction mixture ranged from 3.3 × 10–3
to 1.2 × 10–1 wt %. The reaction time was started from
the moment the catalyst was introduced. After
homogenizing the reaction mixture, the reaction mix-
ture was sampled and analyzed.
In experiments in the continuous mode, a 130-mL
electrically heated glass reactor equipped with a stirrer,
a reflux condenser, a thermocouple sleeve, and a side
outlet was used. The rotation speed of the stirrer was
1200 rpm, providing the efficient mixing of the reac-
tion mass. The temperature in the reactor was moni-
tored using a set consisting of a single-channel micro-
processor programmable temperature meter TRM-
101, an external relay, and a transformer. The standard
reaction temperature was 35°C. Glycerol containing
0.066 wt % of sulfuric acid was continuously fed into
the reactor with a pump at a flow rate of 16.5 g/h.
Independently, acetone was introduced into the reac-
tor at a flow rate of 52 g/h. The contact time was
1.73 h. The reaction products were removed from the
reactor top through the side outlet. Only the experi-
ments with temperature fluctuations of less than 1°C
and a material balance accuracy better than 5% were
taken into account.
The reaction products were analyzed using a Tsvet-
800 gas-liquid chromatograph (OAO Tsvet, Russia)
−
H OH
δ H+
C+ O + O CH2
δ
Acetone HO CH
CH2OH
Glycerol
O CH2
C C
O+ CH
+
C O CH2 H CH2OH
HO CH
O CH2
HO CH2
C CH
O+ CH2
H 2,2-Dimethyl-1,3-dioxan-5-ol
In the first stage, the nucleophilic addition of glycerol
to the carbonyl group takes place to form a semiketal. In
KINETICS AND CATALYSIS Vol. 59 No. 4
505
equipped with a column (3 mm × 2 m) packed with a
Polysorb-1 phase.
RESULTS AND DISCUSSION
At the initial instant of time the reaction proceeds
in a two-phase system due to the limited miscibility of
glycerol with acetone. As the products (solketal and
water) accumulate, the reaction mixture becomes
homogeneous. The kinetics of the reaction were stud-
ied, taking into consideration only the data obtained
after the complete homogenization of the system. A
typical view of the accumulation curves for organic
products (2,2-dimethyl-4-hydroxy-methyl-1,3-diox-
olane and 2,2-dimethyl-1,3-dioxan-5-ol) is shown in
Fig. 1.
It can be seen that 2,2-dimethyl-4-hydroxy-
methyl-1,3-dioxolane is the main product and the
concentration of 2,2-dimethyl-1,3-dioxane-5-ol
decreases with time. The formation of 2,2-dimethyl-
4-hydroxymethyl-1,3-dioxolane is likely to be ther-
modynamically more advantageous and the initially
formed 2,2-dimethyl-1,3-dioxan-5-ol isomerizes in
the synthesis until equilibrium is reached.
The fraction of 2,2-dimethyl-1,3-dioxane-5-ol in
the equilibrium mixture is less than 2–3%. Besides,
both isomers can be used as a fuel component. Thus,
the kinetics of glycerol ketalisation were studied taking
into account the total number of isomers. Further, the
isomer mixture is referred to as solketal.
According to the existing concepts on the forma-
tion mechanisms for semiketals (hemiacetals) and
ketals (acetals) [13, 14], the preparation of solketal can
be described by the following sequence of reactions:
+
H+ +
C O CH2 C O CH2 + H2O (III)
HO CH HO CH
CH2OH CH2OH
O CH2
+ H +. (IV)
O CH
CH2OH
2,2-Dimethyl-4-hydroxymethyl-1,3-dioxolane
O CH2
HO C CH HO + H+. (V)
O CH2
the second stage, a cyclic ketal is formed through the inter-
mediate formation of a carbenium ion. The formation of a
2018
506 DMITRIEV et al.

