Chemical Engineering Science 56 (2001) 5073–5083

www.elsevier.com/locate/ces

Development of membrane–UV reactor for dissolved oxygen

removal from water
K. Li ∗ , Xiaoyao Tan
Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, UK

Received 18 September 2000; received in revised form 12 March 2001; accepted 11 April 2001

Abstract
A novel membrane–UV reactor has been developed for dissolved oxygen removal from water. The reactor was fabricated from
an UV light surrounded by silicone rubber hollow 3ber membranes. Water saturated with dissolved oxygen was fed into the hollow
3ber lumen, while hydrogen gas used as a reducing agent was introduced into the reactor shell. The hollow 3ber membrane served
as a gas distributor for hydrogen to be distributed evenly and then dissolved in water to react with the dissolved oxygen under
the UV irradiation. The dissolved oxygen is, thus, removed due to the chemical reaction between the two dissolved gases. A
mathematical model has also been developed for the novel membrane reactor. The e5ects of membrane resistance, gas and water
6ow rates as well as gas pressures on the overall performances of the reactor for the DO removal were studied theoretically.
Experimental data obtained at various operation conditions were compared with the theoretical results and kinetic parameters for
the dissloved oxygen and hydrogen reaction were evaluated. ? 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Membrane–UV reactor; Ultrapure water; DO removal

1. Introduction particles, organic contaminants, metallic contaminants

There are di5erent gases present in natural water in
dissolved state and oxygen is one of them. Removal of
dissolved oxygen (DO) from water is one of the primary
concerns in various industries such as semiconductor
manufacture, power plants, pharmaceuticals and biotech-
nology. Among all these, the standard for the DO level
in the ultrapure water used in the semiconductor industry
is the most stringent (Chua et al., 1993).
Semiconductors manufactured currently have a multi-
layer structure of thin 3lms. The interface between a thin
3lm and substrate or between two 3lms plays an impor-
tant role in the operation of the semiconductor device.
Therefore, formation of high quality 3lms and ideal inter-
face is important. To achieve this, contamination, stress
and damages to silicon wafer surface must be controlled
(Ohmi, 1993). Contaminants on the wafer surface such as
∗ Corresponding author. Tel.: +44-1225-826372; fax: +44-1225-
826894.
E-mail address: k.li@bath.ac.uk (K. Li).
and native oxide should be suppressed as much as pos-
sible. Particles, organic contaminants and metallic con-
taminants have been controlled to very low levels. The
native oxide formed on the wafer surface during the
cleaning step interferes with the growth of epitaxial sili-
con thin 3lm at low temperatures and a5ects the control
of 3lm thickness and 3lm quality of extremely thin gate
oxides. (Ohmi, Isagawa, Kogure, & Imaoka, 1993).
Currently, ultrapure water (UPW) is often used as a
cleaning agent for silicon wafer. The presence of the
dissolved oxygen in the ultrapure water causes formation
of a native oxide layer on the wafer surface when it is
rinsed with the ultrapure water. The native oxide growth
is dependent on both the exposure time of the silicon
surface to UPW and the dissolved oxygen level in UPW.
There is a formation of a native oxide layer of 3 when the
silicon wafer surface is washed by high purity water con-
taining even a low level of 40 –600 ppb of dissolved oxy-
gen (Morita, Ohmi, Hasegawa, Kawakami, & Ohwada,
1990). To manufacture ultra large-scale integration de-
vices with high performance and reliability in large

