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Toluene Paper PDF
Toluene Paper PDF
a r t i c l e i n f o a b s t r a c t
Article history: The effect and mechanism of the hydrophilic ionic liquids (ILs) with cobalt naphthenate as catalyst on
Received 18 January 2012 the liquid-phase oxidation of toluene were studied systematically. Five ILs with different hydrophilicities
Received in revised form 16 June 2012 were employed as reaction media. The results showed that toluene conversion increased with increasing
Accepted 18 June 2012
hydrophilicity of ILs. The toluene conversion and the corresponding selectivity of benzaldehyde reached
Available online 4 July 2012
19.6% and 19.5%, respectively, in 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim]BF4 ). The solu-
bilities of toluene, benzaldehyde, benzyl alcohol and benzoic acid in [Emim]BF4 were further measured at
Keywords:
temperatures from 299.2 K to 343.2 K. The correlations between solubility and temperature were devel-
Ionic liquids
Liquid-phase oxidation
oped based on the critical point of phase separation or ideal solution model. The low solubility of toluene
Solubility in [Emim]BF4 indicated a heterogeneous oxidation mechanism for toluene. The improvement of toluene
Toluene conversion and product selectivity in [Emim]BF4 was attributed to the interactions between reaction and
Benzaldehyde extraction separation. The sensitivity study demonstrated that the increase in oxygen pressure was ben-
Benzyl alcohol eficial to the reaction. A much lower reaction temperature of 130 ◦ C was achieved in [Emim]BF4 instead
Benzoic acid of a typical 160–170 ◦ C for current commercial plants. The high conversion, low reaction temperature
and high product selectivity for the liquid-phase oxidation of toluene in [Emim]BF4 makes it a green and
efficient hydrocarbon oxidation process.
© 2012 Elsevier B.V. All rights reserved.
0926-860X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apcata.2012.06.026
2 Y. Meng et al. / Applied Catalysis A: General 439–440 (2012) 1–7
Fig. 1. Schematic diagram of the apparatus for the liquid-phase oxidation of toluene.
2.1. Materials
Chemical reagents N-methylimidazole (99%), 1-chlorohexane Fig. 2. Schematic diagram of solubility measurement experimental apparatus.
(99%), bromoethane (99%), sodium fluoborate (98%), lithiumbis
(trifluoromethanesulfonimide) (99%), butyl-3-methylimidazolium
tetrafluoroborate ([Bmim]BF4 ) (99%), [Bmim]PF6 (99%), toluene (GC) (Shanghai Precision & Scientific Instrument Co., Ltd., Shang-
(AR), benzaldehyde (AR), benzoic acid (AR), benzyl alcohol (AR), o- hai, PRC) with a flame ionization detector (FID) and a split injector.
nitrotoluene (CR), benzyl benzoate (AR), dimethyl phthalate (AR), The chromatography column was an FFAP column, with dimen-
and cobalt naphthenate (8% Co), were purchased commercially and sions of 30 m × 0.25 mm × 0.33 m (Lanzhou Institute of Chemical
were used without further purification. Physics, Chinese Academy of Sciences, Lanzhou, China). The anal-
[Bmim]BF4 (≥99%) and [Bmim]PF6 (≥99%) were obtained from ysis methods and procedures were similar to those described in
Henan Lihua Pharmaceutical Co. Ltd. (Henan, China). [Emim]BF4 , detail previously [20].
1-hexyl-3-methylimidazolium tetrafluoroborate ([Hmim]BF4 ) and
1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 2.3. Determination of the solubilities of toluene, benzyl alcohol,
([Hmim]Nf2 T) were prepared using the procedures described pre- benzaldehyde and benzoic acid in [Emim]BF4
viously [17–19]. The synthesized ILs were confirmed by FT-IR
(Nicolet -170sx) and 1 H NMR (Bruker, AVII). The experimental scheme is shown in Fig. 2. A flat-bottom flask
with a magnetic bar was immersed in a thermostatic water bath.