Concentration, wt % Concentration of SK, mol/L

30 1.8
1.7 1
25 2
1 1.6 3
20
1.5
15
1.4
10 1.3
5 1.2
2
1.1
0 100 200 300 400 500 0 100 200 300 400 500
Time, min Time, min

Fig. 1. Time dependence of concentrations of 2,2- Fig. 2. Time dependence of solketal concentration in reac-
dimethyl-4-hydroxymethyl-1,3-dioxolane (1) and 2,2- tion mixture at different concentrations of sulfuric acid,
dimethyl-1,3-dioxan-5-ol (2) in batch reactor at 30°C. Load- wt %: (1) 1.2 × 10–2; (2) 6.5 × 10–3; (3) 3.3 × 10–3. Reaction
ing: glycerol, 25 g; acetone, 80 g; sulfuric acid, 0.0036 g. temperature, 30°C; loading: glycerol, 25 g; acetone, 80 g.

carbenium ion is assumed to be the limiting stage of the Integrating Eq. (2) allows the time dependence of
process. At the same time, the carbenium ion is an inter- the glycerol concentration to be estimated:
mediate in the isomerization of 2,2-dimethyl-1,3-dioxan-
5-ol to 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane. 1
(K1 − K 2 )τ =
According to the mechanism mentioned above, the (С GL
(1)
− С GL
(2)
)
formation of solketal should be described by the fol- (3)
lowing kinetic equation: СGL,0 − С GL
(1)
СGL − С GL
(2)
× ln = Y.
СGL,0 − С GL СGL − С GL
(2) (1)
w = k1СH2SO4CGLСАC − k2СH2SO4 СSKСН2О, (1)
where Сi are the molar concentrations of glycerol, ace- Here τ is the reaction time, CGL is the current concen-
tone, solketal (SK), water, and sulfuric acid in the tration of glycerol (mol/L), CGL0 is the initial concen-
reaction mixture (mol/L); k1 is the constant of the
direct reaction rate for the formation of solketal tration of glycerol (mol/L), and С GL
(1)
and С GL
(2)
are the
(L2 mol–2 s–1); and k2 is the constant of the reverse roots of the quadratic equation found from the expres-
sion for the equilibrium constant
reaction rate for the hydrolysis of solketal (L2 mol–2 s–1).
After the catalyst concentration is included in the K1 СSK СН2О
rate constant, Eq. (1) takes the form Kс = =
K 2 СGL САC
w = K1CGLСАC − K 2СSKСН2О, (4)
(2) (СGL,0 − СGL )(СН2О,0 + СGL,0 − СGL )
= ,
where K1 and K2 are the rate constants of the direct and С GL (САC,0 − СGL,0 + СGL )
reverse reactions, respectively (L mol–1 s–1).
The adequacy of Eq. (1) was verified experimen- where С i and Сi,0 are the equilibrium and initial con-
tally by varying the concentration of the sulfuric acid. centrations of the ith substance (mol/L), respectively.
In Fig. 2 kinetic curves describing the formation of
solketal at different concentrations of sulfuric acid In the coordinates of Eq. (3) the dependence of Y
(1.2 × 10–2, 6.5 × 10–3, and 3.3 × 10–3 wt %) are given, on τ should be a straight line starting from zero, and
with the other conditions being equal. The maximum the tangent of the slope angle is equal to the difference
conversion of glycerol was 79.5%. of the rate constants: tan α = (K1 − K2). The experi-
The experimental data were treated according to mental dependences obtained are given in Fig. 3.
Eq. (2), as the concentration of sulfuric acid in all the
experiments was the same. According to the reaction The values K1 and K2 are equal to the product of the
equation (II), the concentrations of all the compo- concentration of the catalyst (sulfuric acid) and the
nents can be expressed through the initial glycerol rate constants k1 and k2, respectively. Thus, the values
concentration. of k1 and k2 can be calculated from this formula.

