development of recirculating photocatalytic reactor for wastewater remediation final draft

56
The Robert Gordon University, Aberdeen School of Engineering BEng (Hons) in Mechanical Engineering Development of a Recirculating Photocatalytic Reactor for Wastewater Remediation Mokanlasanya Akinyinka Johnson 1217611 April 2016

Upload: akinyinka-johnson

Post on 25-Jan-2017

143 views

Category:

Documents


1 download

TRANSCRIPT

Page 1: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

The Robert Gordon University, Aberdeen

School of Engineering

BEng (Hons) in Mechanical Engineering

Development of a Recirculating Photocatalytic Reactor for Wastewater Remediation

Mokanlasanya Akinyinka Johnson

1217611

April 2016

Page 2: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

Development of a Recirculating Photocatalytic Reactor for Wastewater

Remediation

Mokanlasanya Akinyinka Johnson

1217611

This report is submitted as part of the requirements for the BEng degree in

Mechanical Engineering at The Robert Gordon University, Aberdeen

Page 3: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

Declaration

I declare that this report, except where otherwise stated, is based on my work alone,

and carried out in the School of Engineering of The Robert Gordon University,

between September 2015 and April 2016. To the best of my knowledge and belief,

this report contains no material previously published or written by another person,

except where due reference has been made.

Signed…………………………………………….. Date.………………………..

Page 4: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

iv

Abstract

As the world population rises, availability of clean water supplies diminish. Demand

for effective water treatment methods are now rising, therefore improvements on

current wastewater remediation processes are necessary. Current technologies are

capable of meeting general treatment requirements although as the concern over

the global environment grows, so will standards rise. Photocatalysis shows Potential

of being the ideal solution for improvements upon current tertiary wastewater

treatment practices. The use of a non-harmful and unreactive catalyst prevent the

introduction of harmful substances into effluents and the ability to employ light

energy for activation presents a sense of versatility as it would be deployable in both

rural and urban areas.

Development of Photocatalytic reactors is central to photocatalysis, as they are

central to the development of the photocatalysis process. Many factors are

considered in reactor design like photocatalyst loading and the amount of incident

light, mass transport, agitation etc. such parameters determine the speed and

effectiveness of photocatalytic degradation and are important considerations for

every design.

Most photocatalytic reactors are developed for lab scale testing as implementing

photocatalysis for wastewater remediation at an industrial scale still presents

various difficulties. Most prominent being reactor design at an industrial scale

involves the use of large areas of space to cope with industrial wastewater volumes.

In this report, a recirculating photocatalytic reactor was developed at lab scale to

determine larger scale suitability. Various parameters considered where

incorporated into 4 design ideas and 1 selected for further analysis. Using

Methylene blue as a model compound, the developed design was able to effect 37%

degradation of the methylene blue solution over 60 minutes. Analysis of results

showed that the developed reactor at larger scale would present various problems

and through consideration of successes and drawbacks of the design an improved

concept was recommended for further development.

Page 5: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

v

Acknowledgements

As the author, I would like to thank the following:

CRE+E labs for the provision of the site of my experimental and

developmental process.

Mr. David Allen for Assistance with Design considerations regarding the

Reactor.

Mr. Alan McClean for Assistance and support with risk assessments

Dr. Cathy McCullagh for research assistance and supervision of testing

phases.

Page 6: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

vi

Table of Contents

Declaration ............................................................................................................. iii

Abstract .................................................................................................................. iv

Acknowledgements ................................................................................................. v

List of Figures ....................................................................................................... viii

Nomenclature .......................................................................................................... x

Abbreviations .......................................................................................................... xi

1 Introduction ...................................................................................................... 1

1.1 Project Aim ................................................................................................ 2

1.2 Objectives ................................................................................................. 2

2 Literature Review ............................................................................................. 3

2.1 Introduction ............................................................................................... 3

2.2 Semiconductor Photocatalysis Fundamentals ........................................... 3

2.2.1 Semi-Conductor Photocatalyst ........................................................... 5

2.3 Mechanism of TiO2 Photocatalysis. ........................................................... 6

2.4 Photoreactors and Types of Configurations .............................................. 7

2.4.1 Multi Tubular reactors ......................................................................... 8

2.4.2 Suspended Liquid Reactors ................................................................ 9

2.4.3 Flat Plate Reactors. .......................................................................... 10

3 Design Development...................................................................................... 14

3.1.1 Design Criteria .................................................................................. 14

3.1.2 Recirculation Mechanism .................................................................. 14

3.1.3 Design Development ........................................................................ 14

3.2 Developed Design ................................................................................... 18

3.2.1 Build Procedure ................................................................................ 19

3.2.2 Design Calculations .......................................................................... 20

4 Testing ........................................................................................................... 22

Page 7: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

vii

4.1 Experimental setup.................................................................................. 22

4.1.1 Methylene blue ................................................................................. 22

4.1.2 Catalyst loading ................................................................................ 22

4.1.3 Pump ................................................................................................ 23

4.1.4 UV Light Containment Reactor (illumination source) ........................ 23

4.2 Experimental Procedure .......................................................................... 24

4.3 Results .................................................................................................... 25

5 Discussion ..................................................................................................... 29

5.1 General Overview.................................................................................... 29

5.2 Test Results ............................................................................................ 30

5.3 Improved Design ..................................................................................... 32

6 Conclusion ..................................................................................................... 34

7 Further Development ..................................................................................... 35

References ........................................................................................................... 36

8 Appendices .................................................................................................... 40

Appendix A – Technical drawings ..................................................................... 40

Appendix B – Pump Specifications ................................................................... 44

Appendix C – Unit Conversions ........................................................................ 45

Page 8: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

viii

List of Figures

Figure 2.1 Generation of electron hole pairs .......................................................... 4

Figure 2.2 Photo excitation of Titanium Dioxide ..................................................... 7

Figure 2.3 Thin filmed multi tubular photoreactor and illumination box (M. Adams, et

al. 2012) ................................................................................................................. 8

Figure 2.4 Drum reactor finished model and schematic (C. McCullagh, et al., 2011)

............................................................................................................................... 9

Figure 2.5 Fixed bed Reactor schematic (Nogueira and Jardim, 1994) ............... 11

Figure 2.6 Flat plate reactor prototype (M. Adams, et al., 2008) .......................... 12

Figure 2.7 Comparison of substrate with angle at optimum TiO2 loading (M. Adams,

et al., 2008) .......................................................................................................... 13

Figure 2.8 Multiple thin film plate reactor stack, Lab unit (left) concept design (right)

(M. Adams, et al., 2008) ....................................................................................... 13

Figure 3.1 Paddle concept design ........................................................................ 15

Figure 3.2 Glass Bead concept design ................................................................. 16

Figure 3.3 Internal drum concept design .............................................................. 17

Figure 3.4 Reactor Model ..................................................................................... 18

Figure 3.5 Reactor parts and assembled prototype .............................................. 20

Figure 4.1 Methylene blue Calibration curve ........................................................ 22

Figure 4.2 Ultraviolet Light Containment Reactor (UVLCR) ................................. 23

Figure 4.3 Spectral output for UV lamps .............................................................. 24

Figure 4.4 Experimental setup .............................................................................. 24

Figure 4.5 Temporal absorption spectral pattern of MB under UV radiation only . 25

Figure 4.6 Temporal absorption of methylene blue degradation in the with catalyst

loading under UV irradiation ................................................................................. 26

Figure 4.7 %Absorption of methylene blue at maximum absorption wave length 27

Figure 4.8 Methylene blue concentration over 60 minutes of photocatalysis ....... 27

Figure 5.1 final design concept ............................................................................. 32

Figure 5.2 methyl orange degradation by P25 (purple), silica beads, and %doped

glass tubes (blue & green) (M. Adams, et al., 2012) ............................................ 33

