M6 Meeting25th July 2013 Slide 1

Workpackage: WP4. Evaluation of catalyst activity and stability

Presenter: MTEC - Angkhana Jaroenworaluck

Collaborating teams: UoB / URJC

UCL / UoR,

MTEC / SIRIM / VAST-ICT

WP4: Evaluation of catalyst activity and stability

M6 Meeting25th July 2013 Slide 2

Tasks

WP4: Evaluation of catalyst activity and

stabilityCooperated

Teams Names E-mails 4.1 Standardisation of test

condition duration UoB / URJC Ron Stevens ( UoB) r.stevens@bath.ac.uk

Chris Bowen (UoB) msscrb@bath.ac.uk

Dr. Duncan Allsopp (UoB) d.allsopp@bath.ac.uk

Dr. Javier Marugán (URJC) javier.marugan@urjc.es

4.2 Degradation of model system UCL / UoR Ivan Parkin (UCL) i.p.parkin@ucl.ac.uk

Hendrik Kosslick (UoR)hendrik.kosslick@uni-rostock.de

 

4.3 Testing of industrial effluent degradation using solid-state UV and visible light

MTEC / SIRIM /VAST-ICT

Angkhana Jaroenworaluck (MTEC)

angkhanj@mtec.or.th

Tan Yong Nee (SIRIM) yntan@sirim.my

Luu Cam Loc (VAST-ICT) lcloc@vast-hcm.ac.vn

WP4: Tasks & Teams

M6 Meeting25th July 2013 Slide 3

WP4

WP3

WP5WP2

WP6

WP4: Objectives

New materials to increase visible light activity

Improving TiO2 based systems

Standardization for Photocatalyst reactions

Kinetic and Mechanism Studies

Reactor design, evaluation & scale up

1. Core/shell nanostructure materials2. New photocatalyst types

TiO2 photocatalysts deposited on various type of supports

Tested photocatalyststo be further characterised to maximise results

Test key parameters for the reactor design

M6 Meeting25th July 2013 Slide 4Deliveries

No.

D4.1 Report on the optimum design of a test reactor for the project

D4.2 Performance of new generation of photo-catalysts

D4.3 Industry effluent degradation performance

Description Due

M9

M42

M42

M6 Meeting25th July 2013 Slide 5Milestones

Milestone

M12-18

Milestone name Means of verification Expected

MS14

MS15

Standardised reactor constructed in all sites working on WP4.2 and 4.3. M12 Screening reactor

operational

Initial kinetic analysis doped and non-doped TiO2 powders

Kinetic profiles availableM18

M6 Meeting25th July 2013

OutlineTask 4.1. Standardisation of Test Conditions 1.- Preliminary design of the photoreactor 2.- Proposed reactor design

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M6 Meeting25th July 2013

1. Objective: simple reactor to test different catalysts at equal conditions at the different research locations.

2. The conditions that should be equal, as previously discussed, are: temperature, pH, oxygen supply, indicator concentration and light intensity.

3. To measure the pH, oxygen, and temperature there should be 3 access points for sensors.

4. To be able to control the temperature the reactor should have a cooling/heating jacket.

5. To ensure an equal light intensity the distance between the source and the catalyst and the height of water should be fixed.

Task 4.1. Standardisation of Test Conditions 1.- Preliminary design of the photoreactor

M6 Meeting25th July 2013

Basic Design I

Task 4.1. Standardisation of Test Conditions 1.- Preliminary design of the photoreactor

M6 Meeting25th July 2013

Basic Design I

Task 4.1. Standardisation of Test Conditions 1.- Preliminary design of the photoreactor

The light source will be placed on top of the reactor vessel and integrated with the required access points and sample point

To ensure a fixed distance between the light source and the catalyst a frame to hold the immobilized catalyst.

M6 Meeting25th July 2013

Task 4.1. Standardisation of Test Conditions 2.- Proposed Reactor Design

Reactor Design ConsiderationsFLUID DYNAMICS AND HEAT TRANSFER:

Perfectly mixed conditions should be ensured to:- Discard external mass transport effects Reaction kinetics control.- Homogeneous composition in the withdrawal of samples.- Isothermal conditions.

Proposals:- Magnetic stirring at the bottom.- Air bubbling to improve mixing.- Position of the catalyst inside the liquid at a height around 2/3.- Diameter of the catalyst 1/2 of the reactor diameter.- Cooling jacket to keep temperature constant (bad for wall reflectivity)

M6 Meeting25th July 2013

Task 4.1. Standardisation of Test Conditions 2.- Proposed Reactor Design

Reactor Design Considerations

RADIATION TRANSFER:

Homogeneous irradiation of the catalyst Homogenous reaction rate.Low LEDs-catalyst distance Higher radiation flux (especially for non-reflective walls)Low LEDs-catalyst distance Risk of wetting the LEDs circuits.

