360 “Volumetric and selective heating in agriculture and chemistry applications GS. Vijaya Raghavan’, Jianming Dai, Predrag S. Sunjka Department of Bioresource Engineering, Macdonald campus of McGill University, 21,111 Lakeshore road, Ste-Anne-de-Bellevue, QC, H9X 3V9, Canada. ABSTRACT Microwaves of 2450 MHz have been attracting attention from researchers of various fields. The most distinguished characteristics of microwave from conventional heating are volumetric and selectivity. Due to these characteristics, when combined with convective air, microwave-assisted drying can greatly reduce drying time and energy usage to achieve certain moisture content, These characteristics also make it possible to combine this highly efficient heating method with vacuum ying by passing the energy through a microwave-transparent vacuum chamber. Microwaves also have various applications in chemistry such as extraction of natural products from plant materials and microwave-assisted synthesis. In this paper, the work conducted in ou lab onthe applications of misrowave energy in agiclture and chemistry is briefly reviewed ‘Keywords: Microwaves, drying, extraction, organic synthesi, volumetric heating 1, INTRODUCTION Microwaves are electromagnetic waves with frequencies in the range of 300 MHz to 30 GHz. Besides their intensive applications in RADAR and telecommunications as carriers of signals, microwave energy has found its way into many other areas such as drying, food processing, and various chemistry applications'*. In order to prevent interference with the telecommunications, certain frequencies have been allocated for industrial, scientific, and medical (ISM frequencies) spplications. Among these frequencies, the most commonly used frequencies are 2450 and 915 MHz. Especially the 2450 MHz is used in domestic microwave oven and most commercial microwave-assisted chemistry instruments. “The most distinguished characteristics of microwave energy ae its volumetic and selective heating. As result, the introduction of this energy form into processes like drying food processing and various chemical processes leads to some common phenomena including the reduced processing rate, beter product quality, energy saving and environmentally friendliness. In the following sections, the microwave-matter interaction, how they affect various processes and the more detailed applications of microwave energy in various processes will be discussed. 2. MICROWAVE-MATTER INTERACTION ‘Two major mechanisms are involved in the microwave-matter interaction: dipolar rotation and joni conduction. By fie conduction, ions are accelerated by elect fields causing them to move towards the direction opposite to their own polarity. TH * Vijayaaghavan@megilla; Phone: 1-514-398 87313Fax: 1-514-398 8387 cronave and Opts! Tecnology 2009, ete by oni iroday Hetovay Barmal & Hevet Proceedings of 3 Ye (GP Beinghar WA 200) a7? asxoaate car 1.1117novernent ofthe fons provokes collisions with te morules ofthe material such as water molecules and in consequence causing the collision between the water molecules. A disordered kinetic energy created and in consequence heat is generated Fr non-ionic materials, dipolar rotation is the dominant mechanism. The Encrgy level of microwaves corresponds to the roatonal energy level of polar molecules. Therefore the interaction of microwave energy with matter is through the sls roaton ofthe molecules. For example, polar molecules subjected to microwave irradiation at 2480 MHz will rotate 2.45 x {mes in a second. The friction between the fast rotating molecules generates heat, In either ionic conduction or dipolar rotation, the heating is volumetric, which means the heat is generated through ou the commodity instead of transferring from the surfsce to the inner part as its the case in conventional heating metho. -The physical parameters that measure the micowave-matter interaction include ion conductivity (0), dielectric constant (€*) and the loss factor (e"). The ionic conductivity measures the performance of heating by ‘onic conduction mechanism. Its important in drying processes when plenty of water and electrolytes exist bu less important in most organic chemistry processes when nly organic compounds are involved. The dielectric constant describes the capability of molecules 0 be polarized by electric field andthe loss factor measures te efficiency of molecules to convert microwave energy into heat”. The