Figure 0.1 Lower lid Drawing ................................................................................ 40

Figure 0.2 Top Lid 1 Drawing .............................................................................. 41

Figure 0.3 Top lid 2 Drawing ................................................................................ 42

Page 9: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

ix

Figure 0.4 Glass tube drawing .............................................................................. 43

Figure 8.5 Pump data sheet ................................................................................. 44

Page 10: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

x

Nomenclature

TiO2 – Titanium Dioxide

e- – Electron

h+ – Proton

Eev – Excitation energy

ΔEgap/Eg – Band Gap Energy

ZnO – Zinc Oxide

Zn(OH)2 – Zinc Hydroxide

hv – UV irradiation

e-ch – Conductance band electron

h+vb – Valent band hole

OH- – Hydroxyl ions

OH• – Hydroxyl Radical

O2 – Oxygen

O2•- – Super Oxide

HO2• – Hydroperoxyl Radical

H2O2 – Hydrogen peroxide

Re – Reynolds Number

Q – Volumetric Flow rate

A – Cross sectional Area

V – Flow velocity

D – Diameter

ρ – Density

η – Kinematic Viscosity

Page 11: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

xi

Abbreviations

UV – Ultraviolet

PMMA – Polymethylmethacrylate

PTFE – Polytetrafluoroethylene

RTV – Room temperature Vulcanization

PVC – Polyvinyl Chloride

UVLCR – Ultraviolet Light Containment Reactor

MB – Methylene Blue

MO – Methylene Orange

Page 12: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

1

1 Introduction

With the growing population of the world, the supply of clean water diminishes which

is cause for environmental concern. With the diminishing supply of clean water

wastewater remediation methods are now at a premium and although current

conventional methods for wastewater treatment are capable of meeting current

water standards in most cases, improvements on current processes are necessary.

Photocatalysis shows great potential for improving upon current tertiary cleaning

methods due to its versatility, ease of deployment and suitability for various

pollutants. One of the main concerns with wastewater is that industrial wastewater

can contain a variety of pollutants harmful to the environment, pesticides, heavy

metals or organic compounds which cannot be sufficiently treated by conventional

means most particularly in developing regions where even conventional facilities are

lacking. For both problems photocatalysis is ideally suited as it poses the ability to

completely destroy organic pollutants and toxins as well as bacteria and other

microorganisms within a water stream, and when operated using sunlight it is

suitable for developing regions by requiring less energy in order function. Many pilot

studies have been undertaken in the wastewater treatment field, Adams et al.,

(2013) developed a drum reactor for the remediation of wastewater containing

hydrocarbons, and Chong et al. developed nanofiber catalysts in order to solve

catalyst filtration problems in slurry reactors. Further improvements in this field will

result in better access to clean water which will improve sanitation, hygiene etc.

which would consequently result in healthier populations and environments.

Photocatalysis is the acceleration of a chemical reaction in the presence of a

photocatalyst.

Photocatalysis is beginning to gain traction in industry as it’s applicable for a wide

variety of fields and its various potential environmental applications one of which

includes the treatment of industrial wastewater. Traditional wastewater treatment

methods often employ the use of potentially hazardous materials or pollutants which

poses a problem for the environment, Photocatalysis solves this problem as it

employs the use of non-toxic semiconductor photocatalysts. A Semiconductor

Page 13: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

2

photocatalyst when illuminated at appropriate wavelengths will produce very

powerful oxidants which decompose organic materials into carbon dioxide and water

thereby facilitating the photocatalytic reaction.

The industrial applications of Photocatalysis are ever increasing as research into

photocatalysis develops new methods improved catalyst configuration etc.

photocatalysis will begin to gain traction as it has been proven to be a low cost and

sustainable technology for the treatment of various pollutants in air and water

including organics and heavy metals (Ibhadon and Fitzpatrick 2013). Photocatalysis

can be performed under sunlight or UV radiation, making it extremely cost effective,

environmentally friendly and as such can be applied worldwide. Considering that

photocatalysis can be performed using very basic equipment it is also very suitable

for developing regions. Unfortunately the limitations of this technology for industrial

deployment are still relatively unsolved as very few pilot studies show feasible

results in terms of industrial scale processes as industrial waste output rates and

volumes are still far too great for the capacity of current photoreactor concepts as

there are many variables to be considered when scaling up pilot designs.

One of the major issues being that to tackle industrial waste volumes large area will

be needed in order to construct reactors capable of tackling that load which will incur

high costs which will not justify the redundancy of current means in favour of

photocatalysis.

1.1 Project Aim

To design a lab scale Recirculating Photocatalytic Reactor for the treatment of

wastewater which can later be scaled up for industrial use.

1.2 Objectives

1. To carry out literature review.

2. To develop continuous flow recirculation.

3. To investigate means of effective mixing.

4. To build and test reactor.

5. Evaluate results and determine large scale feasibility.

6. Investigate possible further developments or improvements where required.

Page 14: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

3

2 Literature Review

2.1 Introduction

Semiconductor Photocatalysis over the last few decades has started to gain a lot of

industrial attention as its various applications become even more apparent and as

a result of this interest, a lot of work is being put into determining its validity for

industrial scale uses.

In the 1970s, Fujishima and Honda had discovered the photocatalytic splitting of

water on the surface of Titanium dioxide (TiO2) electrodes. This discovery had now

set the pace for the current research being carried out on Photocatalysis and its

various potential uses, resulting from this more effort was now being put into

researching the fundamentals processes and investigating the efficiency of the TiO2

Semiconductor catalyst, studies in this field had started to advance into energy

storage and renewal and more recently into environmental applications due to the

potential of TiO2 based Photocatalysis for the total destruction of organic pollutants

in wastewater and air. Research in this field now focuses primarily on ways in which

the catalytic reactions can be enhanced and used efficiently in industry. Some of the

most important aspects of these enhancements being reactor configurations and

developments in how the catalyst are deployed.

2.2 Semiconductor Photocatalysis Fundamentals

Photocatalysis is a compound word composed of two parts namely photo and

catalysis. Photo meaning light and catalysis being the term used to describe the

process in which a reaction is accelerated using a substance known as a catalyst.

This Catalyst remains unchanged in the reaction and is not used up after the

reaction takes place. Catalysts use in Photocatalysis are known as photocatalysts.

Semiconductors are beneficial for photocatalysis due to a combination of factors like

their electronic structures, light absorption properties, charge transport

characteristics and life times of the excited state (Kumar P.P., 2005). The Main

contributing factor to their suitability for use as a catalyst however is the electronic

structure comprised of the conductance and valence bands. The Valence band is

comprised of completely occupied orbitals at low energy while the conductance

Page 15: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

4

band is at high energy, enough to allow free movement of electrons between atoms

under the influence of external applied energy and is generally empty (Kumar P.P.,

2005). Between the conductance and valence band of the semiconductor is a space

devoid of charge known as the band gap it is generally small and in order for an

electron to move from the valence band to the conductance band it must be excited

by energy equal to or more than the energy required by the band gap (or band gap

energy). Just as there are different semiconductor materials band gap energy differs

as well. When sufficient photon energy is absorbed by the semiconductor and

electron from the valence band is excited and will jump from the low energy valence

band to the high energy conductance band. This electron is now free to move around

the semiconductor lattice. Although the electron has now left the full valence band

only partially filled leaving behind an electron hole, which is also free to move. This

excitation could cause the electron being promoted to the conductance band to

recombine with vacant holes in the valence band to create heat (undesired effect),

or cause the hoes and electrons to migrate to the surface of the semiconductor to

initiate redox and oxidation reactions with oxidants and reductants absorbed at the

catalyst surface. Which will ultimately result in the complete destruction of organic

compounds with absorbed species in the semiconductor material.