Proposals:- Air chamber above the liquid surface required for air equilibrium.- Highly reflective walls to increase radiation flux and to improve homogeneity.- Optimal distribution of the LED sources to improve homogeneity.

M6 Meeting25th July 2013

Task 4.1. Standardisation of Test Conditions 2.- Proposed Reactor Design

Reactor Design ConsiderationsCHEMICAL REACTION KINETICS:Constant dissolved O2 concentration: Simplifies kinetics and avoids measurement.Nearly constant reaction volume: (withdrawn samples < 10% total volume).Relatively short reaction time:

- Reduces heating problems.- Reduces stripping of chemicals to the gas phase.- Low conversion < 10% Initial reaction rate conditions, intermediates

effects can be discarded in the kinetics.

Proposals:- Relatively high reaction volume- Sampling below <10% of the total reaction volume.- Conversion around 10% optimal for getting significant data above the

experiment error of the analytical method keeping initial reaction rate conditions.

M6 Meeting25th July 2013

Task 4.1. Standardisation of Test Conditions 2.- Proposed Reactor Design

Reactor diameter: D_R = 80 mmLiquid height: H_L = 50 mm

Sample volume: V_S = 2.5 mLSample number (máx): N_S = 10

Catalyst diameter: D_C = 40 mm (1/2 of the reactor)Catalyst height: H_C = 30 mm above bottom, 20 mm below surface.

LEDs height: H_LED = 80 mm (50 mm from catalyst, 30 mm air)

Reaction volume V_L = 250 mL

Max volume V_Smax = 25 mLMin H_L = 45 mm (DH_L 10%)

Proposed Reactor Dimensions

M6 Meeting25th July 2013

Task 4.1. Standardisation of Test Conditions 2.- Proposed Reactor Design

M6 Meeting25th July 2013

Task 4.1. Standardisation of Test Conditions

• Number, dimensions and arrangement of the LED.

LEDs Circuit Preliminary Design

Possibility of switching off some LEDs to modify irradiation flux

M6 Meeting25th July 2013

Task 4.1. Standardisation of Test Conditions 2.- Proposed Reactor Design

Reactor Vessel

LED Circuit

M6 Meeting25th July 2013

Task 4.1. Standardisation of Test Conditions 2.- Proposed Reactor Design

Cover / Catalyst Frame

Catalyst Holder

LEDs Circuit position

Openings

M6 Meeting25th July 2013 Slide 18

Standardization bodies on photocatalyst materials

(CEN vs ISO)

M6 Meeting25th July 2013 Slide 19

CEN: European committee for standardization

CEN/TC386-(Photocatalysis) established in 11/2008

WG3: Water purification WG6: Light sourceWG8: Microbiological effects

Secretariat: AFBOR (France)

Chairman: Dr. Pascal KALUZNY (France)

Source: http://www.cen.eu and http://www.dri.mmu.ac.uk

CEN

M6 Meeting25th July 2013 Slide 20

00386001 Project reference: FprCEN/TS16599

Title: Photocatalysis-Irradiation conditions for testing photocatalytic properties of semiconducting materials and the measurement of these conditions

Candidate citation in OJEU* : No (-)

Current status: Under ApprovalDAV: 2013-12

(*) OJEU-Official Journal of the European Union

Source: http://www.cen.eu

M6 Meeting25th July 2013 Slide 21

ISO: International organization for standardization

ISO/TC206-Fine Ceramics established in 1992 with JISC as secretariat

Secretariat: Dr. Shuji Sakaguchi (AIST, Japan)

Chairman: Dr. Tai-Kyu Lee (Nanopac Co., Korea)

(WG37: Test methods for photocatalytic materials)

Convenor: Dr. Koji TAKEUCHI (AIST, Japan)

Source: http://www.iso.org

ISO

M6 Meeting25th July 2013 Slide 22

ISO/TC206: Photocatalyst materials / water purification/ anti-bacteria /

light sourceISO 10676:2010   Fine ceramics (advanced ceramics, advanced technical ceramics) -- Test method for water purification performance of semiconducting photocatalytic materials by measurement of forming ability of active oxygen.

AbstractISO 10676:2010 describes a test method covering photocatalytic materials formed on, or attached to, another material surface for the purpose of decomposing, and thus eliminating, the pollutants in water, using photocatalytic performance.

This test method is applicable to photocatalytic materials under UV irradiation, and not under visible light irradiation.

Source: http://www.iso.org

Published standards-1

M6 Meeting25th July 2013 Slide 23

ISO 10677:2011   Fine ceramics (advanced ceramics, advanced technical ceramics) -- Ultraviolet light source for testing semiconducting photocatalytic materials.