following equation is sed to calculate the energy ebsorption: P, = 2afe,e"\El wo ‘Where: Pyis the energy developed per unit volume (Wim) fis the frequency (Hz) «is the absolute permitivity of vacuum (Fie) [Bis the elecurc field strength inside the load (V/m), 3, VOLUMETRIC HEATING IN DRYING PROCESSES _Doying of agricultural and food products is an important method for preservation and production of a wide variety of products. “The aim isto prolong storage life. Unfortunately, changes in the physical and biological structures ae inevitable because ofthe product is being treated with thermal, chemicel andor other treatments", Microwaves are suitable for drying, because it offers final product with higher quality than majority of existing methods. Ina drying process, the aim is to remove water from the commodity, Many methods ean be used to facilitate this process e.g ‘convective air, osmosis, and vacuum. The application of heat will accelerate the process in most cases and the introduction of microwave energy will lead to some significant improvement compared with conventional heating methods. 3.1, Microwave-convective drying. tn convective drying, dry sir is used to take away surface water from the commodity therefore creating a pressure gradient between the surface and inner part causing water migration from inside the commodity to the surface. In this process, the increased temperature will enhance the ability of dy air to remove water from the surface and inerease the water migration rate wvithin the commodity. The conventional way of energy supply is mainly through conduction, which means energy transfer from Pree. of SPIE Vol. 8445 361the surface to the inner part. It will take time to reach equilibrium in the process. However with microwave heating, the is heated volumetrically, which means throughout the commodity, and it reacts instantly without causing overheating of the commodity which is crucial for most food or agricultural product involved in drying. As a result of microwave heating, vaporis generated quickly inside the product so that the pressure inside rises very fas. A pressure gradient is thus created and the water (often as vapor) is “pumped” outside, The absorption of MW by a sample depends on its dielectric properties, which are positively correlated with the water content. Because of this phenomenon, the distribution of power in MW drying is selfcontrolled. The areas that receive more power than others dry quicker and will therefore absorb less power later in the process. However, this non-uniform distribution of temperature can lead, when the power level is set to high, to overheating and buming of dry areas. This occurrence is called thermal runaway. That means that the heat and mass transfers should be carefully balanced, 3.2. Microwave-vacuum drying ‘The main purpose of vacuum drying isto enable the removal of moisture at much lower temperature than the boiling point under ambient condition. For example, the boiling point of water will reduce to 28.96 °C at 40 mbar. The low temperature is important for many products that are heat sensitive. Further more, the absence of air especially oxygen will help preserve many components in the commodity that are easy 10 be o ized. All ofthese properties are attractive. The problem with the vacuum drying system is that with no ar, an energy transfer medium, itis hard to transfer energy efficiently tothe commodity. However, the microwave energy provides a perfect combination wih the vacuum system. One ofthe most significant characteristics of microwave energy is that it can pass through the microwave transparent materials such as glass, some plastic, and Teffon container and reach directly to the commodity. Inside the commodity it can also selectively heat the polar components mostly water causing water to boil at very low temperature. With this combination, no only the temperature can be controlled to stay low but also reach accelerated drying rate which is far superior than the conventional drying, 3.3. General advantages and disadvantages of microwave drying processes ‘Compared with the conventional drying methods, microwave drying has the following advantages and disadvantages” 1. Fast and volumetric heating ~ the heat is generated within the commodity. 2. Higher drying rate ~ the volumetric heat generation leads to higher internal temperatures causing the increase in intemal vapour pressure, which helps to push water in liquid form to the surface. 