2.2. Liquid-phase oxidation of toluene in ionic liquids (ILs) The solubility measurement of toluene, benzaldehyde, benzyl alco-
hol in [Emim]BF4 was performed by the following procedure. A
The reaction was performed in a batch reactor as shown predetermined amount of [Emim]BF4 was added into the flask.
schematically in Fig. 1. A stainless steel autoclave with a height After the flask was heated to the desired temperature with con-
of 100 mm and an inner diameter of 37 mm was used as the reac- tinuous stirring, the solute of toluene, benzaldehyde or benzyl
tor. The reactor was equipped with an electrical heater, a pressure alcohol was separately added dropwise into ILs intermittently using
gauge, a thermocouple, a magnetic stirrer and a pressure relief a microsyringe over an interval of 30 min. The solution was consid-
valve. The reaction temperature was controlled and monitored with ered saturated when it remained turbid for 30 min. The solubility
a Heating and Control System. was determined by the weight change of the solution before and
All experiments were performed in batch mode. Briefly, the after the dissolution of solute. The solubility values reported are
toluene, the cobalt naphthenate catalyst, ionic liquids (ILs) and the the mean values from the measurements repeated three times.
benzaldehyde initiator were added into the reactor. The reactor The solubility of benzoic acid in ILs was determined as follows:
was subsequently sealed and oxygen was charged to the desired a predetermined amount of benzoic acid was weighed and placed
pressure. After the oxygen inlet valve was closed and the stir- in the flask. When the flask was heated to the desired tempera-
ring started, the reactor was heated to the desired temperature. ture with continuous stirring, the solvent [Emim]BF4 was added
The time when the reactor reached the desired temperature was dropwise into the flask intermittently by the microsyringe over an
recorded as the start time of the reaction. The pressure was kept interval of 60 min. When the solute benzoic acid was dissolved in ILs
constant with rapid oxygen makeup. After a predetermined reac- completely and the solution became clear, the solution was consid-
tion time, the reaction was stopped by cooling the reactor with ered saturated with benzoic acid. The solubility was calculated by
tap water to room temperature. The gas in the reactor was slowly the weight change of the solution. Each measurement was repeated
released and the reaction liquid was then transferred to a separa- thrice to reduce the experimental errors.
tion funnel. The mixture was extracted thrice by 50 ml of diethyl The solubility of benzoic acid in water at 30, 40, 50, 60 and
ether to separate toluene and reaction products from ionic liquids. 70 ◦ C was measured to evaluate the accuracy and reliability of the
Diethyl ether was evaporated in a rotary evaporator. The result- measurement method. In comparison with the literature data [21],
ing liquid samples were analyzed offline by gas chromatography the maximum error was 3.47% and the average error was only
Y. Meng et al. / Applied Catalysis A: General 439–440 (2012) 1–7 3
Table 1
The toluene conversion and product selectivity with/without [Emim]BF4 as reaction
medium.
Reaction conditions: temperature 130 ◦ C, pressure 2.0 MPa, molar ratio of cobalt
napthenate/toluene 0.125%, mass ratio of [Emim]BF4 /toluene 1.6, mass ratio of ben-
zaldehyde/toluene 0.75%, toluene 7.5 g and reaction time of 1 h.
Fig. 6. Effects of the concentration of [Emim]BF4 on the liquid-phase oxidation of Fig. 7. Effects of catalyst dosage on the liquid-phase oxidation of toluene: (a) the
toluene: (a) the conversion of toluene and (b) the selectivity of reaction products. conversion of toluene and (b) the selectivity of reaction products.
Reaction conditions: temperature 130 ◦ C, pressure 2.0 MPa, toluene 7.5 g, molar Reaction conditions: temperature 130 ◦ C, pressure 2.0 MPa, toluene 7.5 g, mass ratio
ratio of cobalt naphthenate/toluene 1%, mass ratio of ILs/toluene 1.6, mass ratio of ILs/toluene 1.6, mass ratio of benzaldehyde/toluene 0.75% and reaction time 2 h.
of benzaldehyde/toluene 0.75% and reaction time 2 h.