0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 1 ) 0 0 1 7 6 - 2
5074 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083
Fig. 1. Membrane–UV reactor.
volume, the integration level has to be increased. The
native oxide growth and roughness of the wafer surface
will become more and more critical as level of integra-
tion of semiconductor increases. Hence, to suppress the
native oxide growth, it is essential to reduce the dissolved
oxygen level in ultrapure water as much as possible.
Conventionally, the removal of the dissolved oxygen
from water can be achieved by either physical or chem-
ical methods. The physical methods such as thermal
degassing, vacuum degassing or nitrogen bubble deaera-
tion have inherent drawbacks in terms of both operating
costs and bulky construction. Also, with these physical
methods, it is diFcult to reduce the dissolved oxygen
concentration from parts per million (ppm) level down
to a few parts per billion level (Kasama, Yagi, Imaoka,
Kawakami, & Ohmi, 1990; Imaoka et al., 1991; Sato,
Hashimoto, Shinoda, & Takino, 1991). The chemical
methods such as addition of hydrazine or sodium sul3te,
although, provide an alternative to the physical methods,
they are undesirable because of the toxicity of the hy-
drazine material and because the addition of the sodium
sul3te will result in an increase of solid contents in wa-
ter. Reaction with a reducing agent such as hydrogen in
the presence of a catalyst (Li, Chua, Ng, & Teo, 1995)
or an UV light (Saito, 1991; Saito, Hiroshi, Mituru, Ken,
& Tujimura, 1994) to form water is an attractive method
as it produces no by-product to contaminate the product
water.
In the present study, the removal of dissolved oxygen
from water was investigated using a novel membrane–UV
reactor. The reactor, shown in Fig. 1, is made from sili-
cone rubber capillary (hollow 3ber) membranes packed
in a PVC (polyvinyl chloride) tube with an aluminum foil
3nished internal surface. An ultraviolet lamp is placed
at the center of the reactor to provide ultraviolet rays.
Hydrogen used as a reducing agent is fed into the shell
side of the reactor, while water containing saturated dis-
solved oxygen is introduced either cocurrently or counter-
currently into the lumen of the membrane. The removal
of the dissolved oxygen is, thus, achieved by the chem-
ical reaction between the dissolved oxygen and the dis-
solved hydrogen in the presence of the ultraviolet rays.
The e5ects of various operating and system conditions
on the overall performances of the reactor for the DO re-
moval were studied theoretically. Experimental data ob-
tained from the membrane reactor were compared with
the theoretical predictions and capabilities of the mem-
brane reactor for the DO removal were evaluated.
2. Experimental
2.1. Materials
Silicone rubber capillary used as hollow 3ber mem-
branes (brand name: SILASTICJ) are manufactured by
Dow Corning, USA. Their dimensions and the permeance
values determined for O2 and H2 are given in Table 1. The
silicone rubber membrane has a good resistance to UV
(ultraviolet) radiation and chemicals (Anon, 1999a). It is
also quite transparent to UV radiation (Ullmann, 1985).
Ultraviolet light source is a low-pressure mercury lamp
in the form of a tube. This type of lamp is also known
as germicidal lamp as it has a good germicidal e5ect. It
transmits in the short wave or UV-C range (180 –280 nm)
with a peak at 254 nm. The ultraviolet lamp is powered by
220 V electrical mains using the connection kit supplied,
which consists of a starter and ballast normally used with
the domestic 6uorescent lamps. A quartz glass tube used
for housing the ultraviolet lamp is purchased locally. It
is used instead of ordinary glass tubes as it can transmit
radiation in the range of 180 –3000 nm. Aluminum foil
was used as a re6ective layer on the inner surface of the
reactor shell. Among various re6ective materials, it has
one of the highest re6ectivity for UV radiation (Anon,
1999b). It should be noted that high re6ectance to visible
radiation does not necessarily mean high re6ectance to
short-wave UV radiation.
Water used was the tap water. The puri3ed air and hy-
drogen used were obtained from BOC Ltd. Their compo-
sition as per the label details of the supplier is shown in
Table 2.
2.2. Membrane–UV reactor
The novel membrane–UV reactor fabricated in our lab-
oratory is shown schematically in Fig. 1. It is basically
in the shape of a circular pipe (shell) with two 6at ends.
 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083 5075

Table 1
The system parameters and experimental conditions

Parameters Values Units

Fiber OD 0.64 mm
Fiber ID 0.30 mm
Number of 3bers 100 Dimensionless
Length of 3ber 710 mm
Oxygen permeance through the membrane 1:72 × 10−2 mol= m2 s atm
Hydrogen permeance through the membrane 2:13 × 10−2 mol= m2 s atm
Feed water 6ow rate 0:03 ∼ 0:4 l=min
Temperature 299 K
DO concentration in feed 6.7–8.6 ppm
Hydrogen pressure on shell side 0–4 atm
Gas 6ow rate 16.67 ml=s