3. Quality ofthe product ~ the exposure to high temperatu proteins are less damaged. shorter, thus the heat sensitive components like vitamins or 4. Reduced energy consumption ~ microwaves are absorbed only by dielectric materials (water) and therefore energy is ‘ot used for longer time to heat the material itself; also, the drying rate is higher, drying time is shorter, uniformity and selective heating is significant 5. Costs time and maintenance cos. economy is possible in energy savings, cutback of the drying time, increased capacity, reduced handling ‘The disadvantages are the following 1. High initial cost of purchase and installation of the drying equipment, as well as shortage of documented energy | savings. 362. Pros, of SPIE Vol. 54452. ‘There is some evidence ofthe aroma loss and developing of Maillard reactions responsible for generation of colour and specific aromas. 7 3. Some physical damages caused by extensive local heating. Specific sample size and shape are usually required, because it is cfficult to dry big size food with microwaves. 4, VOLUMETRIC HEATING IN CHEMISTRY APPLICATIONS. 4.1, Microwave-assisted extraction Extraction is a solid/liquid separation technique, during which the chemical components in the solids are extracted into the tiquid, and from the later components are recovered by removing the solvents, The basic mechanism involved in the separation process is diffusion caused by a concentration gradient inthe sample and the surrounding solvent, Therefore, the extraction rate ‘can be accelerated by a few methods, e.g. refteshing solvents, stirring, and increased temperature. The introduction of the microwave energy into the extraction procéss can not only increase the temperature ofthe extraction system, but also bring new characteristics into the process due to the special volumetric and selective heating properties of microwave heating. The advantages of microwave-assisted extraction as compared with the conventional heated process include the enhanced extraction rate, reduced solvent usage and higher product quaity*”*. Ganzler et al® reported the extraction of crude fat, vicine, convicine, and gossypol from seeds, foods and feeds with microwave-sssisted extraction method and conventional Soxhlet extraction method. The results showed in 3.5 minutes of microwave epplicetion, the yields of these compounds were comparable with those obtained with 3-hr Soxhlet extraction, Paré™ compared the microwave-assisted extraction method with the steam distillation for producing essential oil from fresh eppermint. The extraction was carried out with hexane as solvent. With 40 of microwaves at 625 W, the yield was 0.371% as ‘compared to the 2-hr steam distillation to obtain 0.277%. Therefore, he suggested an increase of net profit of 94% using the sicrowave-assisted extraction method in the production of essential cil from peppermint. ‘One of the most popular interpretations of the microwave enhancement was proposed by Paré and Belanger’. They use ricrowave-transparent solvent hexane to extract essential oils from the fresh peppermint under microwave radiation. Hexane 1s @ nonpolar solvent, therefore has no absorption effect of microwave energy and is called microwave-transparent solvent. ‘When microwave is applied in such an extraction system, it travels freely through the solvent and reach the sample of interest. Inside the fresh peppermint sample, there are glands containing the components of interest. These micro structures have _memirane systems and the components are extracted tothe solvents through a diffusion process which isa long process. When microwave energy is used, the microwave can reach the sample through the solvent and sclectively heat the intemal micro structures ofthe sample which will lead to localized explosion. This will consequently cause the break of the membrane system and the flow ofthe target components into the solvent, Based on this explanation, they suggest microwave-assisted extraction could greatly accelerate the extraction rate. However, Spiro and Chen" repeated the same experiment but dealt with the scanning lectron microscope results in a statistical manner instead of picking up one micro structure suggesting thatthe rupture ofthe ‘membrane system is caused by solvent not by microwave energy. When analyzing most of the literature repors, itis observed that most of the comparisons are not on the same basis. For