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Environ. Sci. Technol.

2010, 44, 20562063

Simulation of UV Photoreactor for


Degradation of Chemical
Contaminants: Model Development
and Evaluation
SIAMAK ELYASI* AND
FARIBORZ TAGHIPOUR
Chemical and Biological Engineering Department, University
of British Columbia, 2360 East Mall, Vancouver,
BC V6T 1Z3, Canada

Received August 13, 2009. Revised manuscript received


January 31, 2010. Accepted February 2, 2010.

Models simulating the performance of UV reactors enhance


our understanding of the fundamental principles governing the
operation of these units. When modeling the performance of
UV reactors, governing equations for all related phenomena are
derived and solved. This research presents a step-by-step
methodology to setup and solve the governing equations
determining the performance of UV reactors and to evaluate
the results. A computational fluid dynamic (CFD) model
was developed in order to simulate UV photoreactors in the
Eulerian framework for chemical removal using a UVbased hydroxyl radical initiated oxidation process. Verifying
the results of the integrated CFD model, a novel method was
developed using a modified planar laser-induced fluorescence
technique for measuring tracer concentration profiles inside
the UV reactor. In addition, the components of the CFD
modelshydrodynamics and radiationswere evaluated using
experimental profile throughout the entire reactor. This verified
procedure can be applied to the simulation and optimization
of UV photoreactors with various geometries and operating
conditions.

1. Introduction
UV technology, in combination with an oxidant such as
hydrogen peroxide, provides an effective method of water
and wastewater treatment. This photoinitiated oxidation
process (also referred to as the UV-based advanced oxidation
process, AOP) can be applied when treating optically clear
water or wastewater that contains contaminants with concentrations of less than 1000 ppm (1). In UV-based AOP,
hydroxyl radicals which are generated through the reaction
of UV radiation with hydrogen peroxide play a major role in
oxidizing persistent chemicals. A mathematical model simulating the performance of UV reactors can contribute to our
understanding of UV technology for water treatment, allowing
us to obtain the full benefit of UV photoreactors.
The modeling of a UV photoreactor is a challenging area
of research because of the multiphysics nature of this type
of reactor. The model should allow for the effects of fluid
movement and mixing (hydrodynamics), the distribution of
radiant energy (radiation field), the rate of deterioration of
* Address correspondence to either author. Tel.: (+1) 604-8223238. Fax: (+1) 604-822-6003. E-mail: siamak.elyasi@gmail.com (S.E.);
fariborz@chbe.ubc.ca.
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 6, 2010

the chemicals (photochemical/chemical kinetics), and the


interaction of these phenomena with one another. The UV
reactor performance model (semimechanistic approach)
consists of a system of partial differential equations governing
various phenomena in the UV reactor that should be solved
simultaneously. Due to the complexity of the reactor
geometry and interaction of many phenomena, analytical
solutions do not exist, and a numerical solution is the only
practical approach, using relevant techniques such as
computational fluid dynamics (CFD).
The modeling results for reactor performance should be
validated against experimental data (hydrodynamics, radiation, and species concentration) to ensure their applicability
to reactor design and optimization. A number of researchers
have developed models of photoreactor performance (e.g.,
see refs 2-7); however, they have used conventional methods
for model evaluation. These methods compare the modeling
predictions with the experimental results for the overall
reactor performance, which is determined by comparing the
ratio of the outlet to the inlet concentration of the reactor.
This method does not reveal any discrepancies that might
exist between the model predictions and the experimental
values for velocity, radiant energy, and concentration of
species inside the photoreactors. Some other researchers
(8, 9) have compared the hydrodynamics from the reactor
performance model with experimental velocity data inside
the photoreactor obtained using particle image velocimetery
(PIV). But, in these cases, the CFD model predictions have
been typically validated using PIV experimental data for only
a few strategic locations inside the photoreactors, instead of
throughout the entire reactor domain.
In this research, a general methodology is presented for
developing an integrated CFD model of UV reactor performance and evaluating all parts of the model separately. The
results of each part of the integrated model (hydrodynamic,
radiation, species concentration) are evaluated separately
against experimental values in a UV photoreactor in order
to develop a more practical and reliable integrated model.
The approach can be summarized as follows:
The simulated velocity field is compared with PIV
measurements at every point, and velocity vector
profiles for the entire reactor cross-section are
presented.
The radiation field is modeled and compared with
measured values, which are recorded using a photodiode sensor located at discrete positions throughout
for the entire domain of the reactor.
The photoreaction rate of a chemical used as a model
contaminant for the UV-advanced oxidation process is
measured in a bench-scale photoreactor under controlled conditions to obtain a photoreaction kinetic
model.
An integrated model of hydrodynamics, radiation,
and conservation of a chemical species is developed
to determine the concentration profile throughout
the reactor. The integrated model is evaluated using
concentration data obtained with a newly developed
and modified planar laser-induced fluorescence
(PLIF) method. This powerful technique reveals the
concentration profile throughout the entire domain
of the reactor and can be useful to evaluated the full
model.
The strategy presented can be employed for any type of UV
reactor in order to obtain a reliable integrated model for
performance simulation.
10.1021/es902391t

