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abstract
Article history:
A novel mechanistic model that describes the vacuum UV advanced oxidation process in
an annular photoreactor initiated by 172 nm and 185 nm (in combination with 253.7 nm,
with and without exogenous H2O2) is presented in this paper. The model was developed
29 June 2014
from first principles by incorporating the vacuum UV-AOP kinetics into the theoretical
framework of in-series continuous flow stirred tank reactors. After conducting a sensitivity
analysis, model predictions were compared against experiments conducted under a variety
of conditions: (a) photo-induced formation of hydrogen peroxide by water photolysis at
Keywords:
172 nm (for both air- and oxygen-saturated conditions); (b) photo-induced formation of
Vacuum UV
hydrogen peroxide by water photolysis at 185 253.7 nm (in the presence of formic acid,
with and without the initial addition of hydrogen peroxide); (c) direct photolysis of
Hydroxyl radical
hydrogen peroxide by 253.7 nm; (d) degradation of formic acid by 185 253.7 nm (with and
Numerical modeling
without initial addition of hydrogen peroxide); and (e) degradation of formic acid by
Water photolysis
253.7 nm (with the addition of exogenous hydrogen peroxide). In all cases, the model was
able to accurately predict the time-dependent profiles of hydrogen peroxide and formic
acid concentrations. Two newly recognized aspects associated with water photolysis were
identified through the use of the validated model. Firstly, unlike the 185 nm and 253.7 nm
cases, water photolysis by the 172 nm wavelength revealed a depth of photoactive water
layer an order of magnitude greater (~230e390 mm, depending on the specific operating
conditions) than the 1-log photon penetration layer (~18 mm). To further investigate this
potentially very important finding, a computational fluid dynamics model was set up to
assess the role of transport mechanisms and species distributions within the photoreactor
annulus. The model confirmed that short-lived hydroxyl radicals were present at a radial
distance far beyond the ~18 mm photon penetration layer. Secondly, kinetic simulations
showed that the higher penetration depth of hydroxyl radicals was not caused by diffusive
or convective transport phenomena but rather the effect of non-linear behavior of the
complex reaction kinetics involved in the process.
2014 Elsevier Ltd. All rights reserved.
* Corresponding author. Tel.: 1 519 317 6788; fax: 1 519 661 3498.
E-mail addresses: f.crapulli@fastwebnet.it, fcrapull@uwo.ca (F. Crapulli).
http://dx.doi.org/10.1016/j.watres.2014.06.048
0043-1354/ 2014 Elsevier Ltd. All rights reserved.
210
1.
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Introduction
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
2.
2.1.
Experimental set-up
211
212
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
2.2.
Rl
a dt
b dt
c dt
d dt
Pabs l 1
A;l CA a
$ $ $Pp
CA
Fl $
Vuv hcL NA
i1 i;l Ci
2
),
7
ions
(H
,
e
,
OH
,
HO
,
HCO
,
HCOO
,
CO
)
and
7
CO*
3
aq
2
3
3
molecules (H2O, H2O2, H2, O2, CO2, CO, HCOOH).
It should be mentioned that, unlike previous studies where
certain specific reactions were a priori excluded, our approach
was to first include all the documented reactions and then,
based on a sensitivity analysis and in case of lack of computational resources, exclude the unnecessary reactions from
the model. As such, the generalized kinetic model was
mathematically formulated by including all the elementary
reactions available in the literature, including the backward
and forward reactions associated with the main equilibria
affecting the system (Table 1). Specifically, for each species
involved in the process, differential mass-balance equations
were set where both light-independent and light-dependent
rate terms for a generic aA bB / cC dD reaction were
taken into account and mathematically formulated as shown
in Eq. (1):
1 dCA
1 dCB 1 dCC 1 dCD
kx CaA CbB
Rd
a dt
b dt
c dt
d dt
(1)
(2)
PUV
$10Al $rRs
2prL
r Rs
(3)
(4)
A185 H2 O;185 $H2 O H2 O2 ;185 $H2 O2 HCOOH;185 $HCOOH
HCOO ;185 $ HCOO
(5)
A253:7 H2 O2 ;253:7 $H2 O2
(6)
213
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Table 1 e List of elementary reactions and rate constants (compiled from primary and secondary sources) for the 172 nm,
185 nm and 253.7 nm AOP.