Table 2
Composition of gases used

Gas O2 H2 N2 Moisture Hydrocarbons

Puri3ed air 21 ± 1% — — ¡ 2 vpm ¡ 5 vpm

Hydrogen ¡ 2 ppm 99.9995% — ¡ 2 ppm ¡ 0:5 ppm

The 6at ends have holes in their center to allow a quartz
glass tube to pass axially through them and the shell. The
shell is made up of a PVC (polyvinyl chloride) pipe of
2 in nominal pipe size (OD = 2:375; ID = 2:04). An alu-
minum foil layer is attached on the interior surface to
re6ect the ultraviolet radiation. The silicone rubber cap-
illaries were cut to 710 mm length and 3xed onto the
quartz glass tube using epoxy adhesive. These capillar-
ies were 3xed length-wise on the outer circumference
of the quartz glass tube and are 100 in number. The
quartz glass tube with the silicone capillaries 3xed on its
outer circumference was then 3xed axially inside the shell
using epoxy resin, taking proper care to prevent any dam-
age. The 6at end plates were then 3xed to shell by the
bolts, which are four in number on each end. The reac-
tor was then tested for leakage. Rubber gaskets and ‘O’
rings were used at the end cover plates to prevent leak-
age of water. Hydrogen gas and water were supplied by
nylon tubes and connected to the reactor using 6.35 mm
(1=4 in) NPT (non-parallel thread) sockets.
2.3. Experimental setup and procedure for DO removal
The experimental setup is shown schematically in
Fig. 2. In addition to the membrane–UV reactor, which
has been described earlier, the other equipments used
in the setup were the dissolved oxygen meter, chart
recorder, water feed pump, rotameters, 6ow control
valves, pressure regulators and pressure gauges. The ro-
tameters and pressure gauges were connected to the gas
and water supply lines. The hydrogen gas exiting from
the shell side was vented out into the atmosphere by
connecting it to a tube that runs out of a window or a
ventilator. Table 1 also lists the experimental conditions
used in this study.
The dissolved oxygen meter—Orbisphere Model 3600
is made by Orbisphere Laboratories, Switzerland. It was
connected to a Rikadenki chart recorder for continuous
plotting of the readings on a paper sheet. The pump
used was a NEMOJ Pump manufactured by Netzsch
Mohnopumpen Gmbh, Germany. Rotameters used for
water and gas 6ow rates measurement were manufactured
by Tokyo Keiso, Japan while pressure was measured us-
ing the Wika pressure gauge.
The feed water was saturated with puri3ed air prior
to being in pumped into the reactor. Calibration of the
DO meter was carried out and the inlet dissolved oxygen
level was measured and recorded.
The air-saturated water was passed through the 3ber
lumen of the reactor, while puri3ed hydrogen gas was
passed cocurrently or countercurrently through the shell
side. Experimental runs were carried out with variation
of inlet 6ow rates of water and variation of gas feed pres-
sures to study the reduction of dissolved oxygen levels.
The outlet dissolved oxygen levels were recorded after a
steady state was reached.
Hydrogen gas was used to study the removal of dis-
solved oxygen both by physical stripping (without switch-
ing on the UV light) and chemical reduction (with UV
light).
A combustible gas detector manufactured by Gas Tech
Inc., USA was used periodically to check for any explo-
sive levels of hydrogen gas in the vicinity of the exper-
imental apparatus. It was also used at the joints of the
5076 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083

Fig. 2. Experimental setup.

tubes and valves used for the supply of the hydrogen gas (5) The intensity of UV light is constant everywhere in
to test for any leakage. the reactor.
(6) The system is operated isothermally and in steady
state.
3. Theory
Based on the above assumptions, the general mass con-
3.1. Formation of the model servation equations for both oxygen and hydrogen, rep-
resented by a and b, respectively, in the liquid phase can
Con3guration of the membrane–UV reactor has been then be given as
described in the experimental section. Based on the oper-
 2   
ating arrangement, the following assumptions are made r @Ci 1 @Ci @2 Ci
2um 1 − = Di + + i ;
for the model development: Rin @z r @r @r 2
i = a; b (1)
(1) Oxygen and hydrogen concentrations in the liquid
phase are so small that the density and 6ow veloc- The boundary conditions are applied at the centerline,
ity in the liquid stream are constant along the 3ber the membrane wall as well as the inlet of the membrane
length. This assumption approximates the system re- reactor:
alistically and simpli3es the mass balance equations
@Ci
considerably. r = 0; = 0; (1a)
(2) Fully developed laminar 6ow occurs in the 3ber lu- @r
men, and axial dispersion in the liquid stream is neg- @Ci
ligible. This assumption is valid for a Reynolds num- r = Rin ; −Di = Pm; i (Hi Ci − pi ); (1b)
@r
ber not exceeding 2100. The entrance e5ect for the
6ow pro3le in the 3ber lumen is ignored because it z = 0; Ca = Ca0 ; Cb = 0: (1c)
is not signi3cant when compared to the length of the
3ber used. Furthermore, the 6ow velocity in the lu- The mass balance equations for oxygen and hydrogen in
men side can generally be expected to be greater than the shell side can also be formulated as
the axial di5usion. G d pi
(3) Gas 6ow in the shell side is a plug 6ow and the · = Pm; i 2nRin (Hi Ci |r=Rin − pi ) (2)
RT d z
volumetric 6ow rate is considered to be constant.
The radial concentration gradient in the gas stream with the boundary condition
is neglected. z = 0; pa = 0; pb = pb0 : (2a)
(4) Equilibrium is attained instantaneously between the
gas phase and liquid interface, and Henry’s equation In the above model equations, the various symbols are
is applied. de3ned in the notation section at the end of this paper.
 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083 5077