example in the report of Ganzler et al‘, and Pan, etal’, the comparison is based on different extraction times. A yield obtained after long extraction time does not mean they can not be obtained with shorter time. Therefore in order to compare how roo. of SPIE Vol. 5445 963 cle emeemsimamesseaemaasmssmrmmmmmmummaaitlsignificant microwave-assisted extraction over other methods, comparison on the same time basis has to be performed ss the least requirement condition and preferably the extraction performance versus time relationship to be studied. In the report of ‘Paré”, the two methods have two completely different mechanisms that can not be compared directly using the extraction time, tis therefore difficult to confirm that microwave can accelerate the extraction rate in any of these cases. ‘We have been working on the extraction of different plant materials using microwave energy. For the extraction of various part ‘of neem plant, microwave showed acceleration effect on the extrac of neem leaves, petiole while no acceleration was observed on the seed kemel and seed shell’. On the extraction of peppermint leaves, both dry leaves and fresh ones, microwave id not show acceleration effect over the reflux extraction using conventional heating method. When extracting the total ginsenosides from fresh American ginseng root, microwaves showed a little acceleration over the reflux extraction", But on another analysis using the orthogonal experimental design to study the various factor on the extraction efficiency showing the influence of different methods including the microwave-assisted extraction, reflux temperature extraction, room tempersture extraction, and ultrasonic extraction are among the least influenced factors when compared with sample to solvent ratio, extraction time, and sample particle size" 4.2. Microwave-assisted Organic Synthesis Gedye et al’ first reported the microwave energy in organie synthesis. Since then numerous numerous papers regarding the application of this special echnology in this field have been, published. Most microwave-assisted chemical reactions have been focused on the rate-enhancement of the reaction, timesaving, higher yields compared to the conventional heating methods such soil bat, heat-mantle and electric oven. We have investigated esterification reaction the microwave-assisted technique. Liao etal. (2002) reported the synthesis of parabens by esterification method using two different catalyst PTSA and ZnCl Result showed that withthe PTSA as catalyst, the reaction heated with conventional method under reflux condition for 45 min obtained a higher yield (76%) than the microwave-asssted synthesis for 25 min (41%). However using ZnCl, 2s catalyst, the conventional method obtained only 35% While the microwave-assisted one obtained 43% showing great acceleration effect. The reason why microwave energy can accelerate the same reaction with one type of catalyst while not for another catalysts sill under investigation. Itis believed to be the super heating center formed due to the existence of the inorganic compounds caused by the selectivity of microwave encrBy absorption in the matrix, 5. CONCLUSION “Microwaves interact with matter in a volumetric and selective way. This property leads to its applications in many agricultural and chemistry processes including the drying, separation and organic synthesis. The most distinguished characteristics of processes with microwave energy are the enhanced rat ofthe process and better quality of products, especially in the drying processes and microwave-asisted organic synthesis. Inthe microwave-assisted extraction processes, although there ae 2 lot of positive results regarding the rate enhancement, more evidence has tobe collected before deciding whether they really enhence 2 process and to what extent does it enhance. 364 Proc. of SPIE Vol. 5445ACKNOWLEDGEMENT ‘authors acknowledgement the financial support from the Natural Science and Engineering Research Council of e ™ REFERENCES TN. Tulasidas. G.S.V. Raghavan,; and E.R. Norris. Microwave and convective drying of grapes. Transactions ofthe ASAE. 36(6) p. 1861-1865, 1993. Hulls, PJ. Development of the industrial use of dielectric heating in the Power. 17(1), 29-38, 1982. RE, Mudgett. Microwave food processing. Food Technology. 43 (1), 117-126, 1989. RV. Decareau, Microwave food processing: today and tomorrow. Activities Report of the R & d Associates. 