AbstractISO 10677:2011 describes an ultraviolet (UV) light source and specifies a method of measuring the radiation intensity which is used in testing the performance of semiconducting photocatalytic materials in a laboratory.

Source: http://www.iso.org

Published standards-2

M6 Meeting25th July 2013 Slide 24

ISO 10678:2010   Fine ceramics (advanced ceramics, advanced technical ceramics) -- Determination of photocatalytic activity of surfaces in an aqueous medium by degradation of methylene blue.

AbstractISO 10678:2010 specifies a method for the determination of the photocatalytic activity of surfaces by degradation of the dye molecule methylene blue (MB) in aqueous solution using artificial ultraviolet (UV) radiation, and characterizes the ability of photoactive surfaces to degrade dissolved organic molecules on ultraviolet radiation. The test method specified is also applicable to evaluation of the specific photocatalytic self-cleaning activity of surfaces covered with respective coatings.This method is not applicable to characterizing the photoactivity of surfaces on visible illumination, regarding direct soiling, degradation of gaseous molecules and the determination of antimicrobial photoactivity of surfaces.

Source: http://www.iso.org

Published standards-3

M6 Meeting25th July 2013 Slide 25

ISO 13125:2013Fine ceramics (advanced ceramics, advanced technical ceramics) -- Test method for antifungal activity of semiconducting photocatalytic materials.

AbstractISO 13125:2013 specifies a test method covering the determination of the antifungal activity of materials that contain a photocatalyst or have photocatalytic films on their surface, by counting the number of pre-incubated fungal spores that survive exposure to ultraviolet (UV-A) light.ISO 13125:2013 provides for the assessment of different kinds on materials used in various applications, such as construction materials in flat coating, sheet, board or plate form, etc. Powder, granular, fibrous or porous photocatalytic materials are not included.Values expressed in ISO 13125:2013 are in accordance with the International System of Units (SI).

Source: http://www.iso.org

Published standards-4

M6 Meeting25th July 2013 Slide 26

AbstractISO 27447:2009 specifies a test method for the determination of the antibacterial activity of materials that contain a photocatalyst or have photocatalytic films on the surface, by measuring the enumeration of bacteria under irradiation of ultraviolet light.ISO 27447:2009 is intended for use with different kinds of semiconducting photocatalytic materials used in construction materials, in flat sheet, board, plate shape or textiles that are the basic forms of materials for various applications. It does not include powder, granular or porous photocatalytic materials.

This test method is usually applicable to photocatalytic materials produced for an antibacterial effect. Other types of performance of photocatalytic materials, i.e. decomposition of water contaminants, self-cleaning, antifogging and air purification, are not determined by this method.

The values expressed in ISO 27447:2009 are in accordance with the International System of Units (SI).

ISO 27447:2009   Fine ceramics (advanced ceramics, advanced technical ceramics) -- Test method for antibacterial activity of semiconducting photocatalytic materials.

Source: http://www.iso.org

Published standards-5

M6 Meeting25th July 2013 Slide 27

ISO/FDIS 14605Fine ceramics (advanced ceramics, advanced technical ceramics) -- Light source for testing semiconducting photocatalytic materials used under indoor lighting environment.

ISO/DIS 17094Fine ceramics (advanced ceramics, advanced technical ceramics) -- Test method for antibacterial activity of semiconducting photocatalytic materials under indoor lighting environment.

Source: http://www.iso.org

Standards under development

M6 Meeting25th July 2013 Slide 28

Source: from Dr. Takeuchi (AIST, JAPAN), page 18 of 23souran_hyoujyunkiban.pdf

Standards to be proposed: Test method for environment purificationperformance of photocatalyst and appliedmaterials by dissolved oxygen consumption

(Temperary)

Proposed by: Dr. Koji TAKEUCHI (AIST, Japan)Dr. Tsutomu HIRAKAWA (AIST, Japan)

Target dates of proposal and issue of the standards:JIS: Proposal FY 2012 Issued FY 2013ISO: Proposal FY 2012 Issued FY 2017

New proposal for water purification

M6 Meeting25th July 2013

Slide 29MB degradation test of P25 TiO2

Light source

Light off - 24 h

Light on -150 min

filtration

filtration

MB concentration: 4 ppmUVA intensity: 50 W/m2

M6 Meeting25th July 2013 Slide 30

1. Make a simple reactor (closed system) of LED light source from UOB.

2. Set test conditions: Light on-off, P25 TiO2 / MB concentrations / LED intensities.

3. Compare reaction rate from all reactors used.

4. Change catalyst types for the same test conditions.

(started from powder type to pellets and 3D-porous TiO2 catalysts)

5. Draft scientific papers to be published. (if possible)

Future plans

M6 Meeting25th July 2013 Slide 31

Thank You