WP6: Reactor Design and scale-up

1. WP6: Reactor Design and scale-up Dr. Javier Marugán (URJC) MTEC UoB VAST-ICT SIRIM

2. Description of work 6.1. Photoreactor optimization (URJC, MTEC) 6.1.1. Opto-mechanical simulation 6.1.2. Experimental validation 6.2. Solid-state LED reactor optimization (UoB,MTEC) 6.3. Kinetic modelling and scale-up (URJC, UoB) 6.3.1. Intrinsic kinetic modelling 6.3.2. Reactor design 6.4. Field testing (VAST-ICT, MTEC, SIRIM)

3. Position in Project Task 6.1 Photo-catalytic Structure Optim. WP2.1: Catalytic Discovery Task 6.2 LED, material & reactor design opt. WP7.3 Process Life Cycle Assessment WP2.2 Novel Visible Light Active Mat. WP8.2 Technical Documentation Task 6.3 Kinetic Modelling and Scale-up WP3.3 UV LED Matching Selection Task 6.4 Field Testing

4. WP6 Deliverables (none on M1-M6) WP6 Milestones (none on M1-M6) • D6.1) Catalyst morphology (URJC, M30) • D6.2) UV-LED reactor design (UoB, M45) • D6.3) Kinetic model for reactor (URJC, M42) • D6.4) Reactor field testing (SIRIM, M48) • MS26) Impact of reactor geometry calculated by simulation and validated experimentally (URJC, M18) • MS27) Identification of best catalyst scaffold for incorporation in the final reactor (UoB, M27) • MS28) Initial kinetic models of photo-reactor performance determined (URJC, M27) • MS29) LED array-photo-catalytic reactor constructed (UoB, M30) • MS30) Pilot system connected and initial results from field testing obtained (SIRIM, M36)

5. Action Plan M1-M6 (kick-off meeting) • Optomechanical simulation and evaluation of radiation absorption with standard catalyst of the standardized reactor designed in WP4

6. Description of work – 1M-6M 6.1. Photoreactor optimization (URJC, MTEC) 6.1.1. Opto-mechanical simulation 6.1.2. Experimental validation 6.2. Solid-state LED reactor optimization (UoB,MTEC) 6.3. Kinetic modelling and scale-up (URJC, UoB) 6.3.1. Intrinsic kinetic modelling 6.3.2. Reactor design 6.4. Field testing (VAST-ICT, MTEC, SIRIM) Task 4.1. Test Reactor

7. 6.1. Photoreactoroptimization – 1M-6M • Estimation of the distribution of light inside the photoreactor to maximize the average LVRPA. • Inputs: Geometry of reactor Geometry of solar collector / LED system Radiation power and spectrum Optical properties materials / CATALYSTS • Validation: Model organic chemicals degradation Model bacteria inactivation Radiation measurements • Optimization of the configuration of the catalyst

8. Standardisationof Test Conditions 1.- Preliminary radiation calculations • Simulations performed with these main assumptions. • 1 central LED (D = 40 mm) and 8 LED (D = 10 mm) equally distributed. • Emission power: 48 W/m2 of UV-A (highly value of solar irradiation). That would correspond to approximately to 150 and 10 mW electrical power LED respectively with 40% of efficiency of electricity to light conversion. • Direct / Diffuse radiation source • Transparent / Specular / Diffuse Reactor wall • Catalyst disc (D = 40 mm) place at 100 mm below the LED array.

9. Standardisationof Test Conditions 1.- Preliminary radiation calculations • Direct radiation source • Transparent Reactor wall • Average incident radiation flux at the catalyst surface: • > 30 W/m2 • Highly non-homogeneous

10. Standardisationof Test Conditions 1.- Preliminary radiation calculations • Diffuse radiation source • Transparent Reactor wall • Average incident radiation flux at the catalyst surface: • < 5 W/m2

11. Standardisationof Test Conditions To be determined • Dimensions of the light source and cooling system • Dimensions of the immobilized catalyst • Number, dimensions and arrangement of the LED. • Emission geometry, power and spectra of the LED. • Optical characteristics of the reactor materials and surfaces, mainly the outer reactor wall. High Efficacy 365nm UV LED Emitter LED EnginLZ1-00U600