Figure 2.1 Generation of electron hole pairs

Vacuum Label

Valence Band h+

Egap EeV

Conduction Band

e-

Page 16: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

5

2.2.1 Semi-Conductor Photocatalyst

As described previously a catalyst is a substance used in order to accelerate or

instigate a chemical reaction which is not used up and remains unchanged at the

end of the chemical reaction (Jim Clark, 2002), therefore a photocatalyst can be

defined as a substance which upon exposure to light will work as a catalyst to alter

the rate of reactions.

There are various semiconductor photocatalyst that have been reported and tested

in literature, Examples are TiO2 which is generally the preferred catalyst at lab scale

experiments, like with the thin filmed multi tubular reactor developed by Adams M.

et al (Adams M., 2013), or ZnO (ZincOxide) investigated by Roselin et al., (2002)

for degradation of reactive red (RR 22). TiO2 and ZnO are the most widely

researched photocatalyst as of present day but TiO2 is more widely accepted

because although ZnO is tried and proven as an effective catalyst it remains

unstable as it yields Zn(OH)2 on the ZnO particle surface leading to the development

of inactive sites and loss of catalyst efficiency.

TiO2 is more often the catalyst of choice because it has many advantages which

justify its position over other available catalysts as TiO2 is inexpensive, insoluble in

most conditions and chemically stable with respect to Photo corrosion (Kumar P.P.,

2005), it is also a non-reactive substance and can be activated by low energy near

UV light.

TiO2 Photocatalyst comes in many different commercially available samples which

all favour the powder suspension configuration examples are Degussa P-25,

Millennium PC500, and DuPont R-900 etc. Different Samples of TiO2 will show

different photocatalytic activity when placed under identical conditions, this can be

attributed to differences in morphology, crystalline phase, specific surface areas,

doping, presence of impurities etc. TiO2 samples generally exist in two crystalline

configurations, anatase and rutile although still possible they are not commonly

available in brookite form. Anatase has been shown to possess more photoactivity

in comparison to rutile due to its lower band gap energy (3.0eV) in comparison to

rutile (3.2eV) stemming from the small difference in conduction band energies

(Kumar P.P., 2005). This means there will be a higher chance for recombination of

holes and electron in the rutile structure.

Page 17: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

6

Degussa P-25 is fast becoming the industry standard for photocatalysts mainly due

to its high photocatalytic activity which make it a more superior catalyst. The activity

of various TiO2 samples was tested by Sivakumar and Shanthi, (2001) for the

decolourization of reactive textile dyes under illumination by sunlight and both

concluded that Degussa P-25 Produced superior results to other samples tested

(CDH and CERAC).

2.3 Mechanism of TiO2 Photocatalysis.

TiO2 functions as a photocatalyst due to its Semi Conductor nature characterized

by its electron filled valence band and conductance band which is filled with holes

separated by a band gap. When energy equal to or greater than the band gap

energy Eg, is absorbed by TiO2, an electron will move from the valence band to the

conductance band, generating a reducing electron in the conductance band and an

oxidising hole in the valence band. This allows the holes and electron to get trapped

in surface states, and will undergo reactions with electron donating or accepting

species which have been absorbed at the TiO2 surface. This results in highly

charged electrons and holes which will then facilitate redox reactions, which will

result in the mineralisation of aqueous pollutants (Adams M. et al, 2013). Hydroxyl

radicals are generated on the surface of TiO2 through reactions of valence band

holes with absorbed water, hydroxide or surface titanol groups. Conductance band

electrons will react with electron acceptors such as oxygen in order to produce

superoxide (O2-). Redox potential of TiO2 electron/hole pair allows for the production

of hydrogen peroxide, primarily via reduction of absorbed oxygen (eq1-7)

(McCullagh C. et al, 2011)

TiO2 + h TiO2(e-cb + h+

vb) (1)

h+vb + OH-

,ads OH,ads (2)

OH,ads + Reactant Oxidized Products (3)

e-tr + O2,ads O2

- (4)

O2- + H+ HO2

(5)

HO2 + HO2

H2O2 + O2 (6)

H2O2 + e-cb OH + OH- (7)

Page 18: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

7

Figure 2.2 Photo excitation of Titanium Dioxide

2.4 Photoreactors and Types of Configurations

In order to demonstrate viability of semiconductor photocatalysis for industrial use,

Reactor deign is extremely important. Reactor Design research and development

aims to scale up laboratory scale projects into industrially feasible applications,

however this is a complex process as a lot of contributing factors are to be

considered in order to develop an acceptable efficient process. Factors which affect

the reactor design include distribution of pollutant and photocatalyst, pollutant mass

transfer, reaction kinetics and irradiation characteristics (McCullagh C. et al, 2011).

The most important consideration for a photoreactor design however is effective

photocatalyst illumination as it essentially determines the amount of water that may

be treated per effective unit area of deployed catalyst. Central to scaling up of

photoreactor is the problem of providing uniform distribution of illumination across

the sufficiently high specific area of photocatalyst required at larger scale.

Examples of reactor configurations are considered below

OH

O2

O2-

OH-

Bandgap

3.2eV

e-

h+

Conduction Band

Valence Band

UV light

Page 19: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

8

2.4.1 Multi Tubular reactors

TiO2 catalyst has been tested using multi tubular Photoreactors in order to lessen

the demand for excessively large surface area of reactors which could have big

implications for the consideration of reactors for industrial use as one of the biggest

issues surrounding Photoreactors is the need for large reactors due to the

requirement for large surface area for the catalyst. This type of system is

investigated by Adams Morgan et al. Using a lanthide doped Titania catalyst in order

to overcome the TiO2 catalysts restriction to UV wavelengths. The catalyst is used

as a coat for thin glass tubes that serve as the method of catalyst deployment. The

reactor is tested comparing results with similar reactors using alternate methods of

deployment (silica beads and Degussa P25). All reactors are tested under same

conditions, under UV radiation and then visible light. The results show similar

degradation of the methyl orange dye in the coated tube reactor to the use of

powdered catalyst under UV radiation and 70% degradation under visible light. The

use of the multi tubular reactor addresses issues encountered when using powdered

catalyst by eliminating the need for a filtering system as well as the use of excess

power required to run suspended powder reactors, which raises environmental

issues. The report further concludes that the multi tubular reactor can be seen to be

the more industrial friendly option as despite its significant reduction in surface area

degradation displays very comparable results.

Figure 2.3 Thin filmed multi tubular photoreactor and illumination box (M. Adams, et al. 2012)

Page 20: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

9

2.4.2 Suspended Liquid Reactors

TiO2 catalyst are often used in slurry/suspended reactors due to the large surface

area available to facilitate a reaction. Although this is seen as an advantage, the

need for filtration systems to filter out the fine powdered catalyst in order to separate

it from the effluent is an expensive feature and is a very large setback for industrial

consideration. Nan Chong et al. investigate the use of H-titanate nanofibers in an

annular slurry reactor for the degradation of Congo red. The aim was to develop a

potential solution for the catalyst separation problems experienced by conventional

slurry reactor systems. The H-titanate fibres possessed a high settling velocity (8.38

x 10-4 ms-1) as such could be easily separated from the effluent through

sedimentation. This provided a more cost effective approach to catalyst separation.

Although the benefits of this investigation are clear it is stated that irradiation of the

catalyst was difficult due to shielding of the light source by nanofiber particles closer

to the reactor walls therefore light penetration was limited.

Figure 2.4 Drum reactor finished model and schematic (C. McCullagh, et al., 2011)

Alternative to this method it is possible to attach the catalyst to a transparent

support. This method does provide adequate illumination of the catalyst but the

drawback being that it relies heavily on the mass transport of the pollutant to the

catalyst, which could be affected by any number of things within the reactor like the

causing slower rates of degradation.