It should be pointed out that Eq. (2) was written for O = 2k1 Ca − k2 CO Cb − k3 [H2 O]CO ; (6b)
cocurrent 6ow arrangement only. However, it can be
easily extended to the countercurrent operating mode. If
the amount of feed gas used is so large that the oxygen b = − k2 CO Cb ; (6c)
concentration approaches zero in the gas phase and the
where k1 ; k2 ; k3 are the rate constants for individual reac-
hydrogen concentration is approximately uniform
tions, and k1 is proportional to the radiation intensity of
throughout the reactor, i.e. pa = 0 and pb = pb0 , Eq. (2)
the UV light.
can, thus, be dropped.
At quasi-steady state, the rate change of oxygen radical
The bulk average or “mixing cup” values of the dis-
is equal to zero, i.e. O = 0, the overall reaction rate may,
solved oxygen concentration at a given z is
then, be written as
 Rin  Rin
Ca u2r d r 4 k1 ks Ca Cb
Ca = 0 Rin = 2 Ca [1 − (r=Rin )2 ]r d r: (3) a = ; (7)
u2r d r Rin 0 1 + ks Cb
0

The extent of the dissolved oxygen removal is generally where ks is given by

de3ned as
ks = k2 =k3 [H2 O] (7a)
Ca0 − Ca (z = L)
Rev =
Ca0
 Rin 3.3. Dimensionless form of the model
(Ca |z=L =Ca0 )[1 − (r=Rin )2 ]r d r
=1− 0  Rin : (4) By performing the following dimensionless transform:
0
[1 − (r=Rin )2 ]r d r
Similar to the overall mass transfer coeFcient, Kl in the " = z=L; # = r=Rin ; (8a)
pure physical stripping case, the overall mass transfer
coeFcient with chemical reaction, Kl; R in the membrane– xa = Ca =Ca0 ; xb = Hb Cb =pb0 ; (8b)
UV reactor for a particular operating condition may also
be evaluated as
Q ya = pa =Ha Ca0 ; yb = pb =pb0 : (8c)
Kl; R = − ln(Ca |z=L =Ca0 ): (5)
ndL Eqs. (1) and (2) then become
3.2. Reaction kinetics Gz @xa 1 @xa @2 xa xa xb
(1 − #2 ) = + 2 − NH2 Ng ; (9a)
2 @" # @# @# 1 + Ng xb
The reaction mechanism between the dissolved oxy-
gen and hydrogen under the UV light has not been re- Gz @xb
(1 − #2 )
ported so far. However, the following reaction sequence 2 @"
should be reasonable on the basis of the general prin-  
1 @xb @2 xb xa xb
ciples for photo-catalyzed reactions (Harano & Smith, =( + 2 − Nc NH2 Ng ; (9b)
# @# @# 1 + Ng xb
1968). The dissolved oxygen molecule absorbs the ra-
diation of UV light forming activated oxygen radicals. d ya
Subsequently, the oxygen radical reacts with hydrogen Nf = xa |#=1 − ya ; (10a)
d"
molecules to produce water. At the same time, the acti-
vated oxygen radical can also be destroyed by a single d yb
radical termination (Harano & Smith, 1968) by collision Nf = +(xb |#=1 − yb ) (10b)
d"
with inert water molecules. The reaction mechanism may
be illustrated as follows: and the boundary conditions are rewritten as

O2 (l) + h() → 2O∗ ;

k1
(i) @xi @xi
# = 0; = 0; # = 1; = − Shi (xi − yi ); (11a)
@# @#
k
O∗ + H2 (l) →2 H2 O; (ii)
" = 0; xa = 1; ya = 0; xb = 0; yb = 1: (11b)
k
O∗ + H2 O →3 12 O2 (l) + H2 O: (iii) The extent of dissolved oxygen removal is rewritten in
the dimensionless form as
The local rates of formation of each component are:  1
a = − k1 Ca + 12 k3 [H2 O]CO ; (6a) Rev = 1 − 4 xa |"=1 (1 − #2 )# d # (12)
0
5078 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083