2010 American Chemical Society

Published on Web 02/12/2010

2. Theory
2.1. Mass and Momentum Conservation (Hydrodynamics).
The velocity field can be obtained by solving the equations
of mass and momentum conservation. The general forms of
the conservation of mass and momentum (Navier-Stokes
equation) are

(F) + (Fu) ) 0
t

(1)

(Fu) + (Fuu) ) p - + Fg + F
t

(2)

where t, F, u, p, , g, and F are time, medium density, velocity


vector, pressure, viscous stress tensor, gravitational acceleration, and external body force, respectively. An analytical
solution of the system of partial nonlinear differential
equations is not available for complex geometries, so these
must be solved numerically. The three-dimensional, timedependent numerical solution of eq 2 (direct numerical
simulation (DNS)) is only applicable for a very small
computational domain and a laminar flow regime due to the
extensive computational resources required. For the turbulent regime, an acceptable engineering approach to solve eq
2 is the use of statistical methods or the classical approach
that solves the Reynolds averaged Navier-Stokes (RANS) form
of the equations (10). In the RANS approach, the Reynolds
stress tensors are semiempirically correlated using algebraic
(11), one-equation (12), two-equation (e.g., standard k-
(13), RNG k- (14), realizable k- (15), or standard k-
(16)), or multiple equation models of turbulence such as the
Reynolds stress model (RSM) (17-19).
2.2. Radiant Energy Conservation. The simplified form
oftheradiationtransferequation(RTE)(20)istheBeer-Lambert
Law that is applicable in many UV reactors, due to a lack of
scattering (no significant concentration of particulates) and
emission (relatively low temperature) throughout the medium. The differential form of the Beer-Lambert Law for
steady-state conditions is
dI(s, )
+ k(s, )I(s, ) ) 0
ds

(3)

where I and k are the intensity and the absorption coefficient


for a specific solid angle (direction) and position vector
s. For a photoreactor, changes in intensity depend not only
on the medium absorption coefficient but also on the
refraction/reflection through/from different materials in the
medium, such as the quartz body of the UV lamp, the quartz
protector of the UV lamp (sleeve), and the body of the reactor.
These refraction/reflection phenomena should be integrated
into eq 3.
The photoreaction rate is a function of the radiant power
obtained by integrating the intensity over the entire solid
angle (4). Considering all the above-mentioned effects, the
radiant power per unit area, or fluence rate, at a point for
one specific wavelength is (21)
G)

I0() exp[-

i)1

Li)2

i)1

overLi

ki(s, ) ds]

i)1

(4)

where Li, I0, ki, and Ti are the path length of a ray through
the ith medium, intensity at source, absorption coefficient
of medium i, and fraction of the ray transmitted from one
medium to another, respectively. The fluence rate is the key
parameter in the photoreaction rate correlation.

2.3. Species Mass Conservation. For each individual


chemical (species m) in the computational domain, the mass
conservation equation is

(x F) + (xmFu) ) - jeff + Sm
t m

(5)

where x, jeff, and S are mass fraction, effective diffusive flux,


and source/sink term of species m, respectively. The diffusive
term can be derived using Ficks law with the molecular
diffusion coefficient of the species in the medium. It was
shown in our previous work that a turbulent Schmidt number
of 0.7 is an appropriate value to be used for calculating the
effective diffusive flux (22).
The source/sink term depends on the nature of the
reaction occurring in the domain of the reactor. Adding an
oxidant (e.g., hydrogen peroxide) to the UV-based photoreactor produces hydroxyl radicals, very strong oxidants that
can oxidize many chemical contaminants. Three potential
primary reactions occur in parallel for the degradation of a
chemical contaminant: (1) direct oxidation of chemical
contaminant with oxidant; (2) photolysis by UV radiation;
and (3) reaction with hydroxyl radicals (23). The value of the
sink term in the species conservation equation for the reactant
is the sum of these three reaction rates. For many chemicals,
the rates of reactions are available (24); however, for certain
chemicals, the rates need to be measured. In addition, if a
chemical of interest (contaminant) exists in the presence of
other impurities (which is the case in many practical
applications), the rates may be affected and, hence, should
be measured experimentally. The reaction rates can be
determined using a bench-scale collimated-beam UV photoreactor under controlled conditions (i.e., well-mixed with
a known radiation field). It is important to note that the
photoreaction rate is a function of the radiant power (fluence
rate) distribution in the medium. Therefore, the fluence rate
should be simulated prior to photoreaction rate modeling.
In addition to the fluence rate, which appears in the source
term of the species mass conservation equation, the velocity
also appears in the convection term of this equation.
Therefore, the velocity field needs to be simulated. As a result,
for developing an integrated model of reactor performances,
which reveals the concentration profile of species, it is
essential to also develop models of hydrodynamics and
radiation distribution.