In order to increase the degradation rate in slurry reactors an effective way of mixing

is required. M Adams et al. (2013), developed a novel drum reactor for photo

catalytic water treatment with the aims of finding an effective way for catalyst

Page 21: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

10

treatment that could be used at industrial scale. The drum reactor concept proposed

a drum which would serve as the reactor which would be continuously rotated in

order to provide an adequate method of mixing the catalyst-effluent slurry. Three

reactor designs were proposed and developed for batch and then continuous-flow

systems. The first of the three reactors consisted of a drum fitted with agitation

baffles to allow for high level of wastewater-catalyst interaction during rotation. The

second iteration of the reactor was designed based of the first with the aim of

increasing the agitation between the wastewater and catalyst suspension. A series

of paddles are incorporated into the inside of the drum so upon rotation agitation

would occur by the movement of the paddles within the drum resulting in turbulent

flow. The third iteration of the reactor taking inspiration from the first 2 included

paddles on the inside of the reactor constructed along the longitudinal length of the

drum in a V arrangement in order to counteract a corkscrew effect due to rotation

that would cause the catalyst to gather at one end of the vessel. The third design

further developed into a modular system of reactors capable of industrial use. The

third reactor is further investigated and it is found that the addition of the internal

paddles greatly increases mass transport and also the rate of pollutant degradation

showing an 85% reduction in organic content.

Mass transport with respect to slurry reactors has been largely ignored as an

impediment to the use of slurry reactors as the effects are not regarded as

consequential to degradation rates. The effects of photocatalyst irradiation, loading,

flow rates, total suspension volume, and changes in illumination length of the reactor

are investigated by Ballari et al. it is found that the limitations of mass transport can

result from non-uniformity of the irradiation surface. It is further stated that said

limitations are difficult to avoid but can be removed with fully turbulent flow within

the reactor. In Conclusion it is stated that can be overcome using 1g L-1 catalyst

loadings, 1 x 10-7 Einstein’s cm-1 s-1 accompanied by effective mixing.

2.4.3 Flat Plate Reactors.

Flat plate reactors are reactors consisting of a rectangular sheet on which the

catalyst of choice is adhered to. The sheet is positioned at an incline allowing for

laminar flow of the wastewater down the sheet which is irradiated by a light source

usually UV radiation. Flat plate Photoreactors are still very much developmental but

the use of this type of reactor possesses a relatively large catalyst surface area

Page 22: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

11

which means there is more space for the photocatalytic reactions to take place. Also

the flat plate reactors benefit from a uniform light distribution over the catalyst

surface which ensures uniform rate of degradation across the plate. Bearing the

obvious advantages in mind it is also important to note that the flat plate reactors

suffer from being mass transfer limited, and the fact that only a thin layer of

wastewater can be treated at a time massive areas will be needed for industrial

scale up.

Figure 2.5 Fixed bed Reactor schematic (Nogueira and Jardim, 1994)

Nogueira and Jardim developed and immobilised catalyst reactor for water

decontamination using solar light by adhering a TiO2 aqueous suspension to a flat

glass plate in order to produce a thin film of photocatalyst along a the flat plate which

would serve as the reaction site. The immobilised catalyst support (glass pate) is

faced towards the equator at a 22° incline. The reactor would have wastewater

delivered to it by a pump at the top at a pre-determined flowrate and allowed to flow

down by gravity while irradiated by sunlight to be collected and the base. The test

was carried out using single pass and then recirculating configurations. Using

methylene blue as a model substance, the reactor is observed to show 95.8%

degradation at a 22° slope and 89% degradation at a 25° slope.

Page 23: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

12

Figure 2.6 Flat plate reactor prototype (M. Adams, et al., 2008)

Adams et al, developed a flat plate reactor for removal of hydrocarbons from water

subsequently developing a multi-layer lab unit intended as a concept for a scaled

up design. The multi-layer flat plate reactor was developed based on an initial

prototype which was a conventional setup similar to development undertaken by

Nogueira and Jardim. Two Tests were carried out using a TiO2 catalyst testing two

different substrates (plates) one made of polymethylmethacrylate (PMMA) and

titanium metal. Both plates possess their own benefits as PMMA is known to be

transparent to UV light and that titanium produces titanium dioxide (TiO2) upon

oxidation which is also the catalyst of choice also it is thought that the adhesion

between the catalyst and titanium plate will be very good. The catalyst Plates are

prepared by coating the plates in an evenly distributed TiO2 and methanol

suspension and then allowed to dry. The plates are then mounted on to a support

at an angle to allow for effluent mass transport through gravity the support

incorporates a UV lamp help right above the plate. The Prototype setup as seen in

Fig 6. Shows all parameters described above. The Multi-layer system incorporates

the same design with multiple plates beneath each other with effluents moving from

one plate to the next creating a “concertina” multi plate reactor model. The results

from the experiments undertaken show a clear dominance of the PMMA plates to

the titanium plates as can be seen in the graph below (Fig 2.7). The graph also

shows that with a reduction in angle of the plate destructive efficiency increases due

to lower angles providing longer contact times between the catalyst and effluent.

The image below displays the multi-layer concept design developed by Adams et

al., (2008) for industrial scale up.

Page 24: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

13

Figure 2.7 Comparison of substrate with angle at optimum TiO2 loading (M. Adams, et al., 2008)

Figure 2.8 Multiple thin film plate reactor stack, Lab unit (left) concept design (right) (M. Adams, et al., 2008)

Although above a few reactors are considered there are still many reactor types that

have been developed and recorded in recent literature. In a review of photocatalytic

reactors McCullagh et al. produce a list of some reactors recorded in literature over

30 years predating the publication of the journal (2011). Below is a list of other

reactor types in previous literature (McCullagh et al., 2011).

Annular photoreactor

Packed bed photoreactor

Photocatalytic Taylor vortex reactor

Fluidised bed reactor

Coated fibre optic cable reactor

Falling film reactor

Thin film fixed bed sloping plate reactor

Swirl flow reactor etc.

Page 25: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

14

3 Design Development

3.1.1 Design Criteria

Based on research carried out on current technologies and recent developments

Key parameters for reactor design are identified to be an effective means of catalyst

deployment to allow for suitable interaction between catalyst and wastewater,

effective method of mixing in order to eliminate mass transport dependencies,

optimizing design for effective irradiation, method of on line catalyst separation to

eliminate need for additional separation processes.

3.1.2 Recirculation Mechanism

The recirculation mechanism was developed as a simple set of pipe one leading

from the stock solution to the pump and then from the pump to the reactor flow will

continue out the reactor and back into the stock solution.

3.1.3 Design Development

Based on all the parameters listed above a number of design ideas were considered

for development, taking cues from other successful reactors the design ideas are all

evaluated for suitability. Different Reactor configurations are considered for

development but due to time constraints and available resources some design are

cut from the evaluation process as the timescale for production will impede progress

of research. As a result the reactor configuration considered is a slurry/batch type

reactor as they are simple designs and have been extensively research for water

remediation which provides respectable expectations for the final design. Batch

reactors suffer from mass transport limitations and effective catalyst deployments

and as such considered design varied by mixing methods and catalyst deployments.

Design sketches for considered design can be found in the appendix.

Page 26: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

15

Design 1

Figure 3.1 Paddle concept design

The first proposed design featured a paddle mixer deployed on the inside of the

reactor to be powered by a motor. This mixer is to be made of glass as to allow for

light propagation through it in order to allow effective photocatalysis. The mixer

effects agitation allowing for even spread of the photocatalyst within the reactor

vessel.

Disadvantages that this design present are that a design such as this scaled up

would involve development of expensive components for example the glass mixer

would be a relatively costly component to develop. Powering the glass mixer at

industrial scale will also incur more cost as the motor required to power the mixer

would consume energy which will also have to be factored into cost.