Table 3 Combining with Eqs. (10a) and (10b), the modelling

De3nitions of dimensionless parameters system may be accordingly described by 2(N − 1) + 2
Dimensionless parameters Expression 3rst-order ode’s which are rearranged in the following
matrix form:
Pm; i Rin Hi
Modi3ed Sherwood number S hWi =
Di d XW W XW )
= f( (16)
Graetz number Gz =
umd2 d"
Da L
 in which the variable matrix XW is
k1
Modi3ed Hatta number NH = Rin
Da XW = [xa; 1 ; xa; 2 ; : : : ; xa; N −1 ; xb; 1 ; xb; 2 ; : : : ; xb; N −1 ; ya ; yb ]T :
G=RT (16a)
Feed gas modulus Nf =
Pma 2nRin L
2Ca0 These ODEs are easily integrated by using the Runge–
Concentration modulus Nc =
pb0 =Hb Kutta method. The number of di5erence points is chosen
Reaction order modulus Ng = ks pb0 =Hb as N = 12 to attain suFcient accuracy and the Simpson
Kl; R d
integration technique is applied to calculate the average
Sherwood number Sh = DO concentration at a cross section. MATLAB software
Da
Membrane selectivity for H2 = O2 + = Pmb =Pma
has been employed in this work for the calculation.
Ratio of the di5usivity ( = Db =Da

4. Results and discussion

and the removal eFciency expressed in terms of the Sher- Simulations were carried out using basic parameters
wood number may also be written as listed in Table 4, while experimental data were obtained

