R. J. J.
Jachuck
*a,
D. K.
Selvaraj
a and
R. S.
Varma
b
aProcess Intensification and Clean Technology (PICT) Group, Department of Chemical and Biomolecular Engineering, Clarkson University, Potsdam, NY – 13699, USA. E-mail: rjachuck@clarkson.edu
bNational Risk Management Research Laboratory, US Environmental Protection Agency, 26 West MLK Drive, MS 443, Cincinnati OH – 45268, USA
First published on 14th November 2005
In the past two decades, several investigations have been carried out using microwave radiation for performing chemical transformations. These transformations have been largely performed in conventional batch reactors with limited mixing and heat transfer capabilities. The reactions were performed under adiabatic conditions where the enhancements in the reaction rate reported in these publications may be due to the rapid increase in the reaction temperature during the course of the reaction. The concept of process intensification has been used to develop a narrow channel reactor that is capable of carrying out reactions under isothermal conditions while being exposed to microwave irradiation. Oxidation of benzyl alcohol to benzaldehyde has been carried out using the above-mentioned isothermal micro reactor. Results and the findings of this investigation are discussed in this paper.
Benzaldehyde is one of the most industrially useful members of the aromatic aldehyde family. It is used as a raw material for a large number of products in organic synthesis, including perfumery, beverage and pharmaceutical industries.14 Microwave oxidation of benzyl alcohol into benzaldehyde using clayfen was studied by Varma and Dahiya15 and it was found that microwaves did play an influential role in increasing the rate of the reaction.
As part of this investigation, it was intended to design, fabricate and study the performance of a micro reactor capable of operating isothermally under a microwave field. The aim of the study was to investigate the oxidation of benzyl alcohol and obtain experimental data to prove conclusively that the rate enhancement observed by Varma and Dahiya was due to a true microwave influence, such as rotational movement of the bonds, and not just a temperature effect.
Fig. 1 Schematic of the experimental setup. |
The reactor was designed and developed by the PICT group at Clarkson University. Fig. 2 shows that the micro reactor consisted of two main sections: an aluminium section and a Poly Tetra Fluoro Ethylene (PTFE) section, used for the heat transfer side and the reaction side respectively. The overall heat transfer coefficient of the reactor, U, was found to be about 2.5 kW m−2 K−1. The heat generated due to the exposure to a microwave (MW) environment on the reaction side was rapidly absorbed by the heat transfer fluid (H2O) on the heat transfer side. The materials used in the construction were carefully selected in order to allow near 100% transparency to microwave in the reaction zone and 0% transparency on the heat transfer side. The reactor had a volume of 2.7 × 10−7 m3 in the reaction zone and 6 × 10−6 m3 in the heat transfer zone.
Fig. 2 Isothermal continuous narrow channel reactor. |
The following is the chemical reaction studied under the influence of microwave irradiation:
The reactant was prepared at room temperature by dissolving solid Fe(NO3)3·9H2O (98+% ACS Reagent) in the benzyl alcohol solution (99+% ACS Reagent). The mixture was stirred thoroughly and filtered using a Fisherbrand® filter paper. Experiments were performed using the continuous isothermal reactor under the influence of microwave irradiation for a range of residence times (3–17 s) corresponding to different flow rates (1–5 ml min−1) and different microwave intensities (0 W to 39 W). The feed was pumped through the reactor using an HPLC pump (Model: LKB Bromma 2150) and the heat transfer fluid (water) was circulated through the heat transfer zone of the reactor at 120 ml min−1 by using a peristaltic pump (Model: Cole Parmer Instrument Co. 7520-01).
In order to benchmark the performance of the narrow channel reactor under the influence of microwaves, several batch experiments were also carried out without exposure to the microwaves. Limited tests were carried out using a PTFE capillary reactor under microwave irradiation to investigate the rate of reaction under adiabatic conditions. These experiments were carried out under non-isothermal conditions by passing the reactants continuously through the narrow channel PTFE tubing for similar residence times as in the isothermal continuous narrow channel reactor.
The inlet and the outlet temperatures of both the reaction and the heat transfer fluid were monitored continuously using a PICO temperature recorder. All the thermocouples were of K type with an error of ±0.3 °C. Analyses of the results were performed in a Mattson Galaxy Series FTIR-5000. Fig. 3 shows the distinct peaks of benzyl alcohol, in the region of 3100–3600 cm−1 and benzaldehyde in the region of 1670–1720 cm−1. Calibration was done using pure benzyl alcohol and benzaldehyde (99.5+% ACS Reagent) solutions. The peak height ratios obtained from the calibration data were used to find the conversion percentage to benzaldehyde from oxidation of benzyl alcohol. Benzyl alcohol and benzaldehyde peaks in the FTIR spectrum obtained from experimental samples were compared with the FTIR library from Mattson Instruments Inc. Peaks obtained from the samples matched accurately with the peaks of the library spectrum. The findings of the experimental investigations for the above conditions have been discussed in the following section.