3. Experimental Methods
3.1. Flow-Through Pilot-Scale Photoreactor. A flowthrough pilot-scale photoreactor was studied for UV reactor
modeling and model evaluation under different flow
conditions. The dimensions of the reactor were selected
to meet the criteria for planar laser-induced fluorescence
that were recommended by Menton and Lipp (26) in order
to minimize the optical absorbance. The body of the reactor
was built from glass (5 mm thickness), instead of clear
polymeric material such as polymethacrylate, to prevent
its transparency being affected by either UV radiation or
chemicals adsorption over the experiment period. At the
bottom of the reactor, a quartz sleeve was attached to hold
a large UV lamp (low pressure, 200 W, arc length 1.07 m,
with more than 90% of its emission at 255 ( 5 nm, from
Emperor Aquatics). A hole at the end of the sleeve with air
suction at the other end, with flow rate of 0.0013 ( 0.003
m3/s and inlet/outlet temperatures of 22 ( 1/25 ( 1 C,
maintained an ambient skin temperature on the surface
of the sleeve and maintained isothermal conditions. Figure
S1 (of the Supporting Information) shows the dimensions
and configuration of the pilot-scale reactor.
3.2. Material. A fluorescent chemical, Rhodamine WT,
abbreviated as RhWT, was selected as the chemical candidate
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for photoreactor modeling and model evaluation. RhWT, with


the CAS registry number 37299-86-8 and the index name
Xanthylium, 9-(2,4-dicarboxyphenyl)-3,6-bis(diethlamino)-,
chloride, disodium salt in a 20 wt % aqueous solution was
supplied by Turner Designs Inc. Potassium iodide, potassium
iodate, and borax were used to calibrate the UV radiant energy
passing through a collimated-beam bench-scale photoreactor
(used for kinetic measurements). The bench-scale photoreactor contains a low pressure UV lamp with more than
90% of its emission at 255 ( 5 nm from Emperor Aquatics.
Hydrogen peroxide was used as an oxidant and was measured
using potassium iodide, sodium hydroxide, and ammonium
molybdate tetrahydrate. Ammonium molybdate tetrahydrate
was supplied by Acros Organics, and all of the other chemicals
were supplied by Fisher Scientific.
3.3. Concentration Measurement. The absorbance of
different weight percentages of RhWT (10 ppb to 10 ppm) at
different hydrogen peroxide concentrations was measured
at 555.5 nm (maximum absorbance) using a Cary 100 UV-vis
spectrophotometer to obtain its extinction coefficient (21).
The concentration of hydrogen peroxide in the solution was
measured using the method presented by Klassen et al. (25).
Hydrogen peroxide can oxidize iodide solutions under
alkaline pH conditions and generates an I3- ion. The
absorbance of the solution at 352 nm was used to backcalculate the concentration of hydrogen peroxide.
3.4. Velocity Measurement. Particle image velocimetry
was applied to measure the velocity field. The flow-through
photoreactor was installed in a piping network consisting of
pumps, piping, instrumentation, a storage tank, and a particle
image velocimetry (PIV) setup. Figure S2 (of the Supporting
Information) shows a schematic diagram of the PIV setup.
The same setup was used to measure the concentration
profile by planar induced-laser fluorescence (PLIF).
The PIV setup employed was the FlowMap 2D system
from Dantec Dynamics which consists of software for
capturing and processing images; a 12-bit digital camera
(HiSense MKII from Hamamatsu Photonic K.K.) equipped
with a narrow-band filter at 532 nm; and a laser pulse source
at 532 nm (Laser Solo III-15 Hz from NewWave Research
Company). PIV measurement criteria (27, 28) were taken
into consideration in order to minimize errors during the
experiments. Seeding the fine particles (polyamide with
diameters of 10-20 m) causes the reflection of light
produced by the pulsed laser source. During the very short
lifetime of the pulse (5-10 ns), the displacement of the
particle is almost zero, and it can be concluded that the
scattered light represents the location of the particles
captured by the digital camera. After a short period of time,
a second image is captured using a second laser pulse.
Comparison of the two images (cross correlation) using a
proper length scale reveals the length and direction of the
velocity vector in the plane of the laser sheet. To reduce the
noise, a Gaussian window function with a coefficient of 1
was used. Because window functions do not use the
information near the edges of an interrogation area, a 25%
overlap (4 pixels) of the interrogation window of 16-by-16
pixels was considered in the calculations. In addition, to
broaden the narrow correlation peaks and remove the effect
of the neighboring points in the correlation plane, a lowpass Gaussian filter with a coefficient of 1.5 was applied to
the frequency domain of the Fourier transform calculation
(27).
Using the aforementioned criteria, a 0.25 m length of the
reactor (from reactor inlet) was studied using PIV. This zone
was divided into three sections. For each section, 400 double
images were captured at two different mass flow rates of
0.005 ( 0.002 and 0.014 ( 0.002 kg/s. The values are reported
with 95% confidence intervals. The 400 images were processed to reveal the average velocity field. Finally, the velocity
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 6, 2010