  at various experimental conditions given in Table 1. Their
1
Gz 2 results are presented in the following three sections. In
Sh = − ln 4 xa |"=1 (1 − # )# d # : (13)
4 0 the 3rst, e5ect of the membrane resistance on the DO
removal from water is examined. In the second, the ef-
The dimensionless parameters in Eqs. (9)–(13) are de- fects of various operating conditions such as gas and wa-
3ned in Table 3. ter velocities, and hydrogen pressures on the removal of
dissolved oxygen are studied. The simulation results gen-
3.4. Method of numerical solution erated with di5erent reaction rate constants are also ex-
amined. Finally, experimental results are compared with
The model equations are a group of non-linear partial the predicted values and performance of the membrane–
di5erential equations and may be solved numerically. Fi- UV reactor in terms of the dissolved oxygen removal in
nite element di5erence forms in the radial direction are ultrapure water production is presented.
employed to replace the corresponding derivative terms
in Eqs. (9a) and (9b) so as to transform them into a series 4.1. E:ect of the membrane resistance
of ordinary di5erential equations
@x xj+1 − xj−1 In this study, both the oxygen and hydrogen may per-
= ; (0 ¡ j ¡ N ); (14a) meate through the membrane during operation. Hence,
@# 2X#
the membrane resistance may a5ect the overall perfor-
@2 x xj+1 − 2xj + xj−1 mance of the DO removal. In order to study this e5ect,
= ; (0 ¡ j ¡ N ); (14b) a modi3ed Sherwood number, S hWi , has been introduced
@#2 X#2
where j is the di5erence mesh order, N is the total num-
ber of di5erence meshes and X# is the radial di5erence Table 4
Basic parameters used for the simulation
distance: X# = 1=N .
Substituting Eq. (14) into Eq. (11a) gives the concen- Modi3ed Sherwood number, S hWi S hWa = 843; S hWb = 1189
trations on the boundary as Graetz number, Gz 20
Modi3ed Hatta number, NH 2
j = 0; xi; 0 = 13 (4xi; 1 − xi; 2 ); (15a) Feed gas modulus, Nf 1
Concentration modulus, Nc 0.2
Reaction order modulus, Ng 2
4xi; N −1 − xi; N −2 + 2X#S hWi yi Ratio of the di5usivity, ( 1.423
j = N; xi; N = : (15b) Membrane selectivity for H2 = O2 ; + 1.240
3 + 2X#S hWi
 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083
Fig. 3. E5ect of the modi3ed Sherwood number on DO removal at
di5erent Graetz numbers.
Fig. 4. E5ect of gas 6ow rate on the DO removal at di5erent modi3ed
Sherwood numbers.
and was de3ned in Table 3. It can be seen that it is the ra-
tio of liquid di5usion resistance to the membrane perme-
ation resistance and thus re6ects their relative importance
in the operation. For example, S hWi → ∞ means that the
membrane resistance is negligible compared to the liquid
di5usion resistance. Under such a condition, the partial
pressures of the H2 and O2 gases at the membrane=liquid
interface is equal to those at the bulk gas, i.e., xi |#=1 = yi .
Fig. 3 shows the e5ect of the modi3ed Sherwood num-
bers calculated from oxygen, S hWa on the DO removal at
di5erent Graetz numbers. The dashed lines plotted in the
3gure are the calculated data obtained at a condition of
S hWa → ∞. As would be expected, the DO removal in-
creases as the modi3ed Sherwood number is increased.
At S hWa = 80 or greater, the DO removal approaches the
dashed lines indicating that the membrane resistance be-
comes negligible. As the permeance values of oxygen and
hydrogen through the silicone membrane have been mea-
sured to be 1:72 × 10−2 and 2:13 × 10−2 (mol= m2 s atm),
giving the corresponding modi3ed Sherwood number as
843 and 1189, respectively, which are much greater than
80, the membrane used in this study has, therefore, the
negligible resistance compared to that in the liquid phase.
4.2. E:ect of H2 gas ;ow rate
Predicted values for this e5ect are given in Figs. 4
and 5 where the DO removal is plotted against H2 gas
6ow rate, shown as feed gas modulus, Nf , for di5erent
5079
Fig. 5. E5ect of gas 6ow rate on DO removal at di5erent modi3ed
Hatta numbers.
values of the modi3ed Sherwood, S hWa and Hatta num-
bers, NH , respectively. It can be seen from these 3gures
that as the Nf value is increased, the dissolved oxygen
removal is improved but only up to a certain value of
the feed gas modulus, which may be termed as the e5ec-
tive feed gas modulus. Any further increase in the mod-
ulus after this e5ective feed gas modulus does not re-
sult in the better DO removal as shown in the 3gure. In
Fig. 5, the theoretical data obtained at a condition of the
H2 gas 6ow rate at in3nity or ya = 0 and yb = 1 are also
plotted with the dashed lines. As would be expected, the
e5ect of hydrogen 6ow rate decreases with increasing the
modi3ed Sherwood number. This implies that the hydro-
gen 6ow rate would not become a key factor for DO re-
moval if the membrane resistance is small. At S hWa = 50,
the DO removal approaches the dashed line at Nf ≈ 1 in-
dicating that maximum driving force of the oxygen trans-
fer is obtained and further increase in the hydrogen 6ow
rate would result in no e5ect on the DO removal. As indi-
cated in the previous section, the S hWa used in the present
system is 834, which is much larger than 50, i.e. less
hydrogen 6ow rate (Nf = 0:4) is required for the DO re-
moval.
Fig. 5 illustrates the e5ect of hydrogen gas 6ow rate
on the DO removal at di5erent modi3ed Hatta numbers.
As can be seen, the e5ective feed gas modulus varies
slightly with the modi3ed Hatta number (reaction rate).
For example, at the modi3ed Hatta number of NH = 1,
the e5ective feed gas modulus, Nf , is around 0.3. As the
modi3ed Hatta number, NH , increases to 10, the e5ective
feed gas modulus, Nf , reduces to less than 0.1. This result
is, again, expected, as the higher the reaction rate, the less
the amount of feed gas required to achieve the optimum
driving force. Of course, other factors such as higher hy-
drogen pressure, which enhances the reaction rate, would
certainly decrease the e5ective feed gas modulus, Nf .
4.3. E:ect of chemical reaction
When ultraviolet rays are applied to water containing
both the dissolved oxygen and the dissolved hydrogen, the
reaction between these two dissolved gases takes place
to form water as a product (Saito, 1991). Introducing
5080 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083
Fig. 6. Sherwood number versus Graetz number at di5erent modi3ed
Hatta numbers.
the chemical reaction in water enhances mass transfer co-
eFcient, hence, increases the rate of removal of the dis-
solved oxygen. Fig. 6 shows the simulation results for this
e5ect. Again, the mass transfer coeFcient with chemical
reaction, Kl; R , calculated from Eq. (5), as the Sherwood
number, Sh, was plotted against the water velocity, as
the Graetz number, Gz with the modi3ed Hatta number,
NH , as a parameter. As can be seen from the 3gure, with
increasing NH , the curves are higher, signifying a better
mass transfer coeFcient. From the nature of the curves,
it can also be seen that there exists an optimum value
of the Graetz number, Gz for a given NH value (greater
than zero) at which a maximum value of Sh number is
possible. For example, at NH = 3, the maximum value of
Sh number is achievable at the Gz number of 6. When
the NH value increases to 10, the maximum Sh number
could not be achieved until the Gz number is increased
to 14. It is obvious that the optimum Sh number is only
attainable at high NH values, i.e., the chemical reaction
becomes extremely fast.
When a mass transfer is enhanced by a chemical reac-
tion, the mass transfer coeFcient is enhanced by a factor
of E, i.e.
Kl; R = Kl E: (17)
For an extremely fast reaction (instantaneous reaction)
with negligible gas 3lm resistances. The enhancement
factor, E can be expressed as (Danckwerts, 1970)
bDb Cb
E =1 + : (18)
Da Ca
As can be seen from Eqs. (17) and (18), the Sh number
(which is relating to Kl; R ) in Fig. 6 is not only dependent
on Kl , but also dependent on E. Increase of the water
velocity, i.e, increase Gz number, generally increases the
Kl , but certainly decreases E. With these two opposing
e5ects, it is conceivable that an optimum Sh number at
a certain Gz number is attainable when a extremely fast
chemical reaction is introduced. It, thus follows that when
the chemical reaction is introduced, control of the feed
6ow rate is crucial. In order to reduce DO content in
Fig. 7. E5ect of hydrogen pressure on DO removal: (a) NH = 5; (b)
NH = 2.
water to a very low level, the optimum operation of the
feed water 6ow rate in the reactor is essential.
4.4. E:ect of H2 pressure
Fig. 7 plots the DO removal versus the water velocity
shown as the Graetz number with the partial pressure of
hydrogen at the inlet, pb0 as a parameter. It can be seen
from Fig. 7a that as the shell side pressure increases from
0.1 to 5, the DO removal is increased. This can be at-
tributed to the magnitude of driving force that is present
in the transfer of hydrogen. The higher the concentration
of hydrogen in the shell side, the greater the driving force
for the transfer of hydrogen into water, hence the higher
concentration of hydrogen in water. If the chemical reac-
tion between the dissolved oxygen and hydrogen is very
fast, the better DO removal could be obtained as shown
in Fig. 7a where the data were calculated at NH = 5. As
the NH reduces to 2, i.e. slow reaction, the resistance due
to the chemical reaction may become signi3cant and the
higher concentration of hydrogen in water would have
less e5ect on the DO removal (Fig. 7b).
It can be seen from the reaction mechanism that the
hydrogen concentration a5ects directly the types of the
governing equation, re6ected by the reaction order mod-
ulus, Ng in this study. When Ng  1, the reaction is
approximated to the 3rst order with respect to oxygen
concentration. However, it becomes a second order reac-
tion with respect to oxygen and hydrogen concentrations
if Ng is much less than 1. The e5ect of reaction order
modulus, Ng on the DO removal is illustrated in Fig. 8.
The simulation results for the 3rst order reaction kinetics
 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083
Fig. 8. E5ect of reaction order modulus on DO removal
and second order reaction kinetics have also been plotted
with dashed and dash-dotted lines. It can be seen that the
reaction is close to the second order when Ng ¡ 1 and
the 3rst order when Ng ¿ 100, respectively. The two ki-
netic parameters can be exactly estimated if the value of
Ng ranges from 1 to 100.
4.5. Comparison with experimental data
The dissolved oxygen removal corresponding to the
change of water 6ow rate was measured at di5erent in-
let DO concentrations and di5erent hydrogen pressures.
The operating conditions are also listed in Table 1. In
all the experiments, the H2 gas 6ow rate is controlled at
16:67 ml= s, corresponding to the feed gas modulus, Nf
of 0.8, which is considerably higher than its e5ective
value.
As the reaction mechanism was put forward for the 3rst
time, the kinetics parameters have to be estimated by the
experimental results. In this work, the experimental re-
sults were 3tted with the theoretical values using the least
square method where the tolerance function is de3ned as:

