MODELING INTRINSIC KINETICS IN IMMOBILIZED

PHOTOCATALYTIC MICROREACTORS
BSc. Aura Visan
Coordinator : Prof. Dr. Ir. R.G.H Lammertink
Prof. Dr. Guido Mul
Mentor: MSc. D. Rafieian

Photocatalysis for water treatment

Organic synthesis

Gaseous pollutant removal

Water detoxification

Antibiotics
Analgesics
Steroids
Hormones
Pesticides

Modeling intrinsic kinetics in immobilized photocatalytic microreactors

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Catalyst
Most widely used semiconductor catalyst: TiO2

< 390 nm (3.2 eV)

Research

Extend absorption spectrum to visible light: Band-gap tuning

Ion doping, coupling semiconductors, physical metal ion implementation

Use of visible light absorbing molecules (dyes)

Recombination

Structural design

Modeling intrinsic kinetics in immobilized photocatalytic microreactors

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Reactors
Enhanced mass transfer
Slurry
Ineffective light distribution

No catalyst separation required

Immobilized
More approachable design and scale-up
Modeling intrinsic kinetics in immobilized photocatalytic microreactors

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Microreactors
High surface-to-volume ratio

Short molecular diffusion distance

Good light penetration

Modeling intrinsic kinetics in immobilized photocatalytic microreactors

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Photocatalytic reactor modeling

Light distribution model
Fluid dynamics
Mass transport
Reaction kinetics

Modeling intrinsic kinetics in immobilized photocatalytic microreactors

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Photocatalytic reactor modeling

Light distribution model
Fluid dynamics
Local volumetric rate of energy absorption
Mass transport
Reaction kinetics

Radiation transfer equation

Modeling intrinsic kinetics in immobilized photocatalytic microreactors

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Photocatalytic reactor modeling

Light distribution model
Fluid dynamics
Turbulence models
Mass transport
Reaction kinetics

Navier Stokes and Continuity equation

Modeling intrinsic kinetics in immobilized photocatalytic microreactors

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Photocatalytic reactor modeling

Light distribution model
Fluid dynamics

Axial dispersion model

Mass transport
Reaction kinetics

RTD

Pe number

Modeling intrinsic kinetics in immobilized photocatalytic microreactors

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Photocatalytic reactor modeling

Light distribution model

Dispersed systems

Fluid dynamics
Mass transport
Reaction kinetics

Eulerian multi fluid approach

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Photocatalytic reactor modeling

Light distribution model

Dispersed systems

Fluid dynamics
Mass transport
Reaction kinetics

One phase system, large Pe numbers

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Photocatalytic reactor modeling

Light distribution model
Fluid dynamics
Immobilized reactors
Mass transport
Reaction kinetics

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Photocatalytic reactor modeling

Light distribution model
Fluid dynamics

Flowrate independent kinetics

Differential reactor

Mass transport
Reaction kinetics

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Scope of research
Set up a complete model for immobilized photocatalytic microreactors for
both light dependent and light independent kinetics
Validate the model with experimental data for various residence time,
catalyst thickness and photon flux densities and extract intrinsic kinetics
Compare the two models and define a criterion to mark the transition
towards the regime where the incorporation of light is required
Update the performance parameters for the light dependent model

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Numerical modeling Light independent model

Mass balance for the catalyst layer:

Boundary conditions

Concentration profile

Lower boundary condition for the flow channel

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Numerical modeling Light independent model

Governing equation for the flow channel:

Non-dimensionalized governing equation:

Non-dimensionlized boundary conditions:

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Numerical modeling Light dependent model

Mass balance for the catalyst layer:

Concentration profile:

Updated lower boundary conditions for the flow channel

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Experimental - TiO2 immobilization

VP Disp. W 2730 X

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Experimental Catalyst film characterization

Thickness

SEM

Roughness

AFM
Ellipsometry

Porosity
Extinction coefficient

Absorption coefficient

Transmission measurements
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Experimental Catalyst film characterization

Thickness
Roughness
Porosity
Extinction coefficient

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Experimental Absorption coefficient

Ellipsometry measurement

Transmission measurement

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Experimental Tuning the catalyst film thickness

Lower thickness range

Higher thickness range

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Experimental - Microreactor fabrication

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Experimental - Microreactor operation

O2
UV

O2 permeable PDMS !!

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Results Light independent model

kMB = 40 1/s

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Results Light independent model

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Results Light independent model

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Results Light independent model

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Results Light dependent model

transfer coefficient for the electron transfer process
ki rate constant
absorption coefficient
0 incident photon flux density
Bp0 n0 equilibrium recombination rate
photon energy

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Results Light dependent model

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Results Criterion for neglecting light intensity

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Results Updated performance parameters

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Results Updated performance parameters

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Conclusions
1. Highly isotropic catalyst layer. Its properties determined by ellipsometry
2. Models capable of describing reactor performance
3. Intrinsic kinetics
4. Criterion for neglecting light
5. Updated performance parameters for the LDM

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Outlook
1. Repeat the variable irradiance experiments with non-reflective substrate
2. Miniaturized light source
3. Mechanical resistance of the catalyst layer
4. Assess the lifetime of the catalyst

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QUESTIONS?