35(I) p. 41-49, 1983, 5. R.Gedye, F. Smith,; K. Westaway,; H. Alis L. Baldisera, L. Laberge,; and J. Rousel. The use of microwave ovens for rapid organic synthesis. Tetrahedron Lett. 27(3): 279-82, 1986. 6. K.Ganzler A. Salgo,; and K. Valko, Microwave extraction: a novel sample preparation method for chromatography.” Journal of Chromatography. 371: 299-306, 1986. 7. IR. Pate, and J, M. R. Belanger. Microwave-Assisted Process (MAP): a new tool for the analytical laboratory Trends Anal. Chem. 13(4), 176-84, 1994. Inited Kingdom. Journal of Microwave Yaylayan, V.A.; Raghavan, G. S. V.; and J. R. Paré, Extraction and colorimetric determination of azadirachtin related limonoids in the neem seed kemel. J. Agric. Food Chem, 47, 3738-3742, 1998. 9X. Pan; H.Liu; G. Jia; and. Shu. Microwave-assisted extraction of glycytthizic acid from licorice root. Biochem. Eng. J. $(3), 173-177, 2000, 10. DML. Mingos and D.R. Baghurst. Application of micrgwave dielectric heating effects to synthetic problems in ‘chemistry. Chemical sociery reviews, 20: 1, 1991 : 11. C. Ratti and A'S, Mujumdar. Drying of fits, in Processing fruits: Science and Technology, Biology, Principles and Applications, Somogyi LP., Barrett D.M., Hui Y.H., Technomic Publishing Company, Inc, 1996, 12, ESange; AS. Mujumdar, and GS.V. Raghavan. Principles and Applications of Microwave Drying. In: Drying ‘Technology in Agriculture and Food Sciences. Edited by A.S. Mujumdar. Science Publishers, Ine. Enfield, NH. 313 pp, 2000. 13, JLRJ.Pasé, US patent $48897. Various international counterparts, 1995. 14, M. Spiro and S. S. Chen. Kinetics of isothermal and microwave extraction of essential oil constituents of peppermint leaves into several solvent systems. Flavour Fragrance J. 10(4), 259-72, 1995, 15. J.Dai, GS. V. Raghavan and M. Ngadi. Extraction of Ginsenosides from American Ginseng (Panex quinquefolium L.) Root with Different Extraction Methods. Submitted to J. Agric. Food Chem. 16. 5. Dai, GS.V. Raghavan, E, Quintas, and M, Ngadi. J. Dai, Investigation of Different Factors on the Extraction of Ginsenosides from fresh American Ginseng (Panax quinquefolium L.) Root. Presented at the CSAE annual meeting. Paper #03-333. July 6.9, Montreal, Canads, 2008. 17. X, Liao, ,G.S.V. Raghavan, and V.A. Yaylayan, A novel way to prepare n-butylparaben under microwave irradiation. ‘Tetrahedron Letters 43(2002):45-48, 2002 Proc. of SPIE Vol. 5445 985,APPENDIX Figure 1 depicts the difference in moisture ratio change for MWiconvective and convective dried grapes. The difference i ‘obvious, for example, 15% of moisture is achieved after 5 hours for MW/convective, and after 12.5 hours for convective process. MW power density has a significant influence too, which can be seen in Figure 2, higher MW power density offers, shorter process. Table I compares the MW/eoavective and MW/vacuum using two factors - MW density and MW mode indicating the MW vacuum combination is far more energy efficient than the MW/convective combination. 1 2 08 i. - 506 Convective 2 - 50.4 “ ° Microwave = ° bs § 10 15 20 Time, hours ° Figure I: Drying curves for grapes under convective and combined convective and microwave drying (air at 50°C) 2004 O° Convection with reat. Fo. wig F oat + 03Wig % Convection no treat. 8 x 8 Ws ° 0 90 180 270 360 450 540 630 720 Time, min Figure 2: Drying of strawberries-by convection alone and by microwave at three power levels 366 Proc. of SPIE Vol. 8445,sabe 1: MW power-on times and dying FACET for cranberries dried with rWiconvective and MW acum ‘method Ding -MWdensty —- MW mode MW poweron Drying efficiency method (we) (sons off) time (min) (egvaedMD) 1.00 3030 3. ~SOt(«Oa Mw 100 30/60 ns 012 convective 125 3030 a0 125 30060 586 on = 1.00 3080 a oe MW! 3014s 013 vemm (125 aint tess oe O38 125 3045 213 030 Figure 3 shows the comparison of different exact snethods on the extraction of various parts of the neem plant. It showed that forthe extraction of leaf and petiole, rjerowave-assisied extraction showed accelerated effect ‘atracton, but sot forthe extraction of seeds andthe seed shells. cover reflux 400 = (BMAE ORTE RFX Recovery (%) Seed Seedshell Leaf Petiole Figure 3. Comparison of % recovery of AZRL BY rricrowave (150 W) assisted extraction (MAE), root temperature (RTE), and reflux (REX) methods for 20 minues using vvathanol (recoveries are calculated bast on 24h exracton St room temperature with methanol). Average of tree rplcae. Proc. of SPIE Vol. 5485 967 —eEEE