m The two kinetic parameters have been evaluated to
1  exp
Er =
(x − xkcal )2 ; (19)
m k=1 k
where m is the total number of the experiments, the su-
perscripts of exp and cal represent experimental data
and theoretical results, respectively. The estimated kinet-
ics parameters of k1 and ks are equal to 0:184 s−1 and
18:7 m3 mol−1 , respectively. The di5erences between the
experimental data and simulation results are given in
Table 5.
Experimental data obtained with and without the pres-
ence of chemical reaction were also plotted in Fig. 9.
It can be seen from the 3gure and also from Table 5
that the experimental data obtained from the physical
stripping agree very well with the theoretical results cal-
culated at the condition of no UV irradiation. The ex-
perimental results obtained with chemical reaction agree
also well with the predicted values at k1 = 0:184 s−1 and
ks = 18:7 m3 mol−1 . Small deviation occurs at the low
5081
Fig. 9. Comparison of the simulation results with experimental data.
feed water velocity for experiment 4, while at the high
feed water velocity for experiment 3. However, the gen-
eral trends of all the experimental data are clear to merit
a meaningful comparison between the simulation and ex-
perimental results.
5. Conclusions
Removal of dissolved oxygen from water has been
studied theoretically and experimentally in a novel
membrane–UV reactor using puri3ed hydrogen gas as
a reducing agent. The reaction mechanism between the
dissolved oxygen and hydrogen under UV light has
been proposed and a corresponding kinetic expression
containing two kinetic parameters has been formulated.
be k1 = 0:184 s−1 and ks = 18:7 m3 mol−1 , respectively,
from the experimental data obtained from the novel
membrane–UV reactor.
A mathematical model for predicting the performance
of the membrane–UV reactor has also been proposed.
Characteristics of the membrane and various operating
conditions such as gas and water velocities, and hydrogen
pressures on the removal of dissolved oxygen have been
studied extensively by numerical analyses. The simula-
tion results indicate that the membrane resistance is neg-
ligible compared to the di5usional resistance in the liquid
phase. The theoretical results further reveal that the ef-
fective hydrogen gas 6ow rate, characterized by the feed
gas modulus, Nf should be controlled at Nf = 0:4. As the
modi3ed Hatta number, NH increases, the e5ective feed
gas modulus, Nf could be further reduced accordingly.
Experimental results obtained from the reactor at various
operating conditions are in good agreement with those
predicted from the mathematical model developed.
5082 K. Li, X. Tan / Chemical Engineering Science 56 (2001) 5073–5083