12. Standardisationof Test Conditions 2.- UV-A LEDs radiation calculations Suggested arrangement for 12 LZ1-00U600 LEDs in a support plate: Plate = 60 mm (diam.) Foot print = 4.4 x 4.4 mm LED = 3.2 mm (diam.) Separation = 6 mm

13. Standardisationof Test Conditions 2.- UV-A LEDs radiation calculations Case A: Reactor = 90 mm (diam.) Catalyst disc = 40mm (diam.) Distance = 50 – 180 mm Wall: Transparent / Specular Case B: Reactor = 90 mm (diam.) Catalyst disc = 60mm (diam.) Distance = 50 – 180 mm Wall: Transparent / Specular

14. Standardisationof Test Conditions 2.- UV-A LEDs radiation calculations Radiation Balance (%) Catalyst = 40 mm Transparent Wall Catalyst = 60 mm Transparent Wall

15. Standardisationof Test Conditions 2.- UV-A LEDs radiation calculations Radiation Balance (%) Catalyst = 40 mm Specular Wall Catalyst = 60 mm Specular Wall

16. Standardisationof Test Conditions 2.- UV-A LEDs radiation calculations Radiation Flux

17. Standardisationof Test Conditions 2.- UV-A LEDs radiation calculations Radiation Flux (W/m2) LED Emission = 160 mW (Data from 2011 LED Engin Catalog) Catalyst = 40 mm Transparent Wall Catalyst = 60 mm Transparent Wall Catalyst = 40 mm Specular Wall Catalyst = 60 mm Specular Wall

18. Standardisationof Test Conditions 2.- UV-A LEDs radiation calculations Radiation Flux Distribution Catalyst = 40 mm, Distance = 120 mm Transparent Wall Specular Wall

19. Standardisationof Test Conditions 2.- UV-A LEDs radiation calculations Main Conclusions • Working with a bigger catalytic disc decrease the average radiation flux, inherently unhomogeneous, although would reduce the experimental error in the determination of the reaction rate. • Increasing the reflective properties of the wall increases significantly the radiation flux and reduces the non-radial unhomogeneities and the influence of the distance to the LED array. • Even in the worst scenario, with the lower value of the typical emission provided by the manufacturer , transparent walls and the biggest disc the irradiation flux is in the order of the 30-40 W/m2 UV-A solar irradiation of a sunny day. • The possibility of modifying the distance would allow working under different irradiation conditions and with different liquid volumes.

20. Standardisationof Test Conditions To be determined (Task 4.1) • Proposed dimensions for the test reactor. • Number, dimensions and arrangement of the LED.

21. Standardisationof Test Conditions 3.- Radiation calculations in the proposed test reactor LEDs arrangement

22. Standardisationof Test Conditions 3.- Radiation calculations in the proposed test reactor Incident radiation at the bottom (no absorption) Assumption for emission: 32 LEDs x 0.160 mW = 5.76 W of UV-A

23. Standardisationof Test Conditions 3.- Radiation calculations in the proposed reactor Catalyst in suspension Catalyst: AEROXIDE® P25 TiO2(Evonik Industries AG) • Optical properties (Manassero et al., Chem. Eng. J. 225 (2013) 378–386): • Specific Absorption Coefficient (λ=360nm): κ* = 10708 cm2/g • Specific Scattering Coefficient (λ=360nm): σ* = 46519cm2/g

24. Standardisationof Test Conditions 3.- Radiation calculations in the proposed reactor Immobilized Catalyst Incident Radiation = 0.998 W

25. Standardisationof Test Conditions 3.- Radiation calculations in the proposed reactor Immobilized Catalyst Catalyst: AEROXIDE® P25 TiO2(Evonik Industries AG) • Optical properties (unpublished experimental results from URJC) : • Absorption Coefficient (λ=360nm): κ = 8818 cm-1 Optimal absorption P25 TiO2= 2 – 5 mm

26. Standardisationof Test Conditions 3.- Radiation calculations in the proposed reactor Conclusions The proposed reactor design should provided comparable results between the experiments carried out by the different groups, allowing the use of the obtained data for the rigorous kinetic modeling of the process. • The absorption of radiation should be high enough to allow fast reaction rates of degradation. However, the expected decrease in the quantum yield due to the increase in the recombination rate at such high values of irradiation power could reduce significantly the efficiency of the process.

27. Next actions: • Experimental validation • Kinetic Modelling • Estimation of the experimental reaction rate.