Symbol and units
1
Elementary reaction
F1 [mol einstein ]
H2 O hn172nm /HO H
F2 [mol einstein1]
H2 O hn172nm /HO H e
aq
F3 [mol einstein1]
k4 [m mol
1
1
s ]
e
aq
H /H
0.42
0.45
0.42
0.42
0.37
HO H2 /H H2 O
6.0$104
6.0$104
6.0$104
4.2$104
4.6$104
H2 O
3 /O2 OH H
k8 [m mol
1
1
s ]
e
aq
H2 O/H OH
H H2 O/H2 HO
H H /H2
1.0$107
1.0$107
1.0$107
1.0$107
1.5$107
7.8$106
HO H /H2 O
2.4$107
2.4$107
7.0$106
7.0$106
1.5$107
7.0$106
7.0$106
H O2 /HO2
1.0$107
1.0$107
2.0$107
2.1$107
2.0$107
2.1$107
1.4$107
e
aq H H2 O/H2 OH
2.5$107
2.5$107
2.5$107
2.5$107
2.8$107
H OH /e
aq H2 O
H H2 O2 /HO H2 O
214
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Table 1 e (continued )
Symbol and units
Elementary reaction
H HO2 /H2 O2
H O
2 /HO2
e
aq H2 O2 /HO OH
H O /HO
k21 [m mol
1
1
s ]
e
aq
HO
2
H2 O/2OH HO
HO H2 O2 /HO2 H2 O
e
aq HO /OH
O
2 HO /OH O2
HO HO
2 /OH HO2
e
aq eaq 2H2 O/H2 2OH
e
H2 O/2OH
aq O
e
aq O2 /O2
215
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Table 1 e (continued )
Symbol and units
Elementary reaction
e
aq HO2 /HO2
e
aq O2 H2 O/OH HO2
k35 [m mol
1
1
s ]
e
aq
HO
2 /OH
O O
2 H2 O /2OH O2
HO
2 O3 /OH O2 O2
HO
2 H2 O/H2 O2 OH
k40 [m mol
1
1
s ]
HO
2 /OH
O
2
H2 O2 OH /HO
2 H2 O
1
1
H OH /H2 O
O H2 O2 /O
2 H2 O
O O2 /O
3
O O
3 /2O2
k47 [s1]
HO2 /H O
2
O
2
k43 [m mol
k48 [m mol
1
s ]
1
s ]
/HO2
H HO
2 /H2 O2
2.0$103
2.0$103
2.6$103
1.0$103
8.3$102
8.3$102
H2 O2 O
3 /O2 O2 H2 O
O
2 HO2 /O2 HO2
5.0$104
5.0$104
9.7$104
5.0$104
9.7$104
O
2 H2 O2 /OH O2 HO
1.6$102
1.6$102
1.6$102
1.2$103
k55 [s1]
H2 O/H OH
k56 [s ]
H2 O2 /HO
2
2O
2 2H2 O/O2 H2 O2 2OH
HO HO
2 /H2 O O2
H HO
2 /HO OH
1
216
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Table 1 e (continued )
Symbol and units
Elementary reaction
HO O
3 /HO2 O2
H O
3 /O2 HO
O
3 /O2
k62 [s
1
k64 [m mol
1
1
s ]
H O
3 /HO3
H2 /e
aq H2 O
CO2 H2 O/HCO
3 H
HCO
3 H /CO2 H2 O
k67 [m mol
1
1
s ]
1
1
k69 [m mol
s ]
1
1
k70 [s1]
3
k71 [m mol
s ]
k73 [m mol
/HCO
3
HCO
3 /CO2 OH
k68 [s1]
3
CO2 OH
1
1
s ]
/HCO
3
2
HCO
3 /CO3 H
CO2
3
HCO
3
/CO2
3
H2 O
CO2
3 H2 O/HCO3 OH
e
aq
OH
CO2
3 /products
CO2
3 HO /CO3 OH
e
aq HCO3 /products
HCO
3 HO /H2 O CO3
HCO
3 H /products
CO
3 HO /products
CO
3 HO2 /HCO3 O2
2
CO
3 O2 /O2 CO3
2
CO
3 O3 /O3 CO3
HCO
2 CO3 /HCO3 CO2
CO
3
k83 [m mol
1
1
s ]
k85 [m mol
1
1
s ]
k87 [m mol
1
1
s ]
2
CO
2 /CO3
CO2
e
aq CO2 H2 O/HCO2 OH
H 2 O2
CO
2 /HO
OH CO2
HCO
3 CO2 /HCO2 CO3
e
aq
CO2 /CO
2
H HCO
2 /H2 CO2
217
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Table 1 e (continued )
Symbol and units
Elementary reaction
HO HCO
2 /H2 O CO2
3.2$106
3.2$106
3.2$106
3.5$106
CO
2 O2 /CO2 O2
2.4$106
2.4$106
2.4$106
2.9$106
F4 [mol einstein1]
H2 O hn185nm /HO H
1
F5 [mol einstein ]
H2 O hn185nm /HO H
F6 [mol einstein1]
1
F7 [mol einstein ]
H2 O2 hn253:7nm /HO HO
k95 [s1]
HCOOH/HCOO H
k96 [m mol
1
1
s ]
F8 [mol einstein1]
k99 [m mol
1
K100 [m mol
k102 [m mol
1
HCOOH HO /HCOO H2 O
1
s ]
1.0$101 [assumed]
HCOO H /HCOOH
1
s ]
1
1
s ]
HCOOH H /HCOO H2
HCOOH e
aq /products
2.3.