Table 5
Experimental conditions and deviation from theoretical results

Exp. No. H2 pressure in O2 concentration in Di5erence between simulation

feed gas, atm feed water, ppm and experimental results, Er
1 0 8.3 0.005
2 1 8.6 0.009
3 1.5 7.2 0.010
4 2 6.7 0.008
5 3 8.6 0.017
6 4 6.9 0.011

Notation R gas constant, R = 8:206 × 10−5 , atm m3

mol−1 K −1
b Stoichiometric coeFcient, dimensionless r radius variable, m
Rin inner radius of hollow 3ber, m
C liquid concentration, mol m−3
Rev dissolved oxygen removal, dimensionless
Ca mixing cup concentration, mol m−3 Sh Sherwood number, Sh = Kl; R d=Da , de3ned in
Ca0 dissolved oxygen concentration in feed water, Table 3, dimensionless
mol m−3 ,
S hW Modi3ed Sherwood number, de3ned in Table
D di5usivities of gases in water, m2 s−1
3, dimensionless
d inner diameter of hollow 3ber, m
T temperature, K
E Enhancement factor, dimensionless
u liquid velocity in 3ber, m s−1
Er tolerance between simulation and experimental
um average velocity in 3ber, um = Q=nR2i , m s−1
results, dimensionless
x dimensionless concentration in liquid phase, di-
G volumetric 6ow rate of feed gas, m3 s−1
mensionless
Gz Graetz number, Gz = um d2 =Da L, dimensionless
y dimensionless concentration in the gas phase,
H Henry low constant in water, atm m3 mol−1
dimensionless
Kl Overall mass transfer of oxygen with no chem-
z length variable, m
ical reaction, m s−1
Kl; R Overall mass transfer coeFcient of oxygen with Greek letters
chemical reaction, m s−1
k1 rate constant of reaction (i), s−1 ( ratio of di5usivity, de3ned in Table 3
k2 chemical reaction constant for (ii), + membrane selectivity for O2 = H2
m3 mol−1 s−1 # dimensionless radius
k3 chemical reaction constant for (iii), " dimensionless 3ber length
m3 mol−1 s−1 X# radial di5erence distance: X# = 1=N , dimen-
ks reaction kinetics parameter, de3ned by Eq. (7a), sionless
m3 mol−1  chemical reaction rate, mol m−3 s−1
L e5ective 3ber length, m Superscripts
m total number of experiments, dimensionless
N number of di5erence points, dimensionless cal theoretical result, dimensionless
n number of hollow 3bers, dimensionless exp experimental data, dimensionless
Nc concentration modulus, de3ned in Table 3, di- Subscripts
mensionless
Nf feed gas modulus, de3ned in Table 3, dimen- a oxygen, dimensionless
sionless b hydrogen, dimensionless
Ng reaction order modulus, de3ned in Table 3, di- i shortcut for oxygen and hydrogen, dimension-
mensionless less
NH modi3ed Hatta number, de3ned in Table 3, di- j the di5erence mesh order, dimensionless
mensionless O oxygen radical, dimensionless
pb0 hydrogen partial pressure in feed gas, atm
Pm permeance of gas through membrane,
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