General presentation of microwave equipment used by the chemical industry

1. 12 PORTE DU GRAND LYON 01702 NEYRON CEDEX, FRANCE tel. +33 (0)4 72018160 www.sairem.com Microwave and Radio Frequency specialist Dielectric Industrial Heating Any frequency, any power level ...

4. What are microwaves? Transverse electromagnetic waves The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Electromagnetic waves propagated in free space have the electric and magnetic field perpendicular to each other and to the direction of propagation; they are known as transverse electromagnetic waves (TEM). The plane of polarisation for a wave is, by convention, that of the electric field – vertical Magnetic Electric field (H) field (E) WAVELENGTH λ = 12.2 cm for 2450 MHz Direction of wave E E E H H H

6. What are microwaves? Electromagnetic Spectrum The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA

7. What are microwaves? ITU allocated bands for ISM applications The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Fig. 2. Frequency band regions allocated by ITU R1- Europe, Africa, Turkey, Russia (Siberia) & Mongolia, Middle East (without Iran) R2 – South & North America R3 – Remaining countries Radio-frequency and Microwave bands for Industrial, Scientific and Medical (ISM) applications allocated by the International Telecommunications Union (ITU) Frequency band Central frequency Wavelength World regions covered 6.765 – 6.795 MHz 6.78 MHz 44.2 m Under consideration 13.553 – 13.567 MHz 13.56 MHz 22.1 m R1, R2, R3 26.957 – 27.283 MHz 27.120 MHz 11.1 m R1, R2, R3 40.66 – 40.70 MHz 40.68 MHz 7.4 m R1, R2, R3 433.05 – 434.79 MHz 433.92 MHz 0.69 m R1 902 – 915 MHz 915 MHz 0.33 m R1, R2, R3 2400 – 2500 MHz 2450 MHz 0.12 m R1, R2, R3 5725 – 5875 MHz 5800 MHz 0.05 m R1, R2, R3 24 – 24.25 GHz 24.125 GHz 1.24 cm R1, R2, R3 61 – 61.5 GHz 61.25 GHz 0.49 cm Under consideration 122 – 123 GHz 122.5 GHz 0.24 cm Under consideration 244 – 246 GHz 245 GHz 0.12 cm Under consideration

8. Electromagnetic energy i nteractions with matter The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Region of the electromagnetic spectrum Main interactions with matter Radio Collective oscillation of charge carriers in bulk material (plasma oscillation). An example would be the oscillation of the electrons in an antenna. Microwave through far infrared Plasma oscillation, molecular rotation Near infrared Molecular vibration, plasma oscillation (in metals only) Visible Molecular electron excitation (including pigment molecules found in the human retina), plasma oscillations (in metals only) Ultraviolet Excitation of molecular and atomic valence electrons, including ejection of the electrons (photoelectric effect) X-rays Excitation and ejection of core atomic electrons Gamma rays Energetic ejection of core electrons in heavy elements, excitation of atomic nuclei, including dissociation of nuclei High energy gamma rays Creation of particle-antiparticle pairs. At very high energies a single photon can create a shower of high energy particles and antiparticles upon interaction with matter.

9. Microwave energy versus other electromagnetic energy Ionizing or non-ionizing? The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Radiation type Typical frequency (MHz) Quantum (photon) energy Chemical bond type Chemical bond energy (eV) eV kcal/mol eV kcal/mol Gamma ray X-Ray UV Visible Infrared Microwaves Radio-waves 3.0 x 10 14 3.0 x 10 13 1.0 x 10 9 6.0 x 10 8 3.0 x 10 6 2450 1 1.24 x 10 6 1.24 x 10 5 4.1 2.5 0.012 1.6 x 10 -5 4 x 10 -9 2.86 x 10 7 2.86 x 10 6 95 58 0.28 0.037 9 x 10 -8 H-OH H-CH 3 H-NHCH 3 H 3 C-CH 3 PhCH 2 -COOH H-O-H ... O-H H ‌ 5.2 4.5 4.0 3.8 2.4 0.21 120 104 92 88 55 4.8

11. Microwaves & their i nteractions with matter Main parameters The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA P a = absorbed power (watts) K = constant, 0.55 x 10 -10 V = sample volume (m 3 ) f = frequency (Hz) E = electric field inside the sample (V/m)  ’’ = dielectric loss (F/m) 1. Absorption 2. Penetration depth, d d = penetration depth in to material where the power is P a /e or 36% of the P a calculated at the point of entrance Material Penetration depth, d 27 MHz 2450 MHz Air many km many km Water 10 cm 1.5 cm Balsa wood 2 m 20 cm Oak 30 cm 3 cm Rubber 15 cm 2 cm Aluminium 16 microns 1.7 microns

13. Microwaves & their Interactions with Matter Classification of materials The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA INSULATOR Total Transparent ΔT = 0 CONDUCTOR None Reflective DIELECTRIC Partial to total Absorptive ΔT> 0 Examples: quartz, ice, non-polar solvents Examples: metals Examples: water, polar solvents, zeolites Material type Penetration

14. Microwaves & their Interactions with Matter The effect of wavelength (frequency) on heating homogeneity The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Videorogress wave MagnE face.avi Videorogress wave MagnE.avi ~ 2cm  /2 ~ 6 cm (2450 MHz) Hot area Cold areas E a /2 E a ~ 2 m  /2 ~ 5.6 m (27 MHz)