DCA ;kx
F9 [mol einstein ]
PN
i1 CA i;k1 k2 kn CA i;k1 k2 kn kx
N
1
(7)
2.4.
(8)
where Q is the flowrate, Vuv and Vres are the volume of the
photoreactor and the reservoir, respectively, and CA,uv and
CA,res the species concentrations. The formalism shown in Eq.
(8), was extended to all the species and the hydraulic components of the recirculating systems used during the experiments. Additional information about the model can be found
in supporting information (SI) file.
In accordance with the flow regime employed during the
experiments and due to the relatively small hydraulic
218
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
diameter of the annular photoreactor, all MATLAB simulations were conducted assuming a radial velocity distribution
typical of the laminar regime as described in Eq. (9) (Munson
et al., 2002).
1
C 2
B
C ln r
B
C 6
B
1 B
8mQ
1
C 6 RS 2
$
RW R2S
ur
B 2
2 R2 C$4
2
R
B
4m p RW RS R2 R2
W
S C
RW
C ln R
B
W
S
S
A
@
RW
ln
RS
7
r2 R2S 7
5
(9)
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
approach is justified by considering the limited radial masstransfer occurring in the photoreactor due to the fully
laminar regime at which the system was operated (Re
1450e1587) as well as the extremely short life time of hydroxyl
radicals (on the order of a fraction of a second) leading to
negligible convective and diffusive mass transport effects.
This was also verified by means of additional CFD simulations
reported in SI file (Fig. S2).
Both the annular photoreactor and the reservoir were
treated as arbitrary flow reactors. Specifically, the MATLAB
model was implemented to accommodate an arbitrary number n and m of ideal CFSTR-in-series for each of the two system
components (Fig. 4). The use of a laminar velocity profile to
estimate the extent of hydraulic by-pass is not in contradiction with the subsequent hypothesis of photoreactor hydraulics described by CFSTR in-series as the latter is meant to
represent overall mixing behavior of the system, including the
fully mixed recirculating tank.
A symbolic representation of the entire recirculating system is given in Eq. (10):
dCA; uv1
dt
6
6
6
6
6
6 dCA; uv
n
6
6
dt
6
6
6
6
6 dCA; res
1
6
6
dt
6
6
6
6
6
6
6
6
6
6
4
dCA; resm
dt
Vuv1
6
7
6
7
6
7
6
7
6
7
6
7
f
6
7
6 V
7
6
uvn
7
6
7
6
7
6
7
6
7
f
7 Q6
6
7
6 Vres1
7
6
7
6
7
6
7
6
7
6
7
6
7
6
7
6
7
6
7
6
5
4
1
Vresm
2
32
3T
76
CA; resm
76
76
76
76
76
76
76
CA; uvn1
76
76
76
76
76
1 f
76 CA; uvn
CA; resm
76
f
76
76
76
76
76
76
76
76
76
76
76
54
CA; res
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
5
f
Vuv1
m1
6
7
6
7
6
7
6
7
6
7
6
7
f
6
7
6
72
V
6
7
uv
n
CA; uv1
6
7
6
76
6
76
6
76 CA; uvn
1
6
7
Q6
76 CA; res1
6 Vres1 76
6
74
6
7
6
7 CA; resm
6
7
6
7
6
7
6
7
6
7
6
7
6
7
4
5
1
Vresm
2
3
Rl; uv1 Rd; uv1
6
7
6 R
7
l; uvn Rd; uvn 7
6
6
7
Rd; res1
6
7
4
5
Rd; resm
3T
2.5.