fields from the three sections were stitched together to


represent the velocity profile inside the reactor (0.25 m length
of the reactor).
3.5. Radiant Energy Measurement. A radiometer (IL1700,
from International Light Technologies) and a solar blind UV
sensor (SIC01M-C, from Roithner Laser Technik) were used
to measure the irradiance rate at different points inside the
reactor (where no liquid was run through the reactor, which
was filled with air). The top side of the reactor was removed,
and the sensor was inserted into the flow pathway of the
reactor. The midplane inside the reactor was scanned,
changing the position of the sensor inside the reactor (see
Figure S3 of the Supporting Information).
3.6. Photoreaction Rate Measurement. The photoreaction rate of RhWT (as a model contaminant) and hydrogen
peroxide (as an oxidant) in the presence of UV radiant energy
was measured in a customized UV collimated-beam photoreactor under controlled conditions. The reactor consisted
of: two midsize UV lamps on an aluminum reflector below
a beam collimator; a double-jacketed reactor of 250 mL, with
a round quartz window (3 mm thickness) at the bottom; and
a variable speed stirrer at the top. The photoreactor sample
port (bottom) was connected to the flow-through cuvette of
a UV-vis spectrometer (Cary 100) via the circulating pump.
Prior to measuring the photoreaction rate of the RhWT, the
actinometry solution of iodide/iodate and the online spectrometer were used to accurately determine the UV radiant
power passing through the collimated-beam photoreactor
(29). The concentration of RhWT solution was 126 ( 1 ppb,
and the hydrogen peroxide concentration was 10.14 ( 0.05
ppm. These were measured as a function of absorbed
radiation to find the photoreaction rate (see Figure S4 of the
Supporting Information) (21).
3.7. Concentration Profile of RhWT Measurement
(PLIF). Fluorescent chemicals (e.g., RhWT) upon absorption
of light at a given wavelength (e.g., 532 nm) can generally
emit light at higher wavelengths (e.g., 580 nm). The intensity
of the emitted light depends directly on the concentration
of the fluorescent chemical. This behavior allows the
measurement of the fluorescent chemical concentration
profile using the same setup as for PIV. The technique is
referred to as planar laser-induced fluorescence (PLIF).
Replacing the narrow-band filter of the camera in the PIV
setup with a high-pass filter (>550 nm) can convert the PIV
setup to a PLIF setup. Due to the nature of pulsed lasers, the
beam energy is not spatially uniform. In addition, the laser
energy varies over time in consecutive pulses ((7% as
measured in our experiments). To increase the accuracy of
the measurements by considering these variations, the laser
beam was split into two parts using a beam splitter. The
energy of one beam was measured using another 12-bit digital
camera with a narrow-band (532 nm) filter from a reflective
surface as the reference. The other beam excited the
fluorescent solution through the reactor and this was
captured using the second camera with a high-pass filter
(>550 nm). This technique provides a way of accounting for
the pulse-to-pulse variation in laser energy and, hence,
increases the accuracy of the concentration measurements.
For the PLIF calibration process, different solutions of
RhWT (10-130 ppb) with a constant hydrogen peroxide
concentration (9.65 ( 0.56 ppm) were pumped through the
reactor (while the UV lamp was off), and 400 images were
captured for each concentration using both cameras. The
value of each pixel on the resulting image, after subtracting
the dark base (no laser source) was divided by the total value
of reflected light (captured by the second camera) to allow
normalization based on the reference beam. Finally, the
normalized value for each pixel was plotted in relation to the