Fig. 3 FTIR Graph showing the peaks of benzyl alcohol and benzaldehyde. |
(1) Negligible temperature differential (ΔT) between the inlet and the outlet temperature of water (on the heat transfer side), when flowing through the heat transfer side without any reactant flow and the microwave turned off. This was essential in order to prove that any ΔT seen in the inlet and outlet water temperature was due to the heat generated by the reaction when the reactant is exposed to a microwave environment. As can be seen in Table 1, ΔT = 0.2 °C, which is well within the experimental error range.
Condition | Water inlet (T1)/°C | Water outlet (T2)/°C | (T1 − T2); ΔT | Reactant inlet (t1)/°C | Product outlet (t2)/°C | (t1 − t2); Δt | Conclusion |
---|---|---|---|---|---|---|---|
Microwave off | 21.9 | 22.1 | 0.2 | — | — | — | Negligible temperature rise due to friction |
No reactant flow | |||||||
Microwave on | 22.7 | 23.0 | 0.3 | — | — | — | Effective microwave shielding of the cooling compartment |
No reactant flow | |||||||
Microwave on | 22.7 | 25.9 | 3.2 | 21.7 | 21.9 | 0.2 | Water absorbing heat. Reaction under isothermal conditions. |
Reactant flow |
(2) Under the influence of microwaves, with no reactant in the reaction zone, the ΔT in water stream (heat transfer side) remained negligible. This was important to prove that the microwave did not penetrate the heat transfer side but only penetrated the reaction side, as can be clearly seen in Table 1.
(3) The heat generated on the reaction side when the reactor system was exposed to microwave was completely absorbed by the water flowing on the heat transfer side. This test was essential in order to prove that during the course of the reaction there was negligible rise in the reaction temperature (<0.3 °C), ensuring the system was operating under isothermal conditions. As seen in Table 1, when the reaction was operated with both the reactant and the heat transfer fluid flow in their respective chambers coupled with microwave irradiation, a ΔT of 0.2 °C at the reaction zone and a ΔT of 3.2 °C at the heat transfer zone were measured. This clearly showed that the heat generated by the microwave irradiation and the heat of reaction was absorbed by the heat transfer fluid, thus providing isothermal characteristics to the reactor.
This set of experiments clearly proves and validates our claims that the reactor fabricated is, indeed, an isothermal one suitable for operation under the effect of microwave irradiation.
Fig. 4 Conversion of benzyl alcohol as a function of residence time under isothermal conditions. |
Flow rate/ml min−1 | Residence time/s | Re = DhVmρ/μ |
---|---|---|
D h = hydraulic diameter, m; Vm = velocity, m s−1; ρ = density, kg m−3; μ = viscosity, kg m−1 s−1. | ||
1 | 17 | 3.14 |
1.3 | 13 | 4.09 |
1.7 | 10 | 5.35 |
2 | 8.4 | 6.29 |
3 | 5.6 | 9.44 |
4 | 4.2 | 12.58 |
5 | 3.4 | 15.73 |
Fig. 5 Comparison under adiabatic and isothermal conditions. |
Fig. 6 Influence of microwave intensity on benzyl alcohol conversion under isothermal conditions. |
Residence time/s | Microwave intensity (%) | Conversion (%) | Power/W |
---|---|---|---|
17 | 100 | 75.39 | 38.7 |
17 | 80 | 71.56 | 37.2 |
17 | 60 | 59.33 | 28.3 |
17 | 40 | 47.82 | 22.0 |
17 | 20 | 30.50 | 17.0 |
17 | 0 | 8.37 | 0 |
Fig. 7 Equivalent time to convert 100 ml of benzyl alcohol using different methods. |
Conditions | Residence time | Conversion (%) |
---|---|---|
Batch mixing at room temperature (21 °C) | 18 hours | ∼30 |
Batch mixing at 50 °C | 6 hours | ∼40 |
MW assisted isothermal continuous reaction using iron (III) nitrate | 17 seconds | 75 |
MW assisted adiabatic continuous reaction using iron (III) nitrate | 75 seconds | 96 |
MW assisted batch reaction using clayfen15 | 15 seconds | 92 |
Fig. 8 Determination of the order of reaction under isothermal conditions. |
Fig. 9 Determination of the order of reaction under adiabatic conditions. |
The rate constant, k, for the continuous isothermal oxidation of benzyl alcohol under the effect of microwave irradiation was determined to be 0.0176 l mol−1 s−1. The rate law for the isothermal reaction was found to be −rA = 0.0176[A]2, where A = benzyl alcohol. Similarly, the rate constant for the same reaction under adiabatic conditions was found to be 0.029 l mol−1 s−1. The rate law was found to be −rA = 0.029[A]2 for adiabatic oxidation of benzyl alcohol under the influence of microwave irradiation.
The findings of this research have wide ranging implications in not just promoting the concept of green technology, but also addressing the potential commercial opportunity for using a microwave environment for producing chemical feedstock. This reactor in its current form is particularly suitable for high value, low throughput problems seeking high yield, selectivity and conversion. There are several reactions reported in literature which result in products with high selectivity5–11 and sometimes unique structures12 when microwave radiation is used to initiate the reaction. These reactions, we believe, can be carried out continuously in an isothermal narrow channel reactor.
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