Catalyst configuration options for this design would be limited to powder or pelletized

catalyst which present filtration problems as catalyst effluent separation

mechanisms would have to be included.

Page 27: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

16

Design 2

Figure 3.2 Glass Bead concept design

This design features photocatalyst coated glass beads within the reactor. The glass

beads are to remain within the reactor chamber in place with the effluent as to void

the need for mixing as the glass beads provide even distribution of the catalyst

around the reactor. Filtration also becomes unnecessary as the large beads will be

incapable of passing through pipes. This method of catalyst deployment provides a

high surface area for irradiation although less than a powder configuration but

greater than alternative immobilized catalyst configurations.

Drawback for this design are the possibility of a glass bead blocking outflow of

wastewater causing pressurisation of the reactor and then eventual failure of the

reactor. Also despite the availability of good reaction surface area, the glass beads

reduce available volume for the wastewater to occupy the reactor which reduces

reaction sped.

Page 28: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

17

Design 3

Figure 3.3 Internal drum concept design

The third reactor design involved the insertion of a smaller glass cylinder coated

with a catalyst deployed inside of the reactor chamber this smaller glass cylinder

was to feature small paddles along the inner diameter in order to agitate the

wastewater as well as a powdered catalyst which would also be loaded into the

reactor. The benefits of this model were that it the mixer instead of serving no

function other than agitation would also serve as added catalyst surface area to that

of the powdered catalyst within.

The drawback of this design similar to the first, it would involve the use of a motor

for power which would increase energy costs at larger scale as well as the difficulty

in manufacturing the internal cylinder at a larger scale will incur additional cost

making this an expensive system to manufacture. Also filtration methods will need

to be considered for the powdered catalyst.

Page 29: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

18

3.2 Developed Design

In order to develop a suitable system a prototype model was designed for testing.

This model features a simple design with a glass tube and plastics caps on both

ends fitted with ports to accommodate pipe fittings.

Figure 3.4 Reactor Model

The prototype was designed with the aim of testing a variety of catalyst loading and

as such easy access to the reactor chamber is included through the splitting of the

upper end cap into two sections. The upper end are held together with using screws

and bolts while a seal is created using silicone grease at the interface of the two

parts. The outer end caps are fitted with 2 holes each to accommodate pipe push

fittings which would be connected to ball vales to control flow. In operation the

wastewater would be pumped through the top of the reactor and flow out of the

reactor through the bottom back into the stock solution to be recirculated back into

the reactor. Both holes at the base will be kept open to allow flow In order to increase

flow rate out of the reactor to prevent filling the reactor as the filters placed in each

fitting will impede causing the reactor to fill up faster than it can be drained, which

would lead to leaks as the silicon grease seal would not hold up under pressure.

The interfaces between the caps and glass were joined using a silicon sealant in

Page 30: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

19

order to prevent leaks and four tie rods running through all caps secured using nuts

hold the entire reactor together.

In order to eliminate mass flow rate dependencies, the recirculating nature of the

system was considered acceptable agitation as through recirculation all of the

wastewater would pass over the catalyst within the reactor. In order to prevent the

catalyst settling at the base of the reactor, it was assumed that partially filling the

reactor to allow the inflow of water to create a plunge which would move the catalyst

around within the reactor.

3.2.1 Build Procedure

Reactor vessel end caps are made of Polytetrafluoroethylene (PTFE) more

commonly known as Teflon due to its good resistance to UV radiation. Caps are

Machined from Bar according to drawings contained in the appendix. The RS

components bought glass tube is then capped at both ends and bonded to Teflon

caps using a RTV silicone sealant. Tie rods are incorporated at 4 point on both caps

to maintain the integrity of the seal as Teflon is renowned for its not stick properties

and as such the silicon seal will only serve to prevent leaks. Silicone seal is deemed

fit for purpose due to the low pressure the reactor will be operating at. Another four

bolts are used to secure the end caps on the top of the reactor and silicone grease

is applied at the interface in order to prevent leaks from this section. Each port is

connected to a pipe push fitting and then subsequently connected to ball valves

which lead to two tanks on either end of the reactor one for wastewater and one for

effluent. The effluent will then be recirculated into the wastewater tank and then

back into the reactor.

Model technical drawings are as seen in (appendix A)

Page 31: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

20

Figure 3.5 Reactor parts and assembled prototype

3.2.2 Design Calculations

The Design for the prototype was highly reliant on the incoming turbulent flow to

produce sufficient agitation. In order to determine the flow regime of the incoming

solution, Reynolds number of the flow coming into the reactor from the pipes had to

be calculated.

The pipes used in the prototype design were smooth transparent flexible PVC pipes

with dimensions as follows:

Outer diameter: 7.35mm

Inner Diameter: 6.35mm

Flow is classed as turbulent when Reynold’s Number (Re) is greater than 4000

(Re>4000)

𝑅𝑒 =𝜌𝐷𝑉

𝜂 (1)

Where: ρ = density

D = diameter

V = velocity

η = dynamic viscosity

Page 32: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

21

Density of water is taken as 1000kg/m3 while dynamic viscosity is taken to be 1 ×

10−3𝑘𝑔/𝑚𝑠

Pump volumetric flow rates: 9 x 10-6m3/s - 25.7 x 10-6m3/s

In order to calculate required flow rate for turbulent flow, Re was required to be 4100 in

order to avoid possibility of transition flow (Re 1000 – 4000).

Through volumetric flow rate, flow velocity can be calculated using the following equation.

𝑄 = 𝐴𝑉 (2)

Where: Q = Volumetric flow rate

A = Pipe Cross sectional area

V = Flow velocity

𝑖𝑓 𝑅𝑒 = 4100

𝑉 =𝑅𝑒𝜂

𝜌𝐷=

4100 × 1 × 10−3

1000 × 0.00635= 0.6457𝑚/𝑠

𝑄 = 𝐴𝑉 =𝜋 × 0.006352

4× 0.6457 = 20.45 × 10−6𝑚3/𝑠

Therefore in order to implement turbulent flow, incoming flow rate will have to be

set at 20.45 x 10-6m3/s.

Pump specifications located in Appendix B

Pump specs are in imperial values unit conversion calculations are located in

Appendix C.

Page 33: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

22

4 Testing

4.1 Experimental setup

In order to determine the suitability of developed ideas, the reactor was put through

a photocatalysis tests using methylene blue as a model compound for degradation

which would give indications off how this design would fair in larger scale.

4.1.1 Methylene blue

Two Methylene blue stock solutions were prepared at 100𝜇𝑀/𝑙 concentration. The

solutions were prepared by adding 0.03739 grams of methylene blue dye (Fisher

Brand) in 100ml of water. Two sets of solution both 600ml, were then produced at

10𝜇𝑀/𝑙 through further dilutions of the stock solutions. Calibration curve for

methylene blue solution displayed below in (Fig 4.1).

Figure 4.1 Methylene blue Calibration curve

The graph in Fig 4.1 was developed by diluting the methylene blue stock solution at

10μM/L by decrements of 2 in order to develop a linear relationship for methylene

blue concentration and UV absorbance which can be used to asses absorbance of

the solution during test phases to obtain methylene blue concentrations through the

use of the line equation.

4.1.2 Catalyst loading

Pelletized TiO2 was used as the photocatalyst for the reaction for ease of catalyst

and effluent separation. Catalyst loading was set to 30g/l. For the reactor volume of

y = 0.0917x - 0.0151

0

0.2

0.4

0.6

0.8

1

1.2

0 2 4 6 8 10 12

Ab

sorb

ance

Concentration (μM/L)

Calibration Curve

Page 34: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

23

249ml the catalyst loading was calculated to be 7.47g. Catalyst and solution were

allowed to sit in dark prior to testing to reach dark absorption equilibrium.