FIGURE 1. PIV results at mid cross-section of the reactor for two different mass flow rates: 0.005 (A) and 0.014 (B) kg/s. The results
are shown for the first half of the reactor, in which hydrodynamics is most important, due to the flow being far from fully developed.
Because of the light scattering and reflection, unrealistic velocity vectors were generated from some parts of the reactor; these have
been removed (blank areas).
concentration of RhWT to determine a linear correlation for
that pixel. This resulted in a two-dimensional (2D) calibration
map.
A stock solution of hydrogen peroxide (10.30 ( 0.05 ppm)
and RhWT (126 ( 1 ppb) at 21.4 ( 0.3 C was fed into the
reactor while the UV lamp was stabilized. Two different flow
rates of 0.006 ( 0.002 and 0.015 ( 0.002 kg/s were tested. For
each operating condition, the inlet, middle, and outlet of the
reactor were studied, and 400 images were captured for each
section. The average of the normalized images, after subtracting the glowing background image, was used to calculate
the RhWT concentration profiles inside the flow-through UV
photoreactor. This procedure was applied for three zones
through the entire length of the reactor.

4. CFD Model Setup


The details of the CFD model set up are provided in the
Supporting Information.

5. Results and Discussion


5.1. Evaluation of the Hydrodynamic Model. 5.1.1. Velocity
Field Measurement (PIV). The results of the PIV measurement
for the two flow rates for the entrance region of the reactor
are shown in Figure 1. For each image, the length of the
arrows is proportional to the velocity magnitude. The value
of R2 (the square of the correlation coefficient between two
observed data values) for the average of 400 and 350 images
for each of the two flow rates was close to 1, suggesting that
400 images were statistically sufficient for averaging.
The flow pattern within the UV reactor begins at the inlet
jet and passes over the hemisphere of the sleeve in the inlet
section where it diverts to the main section of the reactor.
Due to the high gradient of momentum in different directions
of the jet stream, a back-circulation of the fluid at the inlet
zone is produced causing recycle of fluid near the top of the
reactor. Higher inlet velocities (with higher gradients) result
in greater vorticity and flow rate of the recycled flow and,
consequently, reduce the path height of the main fluid at the
bottom of the reactor (close to sleeve)(see Figure S5 of the
Supporting Information).
5.1.2. Simulation of Hydrodynamics. The average Reynolds numbers corresponding to the flow rates over the entire
cross-section at the round inlet of the photoreactor (Figure
S1 of the Supporting Information) are 530 ( 230 and 1480
( 280 for cases A and B, respectively. Due to variations in
the velocity at each cross-section, the local Reynolds number
differs on any vertical line (from top to bottom) within the
reactor, but the maximum Reynolds number cannot exceed

the inlet average Reynolds number. As a result, in case A, the


flow regime is laminar throughout the entire reactor length;
in case B, however, the area close to the bottom of the reactor
(near the sleeve) is in the transition regime, whereas the area
far from the sleeve is laminar. The aforementioned observations were modeled using different viscous models (laminar,
transitional,andturbulent)withdifferentnumericalapproaches.
The CFD results from laminar and standard k- transitional flow simulations using the first-order discretization
method yielded the best fit of the PIV data for cases A and
B, respectively (Figure 2). Overall, the flow patterns were
well-predicted by the model.
In order to show the deviation of the simulation results
from the experimental measurements (PIV), the velocity
vectors of the simulation results were subtracted from the
PIV measurement for each corresponding point for the two
different cases (see Figure S6 of the Supporting Information).
Considering the scale of the images, the error corresponding
to the PIV measurements, and the instrumental errors, there
is a good correspondence for both cases, although with better
agreement for case B. In the inlet zone, none of the models
could predict the high circulation flow accurately. In addition,
there is a narrow band below the contour of the turning
points for which both models predicted a smaller velocity
field than was found experimentally. The overall degree of
agreement can be evaluated using the coefficient of determination (R2) between the PIV velocity vectors and those of
simulation, which is expressed as

R2 ) 1 -

(Vx - Vx
(Vx - Vx
PIV

PIV

SIM)

+ (VyPIV - VySIM)2

+ (VyPIV - VyPIV,Ave)2

PIV,Ave)