CFD model: governing equation and boundary
conditions
To better understand the spatial distribution of the species
involved in the advanced oxidation process, as well as to
confirm the results obtained with the MATLAB simulations, a
CFD model of the central region of the annular photoreactors
used in the experiments was developed. It should be noted
that the goal of the CFD simulations presented in this paper
was to generate additional supporting information for the
observation made through the use of the comprehensive
MATLAB model, with the intent of trying to elucidate the
spatial distribution and the radial penetration of hydroxyl
radicals within the photoreactor annulus. Due to the axialsymmetric nature of the photoreactors used in the experimental work as well as the well-developed laminar flow
regime induced by the small hydraulic diameter of the system,
a 2-dimensional axisymmetric framework with a fullydeveloped laminar velocity profile was used for the CFD
analysis. Steady state governing equations for continuity,
momentum (axial and radial direction) and scalar transport
(Eq. (11)e14) were used in the model to predict the spatial
distribution of the chemical species involved in the AOP.
1 v
v
rur ux 0
r vr
vx
7
7
7
7
7
5
(11)
ur
vur
vur
1 vP m 1 v
vur
v2 ur ur
r
ux
2 2
r vr r r vr
vr
vx
vr
vx
r
(12)
ur
vux
vux
1 vP m 1 v
vux
v2 ux
r
ux
2
r vx r r vr
vr
vx
vr
vx
(13)
ur
vCA
vCA
1 v
vCA
v2 CA
r
ux
GCA
SCA
2
r vr
vr
vx
vr
vx
(14)
GCA
(10)
219
2:4$108
MW0:71
A
(15)
220
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
3.
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
221
cases. Also, in this case at 253.7 nm, the model predicted very
well the oxidation of the organic carbon pollutant over time
with an error of 1.9$102 mmol L1 (6.3%), showing an
apparent zero-order decay at the investigated initial concentration and treatment time due to the limited extent of
photolysis of hydrogen peroxide (Fig. 7).
The absorption caused by HO
2 was not included in the
model as the simulated results were insensitive such contribution due to the acidic pH range at which experiments were
conducted, resulting in very low HO
2 concentrations (Fig. S8).
The robustness of the model in predicting the photoreactor
behavior under a variety of operating conditions indirectly
provided additional support regarding the role played by the
photoactive water layer which, based on our estimates,
exceeded by far the optical thickness of the fluid. In order to
further investigate this potentially important result, a 2D axisymmetric CFD model was set up to numerically explore the
role played by diffusion and convection transport phenomena
in the annular photoreactor.
Fig. 8 shows the distributions of fluence rate (reported for
both the 172 and 185 nm wavelengths), H2O2 and HO* scaled
and normalized between their maximum and minimum
values. As expected, the fluence rate distribution was more
uniform for the 185 nm than the 172 nm case due to the difference in the absorption coefficient of water at these two
wavelengths. Remarkably, the 172 nm case confirmed our
earlier observation made using the in-series CSTRs model
with bypass: despite the fact that the photon penetration layer
is confined to a layer of ~18 mm, the distribution of HO*, and
particularly of H2O2, significantly exceeded the 18 mm radial
threshold. Such an observation is further supported by Heit
and Braun (1997) who founded experimentally that the O2
concentration in the annulus showed a depletion gradient
very different from the one of 172 nm fluence rate light.
222
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Fig. 8 e Fluence rate, H2O2 and HO* normalized distributions at two conditions: 172 nm (left column) and 185 253.7 nm
(right column).