4.1.3 Pump

For the recirculation mechanism a verderflex EV1500 peristaltic pump was used

with flow rates ranging from 3.17ml/s - 42.83ml/s. The pump also provided a means

of agitation for the reactor so as to circumvent mass transport limitations of the

reactor. Reactor was filled to about 80% capacity to create a plunge within the

reactor chamber which also allowed for better mixing. The pump is run at the mean

flow rate between max and min flows approximately 22.9985 x 10-6m3/s which is

sufficient enough to effect turbulent flow.

4.1.4 UV Light Containment Reactor (illumination source)

The UV Light containment reactor (Fig 3.1) obtained from prior experiments run

within the CRE-E lab consisted of 4 UV lamps, one on each wall of the box. The box

was fitted with ports which accommodated fans to keep the system temperature at

safe levels. The UV lamps used in the UVLCR are commercially available low power

36W compact non-integrated fluorescent lamps the box was constructed using

Perspex which is mirrored on the interior. Spectral output of UV lamps within the

UVLCR are shown in Fig 3.2 below.

Figure 4.2 Ultraviolet Light Containment Reactor (UVLCR)

Page 35: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

24

Figure 4.3 Spectral output for UV lamps

4.2 Experimental Procedure

The photoreactor vessel was placed into the UV light containment reactor (UVLCR)

and two tests were ran.

Figure 4.4 Experimental setup

The first test was a control test with the photoreactor and methylene blue solution

inside the UV light containment reactor without any catalyst. The experiment was

ran for a period of 60 mins with a 1ml sample collected every 10mins using a pipette.

The second experiment was carried out using the photocatalyst and methylene blue

within the photoreactor and then placing it into the UVLCR. The process was

allowed an equilibrium time of 30 mins in the dark (with UVLCR turned off). In order

Page 36: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

25

for the dark absorbance to be determined 1ml sample was taken before and after

equilibrium period. After equilibrium period the UVLCR was turned on and then the

process was allowed to run continuously for 60mins with 1ml samples taken every

10mins. The samples were analyzed using UV-vis spectrometry and the absorbance

recorded. The experiment was run with agitation produced by incoming flow o the

reactor. Catalyst and solution separation was carried out within the reactor by mesh

filters placed inside of each outlet fitting.

4.3 Results

The first experiment carried out on the MB solution irradiated in UV light without any

photocatalyst loading, in order to determine MB degradation under UV light without

the photocatalyst to induce a reaction. The following absorption spectral pattern was

produced as a result.

Figure 4.5 Temporal absorption spectral pattern of MB under UV radiation only

Fi 4.5 above shows the Degradation of the methylene blue solution over 60 minutes

of irradiation by UV light alone. The graph shows a relatively insignificant drop in

absorbance of the methylene blue solution which indicates little or no degradation

can occur without the presence of the photocatalyst.

-0.2

0

0.2

0.4

0.6

0.8

1

1.2

1.4

390 440 490 540 590 640 690 740 790

Ab

sorb

ance

Wavelength, nm

MB absorbance pectral pattern over 60 miuntes

60

Page 37: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

26

The 2nd experiment ran to show methylene blue degradation under UV irradiation

with a photocatalyst loading. The following absorption spectral pattern was

observed.

Figure 4.6 Temporal absorption of methylene blue degradation in the with catalyst loading under UV irradiation

Fig 4.6 shows the degradation of methylene blue over a 60 minute UV irradiation

period in the presence of a TiO2 photocatalyst.as seen over the 60 minute period,

significant drops in the absorbance of the methylene blue solution can be observed

which gives indication of the performance of the reactor.

Following collection of both results Fig 3.7 below is developed through calculating

percentage absorption.

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

390 440 490 540 590 640 690 740 790

Ab

sorb

ance

Wavelength, nm

MB Absorbance spectral pattern over 60 minutes

Page 38: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

27

Figure 4.7 %Absorption of methylene blue at maximum absorption wave length

Fig 4.7 shows a comparison of the percentage drop in absorbance of MB solution

over the 60 mins comparing how much of an effect the photocatalyst has on the

reaction further highlighting the importance of catalyst loadings

Using the equation of the line governing the methylene blue calibration curve, the

following graph showing the drop in methylene blue concentration in both tests.

Figure 4.8 Methylene blue concentration over 60 minutes of photocatalysis

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60

% A

bso

rpti

on

Time (min)

Methylene blue %absorbance at 667nm

UV + Cat

UV

0

2

4

6

8

10

12

0 10 20 30 40 50 60

Met

hyl

ene

blu

e co

nce

ntr

atio

n (

μM

/l)

Time (minutes)

Methylene Blue degredation over 60 mins

UV only

UV+CAT

Page 39: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

28

Figure 4.8 shows a comparison of MB concentration drop as time elapses. With a

near constant degradation in the presence of catalyst and then relatively no

degradation in the UV control test.

Page 40: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

29

5 Discussion

5.1 General Overview

For the design of the reactor various parameters were put into consideration.

Factors like catalyst loadings, effective mixing amongst others play a huge part in

how effective a reactor design will be in the long run. For the final design chosen,

the major challenges involved were finding suitable methods to effect photocatalyst

and wastewater separation within the pump. Although it would have been beneficial

to have incorporated more advanced catalyst loading design like coated silica beads

or the multi tubular design developed by Adams Morgan, time constraints would

prove an obstacle to such endeavors. Regardless however the availability of

pelletized TiO2 proved the ideal solution. Although proven that Degussa P25 powder

would produce more efficient and quicker degradation of methylene blue, it was

ultimately dismissed as an option due to the difficulty that separation of this powder

would create for the reactor. The initial final design which featured just end caps and

glass tube joined by a silicon sealant proved ineffective as the Teflon material used

for the end caps is a non-stick compound and without the use of a primer bonding

of the Teflon to the glass could not be achieved which lead to leaks and caps falling

off in the original design. The revised design which incorporated tie rods served to

better hold the reactor together while silicon grease and a sealant kept fluid from

leaking out of the reactor and proved a better all-round design and held together for

the duration of the experiment.

Under experimental conditions, the implementation of turbulent inflow although

successful coupled with the plunge created by the partially filled reactor, upon

observation was not a successful enough approach as the photocatalyst was drawn

to the bottom of the reactor by the outflowing liquid which could lead to reduced

degradation rates. Regardless of this fact, it can also be said that through

recirculation mass transport is negated as the photocatalyst will make contact with

all the MB solution present as it is passed out of the reactor and back in.

Bearing in mind all fall backs of the final design, improvements can be made in order

to better performance of the reactor. Firstly retention times within the reactor are

relatively a lot lower than you would have in a non-continuous flow system which

leads to less time for photocatalyst and solution to react causing less degradation

Page 41: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

30

rates. This problem can be easily combated by including multiple passes in the

reactor system. This sort of design will also be better suited for handling larger

volumes of wastewater although incurring more cost. Efficient mixing of the catalyst

and MB solution was not achievable using methods discussed in the original design

and as such simplified mixing methods i.e. the use of paddles or rotation of the

reactor are viable options for improvements on the photocatalyst interaction with the

available solution. Improvements upon this area should ensure a more even spread

of photocatalyst around the reactor.

5.2 Test Results

Adsorption of organic pollutants is an important indicator for determining the

degradation rates of photocatalytic oxidation. Methylene Blue (MB) adsorption on

the surface of the TiO2 greatly affects the degradation process as it is theorized that

oxidation of organic compounds occurs following adsorption of the organic

compounds on the photocatalyst surface.