(6)

where Vx and Vy are the x and y components of the velocity


vector, respectively, and indices PIV, SIM, and Ave represent
the PIV measurements, simulation results, and the average
of the measured values (PIV) throughout the entire domain,
respectively. The R2 for cases A and B are 0.86 and 0.92,
respectively (a perfect match would result in R2 ) 1.0). Better
statistical agreement was found between the simulation
results and experimental values for case B. It is expected that
the simulation and experimental concentration profiles,
which are highly affected by the velocity field, will show better
agreement in case B, as well.
5.2. Evaluation of the Radiation Model. Considering the
UV lamp as a line or volume source (I0 modeling in eq 4),
the UV radiant emission from the source can be modeled
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FIGURE 2. Simulated velocity profile (CFD results) at mid cross-section of the reactor for two different flow rates: 0.005 (A) and 0.014
(B) kg/s.

FIGURE 3. Irradiance rate at different distances indicated by ], 0, , , and * for distances 1, 10, 20, 30, and 50 mm from the
surface of the lamp, respectively. Experimental values for the radiation power (symbols) vs the 1D model-predicted values
(continuous lines) and the 3D model, cylindrical emitter with 7 mm diameter, values (dashed lines).
using measured boundary conditions. It is important to note
that the UV lamp does not behave as a uniform emission
source because the moving air (used in this experiment as
a coolant in the gap of the sleeve and lamp to maintain
ambient temperature on the outer sleeve surface) changes
the temperature gradient along the side of the lamp plasma
dramatically. This causes a nonuniform emission that is lower
closer to the lamp tip, where air enters the gap. As a result,
radiant power should be measured close to the surface of
the lamp/sleeve to calculate the intensity of the UV lamp at
the source (boundary conditions). In addition, for a more
realistic model, reflection from the body of the reactor should
be integrated into the model. A comparison of the experimental and modeling results for the irradiance rate inside
the air-filled reactor (absorption coefficient is equal to zero)
is shown in Figure 3.
Modeling the radiation (considering refraction and reflection from the reactor walls), with the radiant source as
a volumetric or linear emitter, provided a reasonable
agreement with the experimental results. However, the results
from the linear source model were more satisfactory over
the various distances from the lamp. As a result, the line
source (1D) model was selected for modeling the radiation
field inside the reactor, taking into account the absorption
coefficient of RhWT and hydrogen peroxide (4.48 m-1), the
reflection/refraction from/through the sleeve and the lamp
quartz body, as well as the reflection from the side walls of
the reactor (21). The simulated fluence rate profiles inside
the photoreactor are shown in Figure S7 (of the Supporting
Information). In the areas about 3 cm above the lamp sleeve
surface, the fluence rate is six times less than in the area
close to the surface of the sleeve.
5.3. Kinetic Model Determination. The total rate of
reaction of the rhodamine WT with hydrogen peroxide in
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the presence of UV is the summation of the three primary


rates of direct oxidation, direct photolysis, and reaction with
hydroxyl radicals (generated from UV photo oxidation of
hydrogen peroxide). The rate of direct oxidation and direct
photolysis were found to be insignificant. The total photoinitiated oxidation rate of RhWT and hydrogen peroxide after
receiving H J/m2 UV fluence was measured to be (21)
ln

CRhWT
) (-4.757 ( 0.092) 10-3H
130

(7)

where CRhWT is the concentration of RhWT after receiving H


(J/m2) fluence. This correlation was developed for the
concentration of RhWT of less than 130 ppb (initial concentration of RhWT) and hydrogen peroxide at 10 ppm.
Considering the volume of the bench-scale collimated-beam
photoreactor (in which the reaction rate was measured) and
the agitation effect of the impeller, the photoreactor is a wellmixed batch reactor. Using the chain rule, the rate of reaction
for such reactor from eq 7 can be written as (21)
dCRhWT
) (-4.757 ( 0.092) 10-3GabsCRhWT
dt

(8)

where Gabs is the absorbed fluence rate.


Considering the temperature of reaction rate tests during
the experimental measurements (21 ( 1 C), eq 8 is valid
only for ambient temperature. Passing cooling air over the
UV lamp in the PLIF measurements maintained the temperature of reaction zones at 21 ( 1 C. During all tests, the
skin temperature of the sleeve while the UV lamp was
operated did not exceed 24 C, and hence, the isothermal
assumption using eq 8 is valid.

FIGURE 4. Concentration profile of rhodamine WT (ppb) in the UV reactor with the laser energy at a steady-state condition for two
different mass flow rates: 0.006 (A) and 0.015 (B) kg/s.