For benzaldehyde,
H fus (Tm )
T
Cp
Tm T
ln x1 1 = − 1− − 1− + ln (7)
RT Tm R T Tm
It is assumed that Cp is negligible and the solution is consid-
ered an ideal solution, so Eq. (7) becomes,
H fus (Tm )
T
ln x1 = − 1− (8)
RT Tm
Define,
H fus (Tm )
m=
RTm
H fus (Tm )
Fig. 8. Solubilities of benzaldehyde, toluene, benzyl alcohol and benzoic acid in n=
[Emim]BF4 . R
, ♦, , : Experimental solubilities of benzoic acid, benzaldehyde, toluene and Then, Eq. (8) becomes,
benzyl alcohol respectively. —, - - -, ·······, –· –· –·: Fitting lines of the experimental
solubility of benzoic acid, benzaldehyde, toluene and benzyl alcohol respectively. n
ln x1 = m − (9)
T
extracted from the toluene phase to the [Emim]BF4 phase. More Eq. (9) is used to fit the experimental solubility of benzoic acid in
benzoic acid can migrate from the toluene phase to the [Emim]BF4 [Emim]BF4 . From Fig. 8, it is seen that Eq. (9) fits the experimental
phase due to its large solubility in the [Emim]BF4 . When the bulk data very well. The values of m and n were obtained by fitting Eq.
temperature is higher than 333.2 K, the solubility of benzoic acid (9) to the experimental data to obtain.
in [Emim]BF4 is larger than 34.7 mol%. The extraction separation 1072.91021
leads to a decrease of the product concentrations in the toluene ln x1 = 2.15133 − (10)
T
phase, which is favorable for the forward chemical reactions and
increases the final extent of reactions. Since the reaction products 4. Conclusions
can be efficiently separated from the toluene phase, the over oxida-
tion of the products are reduced to some extent. The liquid-phase Five ionic liquids (ILs) were used as reaction media for the liquid-
oxidation of toluene in [Emim]BF4 is therefore a coupling process phase oxidation of toluene. The ionic liquids with strong polarity
between catalytic reaction and extraction separation. substantially improved the reaction performance by increasing
In this study, thermodynamic criteria for phase equilibrium in both toluene conversion and benzaldehyde selectivity. On the con-
multi-component liquid systems were used to correlate the sol- trary, the conversion of toluene was low when hydrophobic ILs such
ubility with temperature. The critical point of phase separation as [Bmim]PF6 were used as reaction medium. The low solubility of
was used as a criterion for the measurement of the solubilities toluene in [Emim]BF4 indicates that the liquid-phase oxidation of
of toluene, benzaldehyde and benzyl alcohol. The one-parameter toluene in [Emim]BF4 is a heterogeneous reaction. The solubility
Margules model was used to describe the simulation. Therefore, at of reaction products, especially benzoic acid, is much higher than
the critical point of phase separation, the solubility and tempera- that of toluene in [Emim]BF4 . The improvement of toluene con-
ture should satisfy the following equation [24]: version and high product selectivity was attributed to the coupling
effect of catalytic reaction and extraction separation. The sensitivity
RT = 2Ax1 (1 − x1 ) (1)
study revealed that increasing oxygen pressure was favorable for
where A is the parameter; R the gas constant; T the temperature the reaction, and the reaction performance at 130 ◦ C, which was
(K) and x1 is the mole fraction of solute in [Emim]BF4 . much lower than the typical reaction temperature of 160–170 ◦ C
The parameter A is a function of temperature. Simply, it is for commercial plants. The results confirm that [Emim]BF4 offers
assumed, a green and highly efficient approach to perform the liquid-phase
oxidation of toluene with high conversion of toluene, low reaction
RT
A= (2) temperature and high product selectivity.
2(aT 2 + bT + c)
So, Acknowledgments
x1 (1 − x1 ) = aT 2 + bT + c (3) We would like to thank the Joint Funds of the National Science
The correlation (3) is used to fit the solubilities of toluene, ben- Foundation of China and China National Petroleum Corporation
zaldehyde and benzyl alcohol. The results are shown in Fig. 8. Eq. (Grant No. 20736009) and the Research Fund of Young Scholars
(3) fits the experiment data well, and the different coefficients are for the Doctoral Program of Higher Education of China (Grant No.
obtained for different solutes. The correlations are as follows: 20070610128) for financial support.
For toluene,
Appendix A. Supplementary data
x1 (1 − x1 ) = −6.41186 × 10−6 T 2 + 0.00711T − 1.50964 (4)
Supplementary data associated with this article can be
For benzyl alcohol,
found, in the online version, at http://dx.doi.org/10.1016/
x1 (1 − x1 ) = −5.5047 × 10−6 T 2 + 0.00703T − 1.5802 (5) j.apcata.2012.06.026.
Y. Meng et al. / Applied Catalysis A: General 439–440 (2012) 1–7 7