KINETICS AND CATALYSIS Vol. 59 No. 4 2018

 KINETICS OF THE FORMATION OF SOLKETAL 507

Time ×10–3, s In Table 1 it is seen that the deviation of the rate

0 5 10 15 20 25 30
0.02
0.04
3 activation energy. In this range the conversion of glyc-
0.06
2 erol under equilibrium conditions ranged from 74.9 to
0.08 1 87.2%. The temperature dependences of the rate con-
0.10
Y
Fig. 3. Linearization of kinetic curves of solketal synthesis
according to Eq. (3) at 30°C and different concentrations
of sulfuric acid, wt %: (1) 1.2 × 10–2; (2) 6.5 × 10–3;
(3) 3.3 × 10–3. Loading of glycerol, 25 g; acetone, 80 g.
The equilibrium constant for the formation of
solketal in the presence of sulfuric acid in the tempera-
ture range 0–50°C is described by the equation [8]
lnK c = 1745.8 1 − 6.0.
T (mol L
According to Eq. (2), it is a first-order reaction
with respect to all the reagents. Until the equilibrium
is reached, the dependences shown in Fig. 3 are linear.
This confirmed the adequacy of Eq. (2). In Fig. 3, a
dependence of the slope of the straight lines on sulfu-
ric acid concentration is observed. The reaction rate
increases with the catalyst concentration, while the
equilibrium time becomes shorter.
In Eq. (2), K1 and K2 can be easily calculated by
Eq. (5) from the slope of the line and the equilibrium
constant at a given temperature. Having divided these
values by the concentration of sulfuric acid, we find
the rate constants for the direct (k1) and reverse (k2)
reactions in Eq. (1). The data are given in the table.
constants for the direct and reverse reactions from the
mean values is less than 2.4%. This indicates that the
experimental data are adequately described by the
kinetic equation (1).
The experiments were carried out in the tempera-
ture range from 0 to 50°C in order to determine the
stants k1 and k2 in the Arrhenius coordinates are
shown in Fig. 4.
According to the data obtained from the experi-
ments, the kinetic equations for the direct reaction of
the formation of solketal (6) and the reverse reaction
of hydrolysis (7) have the form:
−87110
w1 = 4.36 × 10 e CH2SO4CGLСАC
13 RT
(6)
−1 −1
(mol L s ),
−101670
w2 = 1.8 × 10 e
16 RT
CH2SO4CSKСН2О (7)
(5) −1
s −1).
For the industrial implementation of the process, it
is preferable to use a continuous flow mixing reactor.
The applicability of the suggested kinetic model for
the calculation of such a reactor was estimated by
comparing the experimental data with the calculation
results from the kinetic equations (6) and (7). The
conditions for a continuous flow mixing reactor were
described in the experimental section. The experi-
mental and calculated glycerol conversions were 68.4
and 69.0%, respectively. Thus, the experimental data
in both batch and continuous reactors can be assumed
to be adequately described by Eqs. (6) and (7). These
equations can be used in the calculation of the instal-
lation for the synthesis of solketal in the presence of
sulfuric acid as a catalyst.

Table 1. Results of processing experimental data obtained at different concentrations of sulfuric acid, with other conditions
being equal (30°C; glycerol, 25 g; acetone, 80 g)
Concentration of H2SO4 k1 k2
tanα = K1 − K2 Kc
mol/L wt % L2 mol–2 s–1

1.0 × 10–3 1.2 × 10–2 −1.24 × 10–5 0.77 4.11 × 10–2 5.33 × 10–2

5.8 × 10–4 6.5 × 10–3 −6.98 × 10–6 0.77 4.06 × 10–2 5.27 × 10–2

2.9 × 10–4 3.3 × 10–3 −3.11 × 10–6 0.77 3.94 × 10–2 5.12 × 10–2

Mean value 4.04 × 10–2 5.24 × 10–2

KINETICS AND CATALYSIS Vol. 59 No. 4 2018

508 DMITRIEV et al.

1/T ×103, К–1 the Federal Agency for Scientific Organizations

(FASO) Russia.
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7
0
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the Institute of Petrochemical Synthesis of the Rus-
sian Academy of Sciences with the financial support of Translated by D. Yakusheva

KINETICS AND CATALYSIS Vol. 59 No. 4 2018