FIGURE 5. Concentration profile of rhodamine WT in the UV photoreactor calculated by the integrated model for two different mass
flow rates: 0.006 (A) and 0.015 (B) kg/s. Concentrations less than 80 ppb are shown as white.
5.4. Evaluation of the Integrated Model. The concentration profile of RhWT is the result of the interaction of
hydrodynamics, fluence rate, and reaction rate. Therefore,
measuring the concentration profile throughout the entire
reactor is the best indicator for the evaluation of the
photoreactor model performance. As far as the authors are
aware, no experimental measurement of the concentration
profile in a photoreactor has been reported in the open
literature. Figure 4 shows the measured concentration of the
RhWT profile through the midcross-section of the photoreactor. The concentration profile through the entire length
of the reactor was studied by investigating three sections of
the reactor from inlet to outlet separately. The three images
(averaged from 400 images for each zone) were combined
and stitched together. Due to the technical limitations in
keeping the setup perfectly consistent while studying different
zones, it was not possible to obtain a perfect match in the
areas where two adjacent images overlapped. The values
close to the boundaries of the reactor walls were masked
because they did not represent the true concentrations (as
a consequence of reflections from the white glue joints in
these regions of the reactor). For all images, a horizontal
median filter of rank 40 was applied to remove the shadowing
effects of the laser sheet in the images.
Radiation measurement in the inlet zone (-5 to 1 cm
from the tip of the lamp) showed a very low level of radiant
energy (almost zero). This implies that the rate of conversion

of RhWT was very low. In other words, higher concentrations


of RhWT are expected in this zone, in contrast to what was
observed experimentally (Figure 4). This can be explained
by considering the flow pattern in the reactor (Figure 1),
which plays a major role in controlling the concentration.
Low velocity (flow) of fluid at the reactor inlet zone increases
the residence time of chemicals and consequently enhances
the conversion consequently. In addition, the recycled flow
of low concentration fluid from downstream to upstream
dilutes the concentration of the inlet stream. As a result,
lower concentrations levels of RhWT are expected at the inlet
zone. In the area closer to the lamp (sleeve) where the fluence
rate is at its maximum level, a minimum concentration of
RhWT should be observed. These features are clearly
demonstrated in Figure 4. Error in concentration can occur
where the concentration gradient is high, with higher
concentration at top is higher (due to a high absorption of
laser light at the reactor exit) than at the bottom. Therefore,
the measurements in the outlet sections are expected to have
a relatively high degree of uncertainty for all cases and this
explains the similar concentration profiles found for both
cases in Figure 4, at the end of the reactor.
The integrated model of reactor performance simulated
the concentration profile in the UV reactor by solving the
governing equations of mass, momentum, radiant energy,
and species conservation. The results are shown in Figure
5. The main features of the concentration profile through

FIGURE 6. Concentration difference (CPLIF - CSimulation) in parts per billion for two different mass flow rates: 0.006 (A) and 0.015 (B) kg/
s. Concentration differences higher than 30 ppb are shown as white.
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the reactor is well-predicted by the model. The difference


between the modeling and experimental results of RhWT
concentration for the two flow rates (cases A and B) are shown
in Figure 6. The reliability of the simulation results (Figure
6) should be compared with the uncertainty associated with
the calibration map for calculating the concentration contours in the PLIF procedure (see Figure S8 of the Supporting
Information).
Overall, there is close agreement between the modeling
and experimental results throughout the entire cross-section
of the reactor. The relatively high degree of disagreement at
the lower end of the reactors is likely due to the difficulties
in PLIF measurements as a result of light reflection in these
regions. The differences between the model predictions and
the experimental results are in the range of measurement
uncertainty (see Sources of Uncertainty and Errors in the
Supporting Information). The agreement is better for case
B, likely due to a better prediction of the velocity profile. For
both cases, in a small zone at the end of the reactor, adjacent
to the UV lamp, the difference in concentration shows a
notable deviation. In that zone, the significant vertical
concentration gradient causes an error in the PLIF measurement. Overall, the disagreement between the results can be
attributed to the uncertainty associated with experiments,
such as instrumental error and error of the PLIF method, as
well as the errors associated with numerical methods and
model parameters.
The PLIF method presented here cannot be used directly
for industrial photoreactors; considering it requires the body
of the reactor to be manufactured from optically accessible
(transparent) material. In addition, for reactors with relatively
large diameter, a scanning method should be employed to
first find the concentration close to the reactor wall and then
continue the scanning up to the center of the reactor, taking
into account any absorbance correction. However, this
technique could be directly used for small pilot scale
transparent reactors for better understanding of the reactor
behavior or for evaluating the general-purposed integrated
models of reactor performance.
To summarize, conventional methods for evaluating
photoreactor models typically rely exclusively on concentration measurements at the reactor inlet and outlet. These
methods cannot show the discrepancies between the model
predictions and real values inside the photoreactor, nor can
they reveal the causes of the deviation. The methods utilized
in this research can be applied to evaluate photoreactor
models, as well as models of similar systems. This approach
evaluates the accountability of each component of the
integrated model as well as the results of the integrated model
for the entire computational domain. As a result, the
discrepancy for each component is revealed, and the model
can be applied to a wide range of operating conditions. This
approach reduces uncertainty in the integrated model setup
and provides a solution for individual phenomena. Consequently, it decreases the bias of the final integrated model
solution.
Considering the uncertainties in the measurements of
velocity, fluence rate, and concentration, overall, the favorable
agreement between the experimental data and the simulated
results for each governing equation (momentum, mass, and
radiant energy), and the integrated system of equations
(species mass conservation) verifies the reliability of the
presented methodology.