Additional axial-symmetric CFD simulations were performed in order to compare whether the distribution of HO*
radicals was sensitive to the length of the photoreactor
included in the model. As shown in Fig. S9, the radial distribution of HO* radicals was independent of the photoreactor
length and residence time used in the CFD simulations. To
better elucidate the reasons behind a greater than expected
presence of HO* beyond the 1-log photon penetration layer, a
new set of CFD simulations was performed. By artificially
changing the value of diffusion and convection (both the
diffusion coefficient and the flowrate increased by an order of
magnitude), we determined that neither of those two mechanisms were responsible for transporting HO* outside the 1log photon penetration layer (Fig. S1). At this point, attention
was paid to the kinetic behavior caused by the nested network
and the rate of elementary reactions involved in the VUV
process. Using the kinetic model presented in Table 1, kinetic
simulations for different fluence rates (1e10e100 W m2) were
conducted and the steady-state HO* concentration quantified
for each of the three AOPs considered in this study (172,
185 253.7 and 253.7 nm with initial 10 ppm of H2O2). As
shown in Fig. 9 (and confirmed by Fig. S10 and Fig. S11), for the
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
223
4.
Conclusions
references
224
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Santoro, D., Raisee, M., Moghaddami, M., Ducoste, J., Sasges, M.,
Liberti, L., Notarnicola, M., 2010. Modeling hydroxyl radical
distribution and trialkyl phosphates oxidation in UV-H2O2
photoreactors using computational fluid dynamics. Environ.
Sci. Technol. 44 (16), 6233e6241.
Schulz, K.G., Riebesell, U., Rost, B., Thoms, S., Zeebe, R.E., 2006.
Determination of the rate constants for the carbon dioxide to
bicarbonate inter-conversion in pH-buffered seawater
systems. Mar. Chem. 100 (1e2), 53e65.
Schwarzenbach, R.P., Gschwend, P.M., Imboden, D.M., 2003.
Environmental Organic Chemistry, second ed. WileyInterscience, New York.
Segelstein, D.J., 1981. The Complex Refractive Index of Water.
University of Missouri-Kansas City, USA. M.S. thesis.
Sosnin, E.A., Zakharova, E.A., Moskaleva, M.L., Batalova, V.N.,
2006. An electrochemical methanol actinometer and its
application to measurements of the intensity of vacuum UV
radiation of a Xe2 Excilamp. Instrum. Exp. Tech. 49 (1),
101e105.
Weeks, J.L., Meaburn, G.M.A.C., Gordon, S., 1963. Absorption
coefficients of liquid water and aqueous solutions in the far
ultraviolet. Radiat. Res. 19 (3), 559e567.
Zvereva, G.N., 2010. Investigation of water decomposition by
vacuum ultraviolet radiation. Opt. Spectrosc. 108 (6),
915e922.
Glossary
Al: Absorption coefficient of the solution at specified wavelength
[m1]
a, b, c, d: Generic stoichiometric coefficients
CA, CB, CC, CD: Concentration of the generic species A, B, C, and D
[mol m3]
CA,res: Concentration of the generic species A in the reservoir
[mol m3]
CA,uv: Concentration of the generic species A in the photoreactor
[mol m3]
cL: Light speed in vacuum (2.99$108 m s1)
f: Fraction of flowrate entering in the active layer of the
photoreactor
h: Plank's constant (6.626$1034 J s)
I: Fluence rate [W m2]
kx: Reaction rate constant, second order [m3 mol1 s1] or first
order [s1]
L: Lamp arc length [m]
MWA: Molecular weight of the generic species A [g mol1]
N: Number of data points over time
n: Number of CSTRs in series in the photoreactor zone
NA: Avogadro's number (6.022$1023 molecules mol1)
m: Number of CSTRs in series in the reservoir zone
P: Pressure [Pa]
p: Total number of absorbing light species
Pabs: UV power absorbed by the solution [W]
PUV: UV power emitted from the sleeve [W]
Q: Flowrate [m3 s1]
r: Radial distance from the lamp axis [m]
Rd: Generic light-independent reaction rate [mol m3 s1]
Rl: Generic light-dependent reaction rate [mol m3 s1]
RS: Sleeve radius [m]
RW: Reactor wall radius [m]
SCA : Source term for the generic scalar CA [f s1]
t: Time [s]
ur: Radial velocity profile in the annular photoreactor [m s1]
ux: Axial velocity profile in the annular photoreactor [m s1]
Vres: Reservoir volume [m3]
Vuv: Photoreactor volume [m3]
x: Axial distance along the lamp [m]
w a t e r r e s e a r c h 6 4 ( 2 0 1 4 ) 2 0 9 e2 2 5
Greek symbols
GCA : Molecular diffusion of the generic species A [m2 s1]
dr: Depth of photoactive layer [m]
DCA ;kx : Relative error in predicting the scalar CA when the reaction
kx is omitted from the kinetic model [mol m3]
225