15. Microwaves & their Interactions with Matter - Examples The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA The transmitted electromagnetic energy penetrates into the interior of materials and attenuates to an extent depending on the dielectric constant. The inverse of the attenuation constant is defined as the skin depth/depth of penetration . Material Depth of penetration Classification Glass Quartz 150 m Insulator Pyrex 2 m Insulator Plastics PTFE 25 m Insulator Polyethylene high density 25 m Insulator Polypropelene 18 m Insulator Foods Ice 12 m Insulator Water 30 mm Dielectric Meat 12 mm Dielectric Metals Aluminium 2 μm Conductor

17. Microwaves & their Interactions with Matter Rates of heating for solids (powder ) The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Effect of microwave heating on temperature of solids 1 kW, 2.45 GHz Sample 25g (particle size 5-80 μm) Chemical T, 0 C Time, min Al 577 6 C 1283 16 Co 2 O 3 1290 3 CuCl 2 619 13 FeCl 3 41 4 NaCl 83 7 Ni 384 1 NiO 1305 6.25 CaO 83 30 CuO 701 0.5 Fe 2 O 3 88 30 Fe 3 O 4 510 2 TiO 2 122 30 WO 3 530 0.5 B 4 C (>400μm) 214 2 B 4 C (5 - 80μm) 665 2

19. Microwave heating vs. Conventional heating The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Microwave heating / Dielectric heating Conventional heating / Heat conduction Heating of polar molecules with an electric dipole moment; energy transferred directly from the electric field to molecules if walls of containment vessel are ‘microwave transparent’ Transfer of thermal energy from outside - energy transferred indirectly from containment vessel to reaction mixture. The time of heating depends on the thermal conductivity of the material to be heated and the distance from the heating source to the material. Superheating of absorptive molecules due to rapid & selective energy transfer from the electric field  temperature gradients in solution Temperature of containment vessel walls is higher than the reaction temperature p = power density,  = field frequency  ’’ r = relative permittivity;  0 = permittivity of free space E = electric field strength Fourier’s law

20. Microwave heating vs. Conventional heating Magic effect? The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Arrhenius equation: E a = 50 kcal/mol Temperature 0 C Reaction rate increase 100 4.7 x 10 -30 1 110 2.73 x 10 -29 5.8 120 1.46 x 10 -28 31 130 7.16 x 10 -28 152 150 7.16 x 10 -26 2914

21. Microwave Equipment for Heating Applications Basic equipment The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Microwave generator Antenna for direct irradiation Multimode cavity Monomode cavity MICROWAVE APPLICATOR POWER SUPPLY AND PROTECTION SYSTEMS MAGNETRON

22. Microwave Equipment for Heating Applications Multimodal Applicators The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Applicators are devices designed to ensure the transfer of electromagnetic energy from the transmission line to the material to be treated. Waveguide launcher Circulator Dummy load Magnetron Mode stirring Sample Waveguide Antenna

24. Microwave Equipment for Heating Applications Single Mode Resonant Cavities The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Electric field distribution & intensity in TE 10 mode waveguide, 2.45 GHz a b Standard waveguide a mm b mm WR340 86.36 43.18 WR430 109.2 54.60

25. Microwave Equipment for Heating Applications Single Mode Resonant Cavities – Standing wave formation The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA The superposition of the incident and reflected waves gives rise to a standing wave pattern which for some simple structures is very well defined in space Videotanding wave MagnE3.avi Videotanding wave MagnE.avi Videotanding wave MagnE2.avi E 1 E 2 λ 0 /2 In air = 61 mm

28. The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA HIGH FREQUENCY GENERATOR REACTOR (APPLICATOR) Energy transmission line

29. The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA HIGH FREQUENCY GENERATORS MICROWAVE GENERATORS 915 MHz & 2450 MHz RADIO-FREQUENCY GENERATORS 13.56 MHz & 27.12 MHz GENERATORS > 2450 MHz

34. The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA ENERGY TRANSMISSION LINE COAXIAL CABLE WAVEGUIDE

35. The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA REACTORS (APPLICATORS) BATCH CONTINUOUS FLOW

36. Industrial microwave chemistry Treatment of residual acids from nitrocellulose fabrication The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Residual acid treatment Nitroglycerin destruction Microwave: 8 kW (2 kW + 6 kW) 2.45 GHz Capacity: 300 kg/h Process temperature: 150 °C Preheated residual acid PROCESS DIAGRAM Residual acid mixture Regenerated acids Heat exchanger MW Head

37. Industrial microwave chemistry Laurydone  synthesis The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA 6 kW 2.45 GHz Laurydone  synthesis MW reactor Pyroglutamic acid + Lauryl alcohol NO NEED FOR CATALYST (p-toluene sulphonic acid) and solvent (toluene) Microwave power : 6 kW 2.45 GHz Batch production : 150 kg in 4 hours Reaction time reduced 5 times

40. LABOTRON X and S, Microwave-assisted extraction and synthesis The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA LABOTRON 6 kW with batch reactor LABOTRON 2 kW with CF reactor

41. LABOTRON X and S - Batch reactors The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Batch reactor 1.7 L Batch reactor 17 L

42. LABOTRON X and S - Continuous flow reactors The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA SPIN S SPIN M

43. LABOTRON X and S - Batch Reactor The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA

44. Minilabotron 2000 with batch reactor The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA

45. Minilabotron 2000 with CF reactors The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA Minilabotron 2000 with horizontal SPINreactor Minilabotron 2000 with horizontal column reactor

46. The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA PILOT-scale up to 30 kW, 915 MHz

47. The content of this presentation is confidential and should not be distributed to a third party without prior authorization from SAIREM SA PILOT up to 30 kW, 915 MHz – Reactors Batch reactor 100 L Continuous flow reactor