Appendix A
Nomenclature
CRhWT ) concentration of rhodamine WT (ppb)
F ) volumetric external forces (N/m3)
G ) fluence rate (W/m2)
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 6, 2010

Gabs ) absorbed fluence rate (W/m2)


g ) gravitational acceleration (m/s2)
H ) local absorbed fluence (dose) by microorganisms or
chemicals (J/m2)
I ) average radiant intensity of entire spectrum (W/sr)
I0 ) average radiant intensity of entire spectrum at source
of radiation (W/sr)
jeff ) effective molecular diffusive rate (kg/s m3)
k ) absorption coefficient of the medium for the whole
spectrum (1/m)
ki ) absorption coefficient of medium, ith (1/m)
Li ) pathway length of ray through medium, ith (m)
p ) pressure (Pa)
R2 ) coefficient of determination
Sm ) source term of species m (kg/s m3)
s ) position vector (m)
t ) time (s)
u ) velocity vector (m/s)
Vx ) x component of velocity vector (m/s)
Vy ) y component of velocity vector (m/s)
xm ) mass fraction of species m
F ) density (kg/m3)
) viscous stress tensor (Pa)
) solid angle (steradians)

Supporting Information Available


CFD model setup (30), source of uncertainty and errors,
and Figures S1-S8. (Figure S1) The photoreactor used for
PLIF measurements (all internal dimensions are expressed
in cm). (Figure S2) Schematic view of pilot-scale photoreactor, which consists of: product reservoir (1), feed
reservoir (2), stirrer (3), centrifugal pump (4), flow/
pressure/temperature meter (5), photoreactor (6), laser
source (7), digital camera (8), PIV/PLIF control unit (9),
data acquisition system (10), and online spectrophotometer
(11). (Figure S3) Reflector glasses over the UV lamp in the
quartz sleeve. The apparatus consists of two window glasses
(1), a UV photodiode extension arm (2), a UV sensor (3),
a UV lamp (4), a quartz sleeve (5), and the position of the
hole in the sleeve (6). (Figure S4) Schematic diagram of
bench-scale collimated-beam UV photoreactor: parabolic
reflector (1), UV lamp (2), collimator (3), double jacket
rector (4), stirrer (5), and thermometer (6). (Figure S5)
Velocity (x-component) profile and contour of turning
points at different sections of the reactor for two different
flow rates. Vertical lines indicate different xpositions in
centimeters. (Figure S6) Velocity difference (vectors), VPIVVSIM, and x-components of velocity reactor. Vertical lines
indicate x-position, and curves show zero axial velocity
difference (VxPIV-VxSIM). The color bar (linear scale)
indicates the velocity difference (vectors) from 0.015 (red)
and 0.03 (red) to 0 m/s (blue) for cases A and B, respectively.
The arrows show the flow directions. The velocity measurements near the surfaces are removed (white regions)
because of the high uncertainty in the measurement due
to the reflections. (Figure S7) Fluence rate (W/m2) profile
at the mid-cross-section of the photoreactor. (Figure S8)
Uncertainty in the RhWT concentration profile measurement (ppb) with a 95% confidence interval in the UV reactor
for two different mass flow rates: 0.006 (A) and 0.015 (B)
kg/s. The color bar (linear scale) indicates the concentration uncertainty from (30 (red) to 0 ppb (blue), and the
arrows show the flow directions. This material is available
free of charge via the Internet at http://pubs.acs.org.

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