The control experiment which was carried out using the methylene blue within the

reactor irradiated within the UVLCR. Using ultraviolet visible spectral analysis, to

monitor the MB absorbance the absorption spectral pattern in Fig 4.5 was produced

in order to show how much degradation the UV light alone was responsible for this

would demonstrate how much degradation of the MB solution is truly photocatalyst

reliant. As seen in the Fig 4.5, the drop in absorbance over the 60 minute irradiation

period was quite minimal. Over the first 30 mins it can be seen that the UV does

degrade the methylene blue to some extent before the absorbance eventually

stagnates. Fig 4.6 which represents the photoreactor experiment carried out with

the photocatalyst loading of a concentration of about 30g/l of pelletized TiO2. This

graph shows that over the 60 minutes about 47% of the MB has been degraded

within the solution. This in stark contrast to the experiment carried out with UV alone

and shows just how much the effect of the photocatalyst has upon the entire

process. The methylene blue solution shows peak absorbance at around 667nm

wavelength. At that peak the drop in methylene blue absorbance is clearly

pronounced when photocatalyst absorbs UV radiation work to initiate the

photocatalytic reaction. Although, it is important to note that in prior experiments of

this type most notably the drum reactor developed by Adams et al., (2013), 90%

degradation over a 60 minute period was reported for continuous flow using 36W

Page 42: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

31

UV lamps deployed through the drum reactor. Failure of the reactor designed in this

report to reach benchmarks of similar systems reported in literature can be attributed

to the lack of multiple passes, insufficient agitation for the mixing of the catalyst, or

distance from illumination source.

Assessing results at peak absorbance (667nm wavelength), a comparison of the UV

and UV + Catalyst tests can be developed Fig 4.7 depicts the percentage drop in

absorbance of the methylene blue over the 60 minute irradiation time. For the UV

only test it shows the absorbance reaches an equilibrium at the 30 minute mark

where after that point degradation ceases to take place Whereas the UV +

photocatalyst test shows a relatively constant degradation in MB. This comparison

serves to further highlight the importance of the photocatalyst loading within the

photoreactor. Fig 4.8 the drop in methylene blue concentration as calculated using

the calibration curve using absorbance at the same wavelength as the calibration

curve. Although the concentration of methylene blue in the experiments was higher

or lower in the UV and UV+CAT experiments due to difficulties in precisely weighing

out the exact amount of methylene blue required, the rate of degradation is the

relevant parameter. This just reiterates the findings of Fig 4.7 but better depicts the

near constant degradation of methylene blue in the UV and photocatalyst test.

The testing phase for the photoreactor was carried out to achieve only the most

essential results to prove functionality of the proposed design. The tests carried out

do provide sufficient information which allows for assessments of how a similar

design at larger scale would fare.

Page 43: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

32

5.3 Improved Design

Figure 5.1 final design concept

For the improved design taking information from results derived from the prototype,

this final concept design was created. The tested photoreactor’s performance gives

indication of how a singular pass system would perform and through analysis of

results covered in the sections ahead, a multiple pass system was developed

incorporating the same accommodation for versatility in catalyst loadings. The

concept system would include a 3 pass system designed on the premise of the

prototype with the wastewater flowing through 3 reactor vessel sections before

finally flowing into the stock solution for recirculation. The addition of the 3 phase

system would allow for larger volumes of waste water to be treated within a given

time and also faster degradation rates as the photocatalyst surface area would triple

as well as contact time for the wastewater. Improvements on catalyst loading would

also be necessary and tighter seas effected by O-rings and sealants would allow for

higher pressure flow than the prototype. Suggested catalyst loading would be

coated Multi tubular set up similar to those developed by M. Adams, et al (2012) as

they would void the need for mixing of the catalyst and wastewater which is

beneficial for the recirculation as mixing would interfere with flow. The coated tubes

system have also been shown to produce highly efficient degradation in comparison

to what is reported as the most efficient catalyst choice (Degussa P25 powder). Fig

5.2 shows the relation developed by M. Adams, in the investigation carried out on

Multi-tubular and silica bead systems under UV irradiation clearly displaying the

multi tubular system at different doping percentages( green and blue) showing

Page 44: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

33

equally as high efficiencies as the powder catalyst (purple). Using coated tube

although reducing available volume within the reactor will allow for quicker reaction

times due to increase in surface area.

Figure 5.2 methyl orange degradation by P25 (purple), silica beads, and %doped glass tubes (blue & green) (M. Adams, et al., 2012)

Page 45: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

34

6 Conclusion

All things considered, the prototype design achieved the intended primary result

which was to effect degradation of methylene blue through photocatalysis. The

primary aim was to design a labs-scale recirculating photocatalytic reactor for

wastewater remediation. Although the first iteration did fail to hold together, the

addition of tie rods served to solve the problem. The photoreactor successfully

degraded approximately 4 of the MB within a stock solution of about twice its volume

over a 60 minute time period. Given that other batch processes run with similar

reactor set ups show about 90% degradation at the reactors capacity without

recirculation, the prototype can be deemed a success.

Assessing the suitability of a lab scale reactor for larger scale development is a

difficult process as many factors come into play. As at larger scale effective

irradiation might prove problematic as well as ability to handle the massive volumes

of wastewater at an industrial level as well as the pumping power that would be

required for a photoreactor at that size. Adding all those factors the cost of such

operations begin to grow. The lab scale reactor designed in this project although

effecting successful degradation, was very reliant on pumping power for the

effective mixing which at larger scale will drive up cost. Also development of UVLCR

at larger scale might prove difficult as energy consumption will rise and the heat

produced by the UVLCR would have to be managed in for safety reasons.

Design stage problems like sealant failure could have been avoided through better

material selection or further research on the Teflon material used in order to have

implemented the use of a primer. Discrepancies in the testing phase like the

difference in base absorbance of the methylene blue solution arose from slight

differences in the concentrations of the two prepared solutions. This could have

been avoided through preparation of one larger stock solution which could then be

divided for testing. Regardless of errors present, the design can be concluded as a

success as the results provide an adequate benchmark for the development of the

improved concept design.

Page 46: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

35

7 Further Development

For further development on the photoreactor tested in this report, the suggested

improved design would be an ideal start as that design shows greater potential for

industrial scale use due to use of multiple phases. Further work will also benefit from

more extensive testing on developed reactor such as implementing various catalyst

loadings, or methods of catalyst deployment. Other improvements to consider are

development of integrated UV illumination into the design so as to reduce the

reliance on an external UVLCR system as used in the experiments detailed in this

report. Also recommended is developing the improved design into a modular system

which would allow for the addition of various phases which will increase the available

volume for reaction and as such fair better in industrial processes and also possess

a sort of versatility to be able to handle different volume requirements. Further

testing should include the development of multiple reactor sizes to discern a certain

linearity of degradation if any so as to accurately determine what a much larger scale

design would require for successful operation. Investigation into developing

catalysts for use in the visible light spectrum should also be considered as this is

seen as an ideal way to drive down cost as it would allow the photocatalysis process

ease of deployment in rural areas without easy access to electricity implement

sunlight for efficient irradiation.

Page 47: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

36

References

ADAMS, M., CAMPBELL, I. & ROBERTSON, P. K. J. (2008) Novel

Photocatalytic reactor development for removal of hydrocarbons from water.

International Journal of Photoenergy, 2008, pp1–7.

ADAMS, M., CAMPBELL, I., RUSSELL & ROBERTSON, D. W. (2014) Citation

details citation for the version of the work held in ‘OpenAIR@RGU’.

International Journal of Chemical Reactor Engineering. [Online]. Available

from:

https://openair.rgu.ac.uk/bitstream/handle/10059/1060/Adams?sequence=1

[Accessed 04/04/2016].

ADAMS, M., CAMPBELL, I., MCCULLAGH, C., RUSSELL, D., BAHNEMANN,

D. W. & ROBERTSON, P. K. J. (2013) From ideal reactor concepts to reality:

The novel drum reactor for Photocatalytic wastewater treatment. International

Journal of Chemical Reactor Engineering, 11(2).

ADAMS, M., SKILLEN, N., MCCULLAGH, C. & ROBERTSON, P. K. J. (2013)

Development of a doped titania immobilised thin film multi tubular photoreactor.

Applied Catalysis B: Environmental, s 130–131, pp99–105. [Online]. Available

from:

http://www.sciencedirect.com/science/article/pii/S092633731200476610.1016/j.

apcatb.2012.10.008 [Accessed 04/04/2016].

ALEXIADIS, A. & MAZZARINO, I. (2005) Design guidelines for fixed-bed

photocatalytic reactors. Chemical Engineering and Processing, 44(4), pp453–

459.

BAGHERI, S., JULKAPLI, M., NURHIDAYATULLAILI, HAMID, B. A. &

CORPORATION, H. P. (2014) Titanium dioxide as a catalyst support in

heterogeneous Catalysis [online]. Hindawi Publishing. Available from:

http://www.hindawi.com/journals/tswj/2014/727496/10.1155/2014/727496

[Accessed 04/04/2016].

BRANDI, R. J., ALFANO, O. M. & CASSANO, A. E. (1996) Modelling of

radiation absorption in a flat plate photocatalytic reactor. Chemical Engineering

Science, 51(11), pp3169–3174.

Page 48: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

37

CASTELLOTE, M. & BENGTSSON, N. (2011) Principles of TiO2

Photocatalysis, Springer Science + Business Media.

CHIOVETTA, M. ., ROMERO, R. . & CASSANO, A. . (2001) Modelling of a

fluidized-bed photocatalytic reactor for water pollution abatement. Chemical

Engineering Science, 56(4), pp1631–1638.

CHONG, M. N., JIN, B., ZHU, H. Y., CHOW, C. W. K. & SAINT, C. (2009)

Application of h-titanate nanofibers for degradation of Congo red in an annular

slurry photoreactor. Chemical Engineering Journal, 150(1), pp49–54.

FUJISHIMA, A., RAO, T. N. & TRYK, D. A. (2000) Titanium dioxide

photocatalysis. Journal of Photochemistry and Photobiology C: Photochemistry

Reviews, 1(1), pp1–21. [Online]. Available from:

http://www.sciencedirect.com/science/article/pii/S138955670000002210.1016/

S1389-5567(00)00002-2 [Accessed 04/04/2016].

HERRMANN, J.-M. (1999) Heterogeneous photocatalysis: Fundamentals and

applications to the removal of various types of aqueous pollutants. Catalysis

Today, 53(1), pp115–129. [Online]. Available from:

http://www.sciencedirect.com/science/article/pii/S092058619900107810.1016/

S0920-5861(99)00107-8 [Accessed 04/04/2016].

IBHADON, A. & FITZPATRICK, P. (2013) Heterogeneous Photocatalysis:

Recent advances and applications. Catalysts, 3(1), pp189–218.

KANKI, T., HAMASAKI, S., SANO, N., TOYODA, A. & HIRANO, K. (2005)

Water purification in a fluidized bed photocatalytic reactor using TiO2-coated

ceramic particles. Chemical Engineering Journal, 108(1-2), pp155–160.

KUMAR, P. P. (2005) Photocatalysis of organic pollutants by catalyst

supported on adsorbents.

LINSEBIGLER, A. L., LU, G. & YATES, J. T. (1995) Photocatalysis on TiO2

surfaces: Principles, mechanisms, and selected results. Chemical Reviews,

95(3), pp735–758.

Page 49: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

38

MCCULLAGH, C., SKILLEN, N., ADAMS, M. & ROBERTSON, P. K. J. (2011)

Photocatalytic reactors for environmental remediation: A review. Journal of

Chemical Technology & Biotechnology, 86(8), pp1002–1017.

MILLS, A., O’ROURKE, C. & MOORE, K. (2015) Powder semiconductor

photocatalysis in aqueous solution: An overview of kinetics-based reaction

mechanisms. Journal of Photochemistry and Photobiology A: Chemistry, 310,

pp66–105. [Online]. Available from:

http://www.sciencedirect.com/science/article/pii/S101060301500138010.1016/j.

jphotochem.2015.04.011 [Accessed 04/04/2016].

NOGUEIRA, R. F. P. & JARDIM, W. F. (1996) TiO-fixed-bed reactor for water

decontamination using solar light. Solar Energy, 56(5), pp471–477. [Online].

Available from:

http://www.sciencedirect.com/science/article/pii/0038092X9600036910.1016/0

038-092X(96)00036-9 [Accessed 04/04/2016].

SCHNEIDER, J., MATSUOKA, M., TAKEUCHI, M., ZHANG, J., HORIUCHI, Y.,

ANPO, M. & BAHNEMANN, D. W. (2014) Understanding TiO 2 Photocatalysis:

Mechanisms and materials. Chemical Reviews, 114(19), pp9919–9986.

SKILLEN, N., ADAMS, M., MCCULLAGH, C., RYU, S. Y., FINA, F.,

HOFFMANN, M. R., IRVINE, J. T. S. & ROBERTSON, P. K. J. (2016) The

application of a novel fluidised photo reactor under UV–Visible and natural

solar irradiation in the photocatalytic generation of hydrogen. Chemical

Engineering Journal, 286, pp610–621. [Online]. Available from:

http://www.sciencedirect.com/science/article/pii/S138589471501514410.1016/j.

cej.2015.10.101 [Accessed 04/04/2016].

SPASIANO, D., MAROTTA, R., MALATO, S., FERNANDEZ-IBAÑEZ, P. & DI

SOMMA, I. (2015) Solar photocatalysis: Materials, reactors, some commercial,

and pre-industrialized applications. A comprehensive approach. Applied

Catalysis B: Environmental, s 170–171, pp90–123. [Online]. Available from:

http://www.sciencedirect.com/science/article/pii/S092633731500002810.1016/j.

apcatb.2014.12.050 [Accessed 04/04/2016].

Page 50: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

39

WANG, Y., SUN, D. D. D., LIU, J. & LIU, L. (2012) Enhancing stability and

Photocatalytic activity of ZnO Nanoparticles by surface modification of

Graphene oxide. Journal of Nanoscience and Nanotechnology, 12(5), pp3896–

902. [Online]. Available from:

https://www.researchgate.net/publication/230593575_Enhancing_Stability_and

_Photocatalytic_Activity_of_ZnO_Nanoparticles_by_Surface_Modification_of_

Graphene_Oxidehttp//dx..org/10.1166/jnn.2012.6174 [Accessed 04/04/2016].

YONG YONG, E. (2005) Application of photocatalysis and ferrate (VI) oxidation

in removal of organic compound for water purification.

ZHANG, Y. (2013) Modelling and Design of Photocatalytic reactors for Air

Purification.

Page 51: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

40

8 Appendices

Appendix A – Technical drawings

Figure 8.1 Lower lid Drawing

Page 52: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

41

Figure 8.2 Top Lid 1 Drawing

Page 53: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

42

Figure 8.3 Top lid 2 Drawing

Page 54: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

43

Figure 8.4 Glass tube drawing

Page 55: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

44

Appendix B – Pump Specifications

Figure 8.5 Pump data sheet

Page 56: Development of Recirculating Photocatalytic Reactor for Wastewater Remediation Final Draft

45

Appendix C – Unit Conversions

If 1litre = 10-3 m3

1mililitre = 10-6m3

Max and min flow rate of pump =

2570 𝑚𝑙/𝑚𝑖𝑛 =2570 ×10−6

60= 42.83 × 10−6𝑚3/𝑠

190𝑚𝑙/𝑚𝑖𝑛 =190 ×10−6

60= 3.167 × 10−6𝑚3/𝑠

Mean flow rate

42.83+3.167

2= 22.9985

22.9985 × 10−6𝑚3/𝑠