Membrane Contactors for

Textile Wastewater Ozonation

GIANLUCA CIARDELLI,a INGRID CIABATTI,a LAURA RANIERI,a
GUSTAVO CAPANNELLI,b AND ALDO BOTTINOb
aTecnotessile

S.r.l., via del Gelso 13, Prato, Italy

bDipartimento

di Chimica e Chimica Industriale, Universit di Genova,

Via Dodecaneso 31, Genoa, Italy

ABSTRACT: This paper deals with the application of a membrane contactor for
the ozone treatment of textile wastewater. Ceramic (
-Al2O3) membranes were
chosen because of their ozone resistance. A thin metal oxide (TiO 2 and -Al2O3)
layer was deposited on the membrane surface to eliminate large defects. Membranes were characterized by bubble pressure and gas permeability tests. Mass
transfer coefficients were calculated by using the double-film theory. Decolorization kinetics were studied with model dye solutions. Decolorization experiments with a real exhausted dyebath (untreated and after biological treatment)
were also carried out. The potential advantages of membrane contactors for the
treatment of these types of effluents are demonstrated.
KEYWORDS: membrane contactors; ozonation; reuse; textile wastewater

INTRODUCTION
Water is used extensively throughout textile processing operations and its
consumption varies widely depending on the type of unit process and the type of
equipment employed. Textile wastewater may include a large variety of dyes, detergents, insecticides, pesticides, fungicides, grease and oils, sulfide compounds, solvents, heavy metals, inorganic salts, and fibers in amounts that vary from industry to
industry.1
Dyeing is among the most water-intensive processes in textile production, which
in turn produces waste streams with high environmental impact, mainly because of
their color (due to soluble and insoluble dyes). It has been estimated that the dye loss
in the discharged effluent is around 520% for acid dyes, 10% for disperse dyes, and
530% for direct dyes. Even if dyes are generally non-toxic, the dark color in water
streams reduces light penetration that affects plant growth and wildlife, among other
environmental concerns. Furthermore, color can cause sthetic problems to the surroundings.2
Textile wastewaters are often purified by means of biological processes but
because dyestuffs are highly structured, complex polymers that are very difficult to
biologically decompose,3 they only partially remove color. For example, it is known
Address for correspondence: Gianluca Ciardelli, Tecnotessile S.r.l., via del Gelso 13,
I-59100 Prato, Italy. Voice: +39-0574-634040; fax: +39-0574-634045.
chemtech@tecnotex.it
Ann. N.Y. Acad. Sci. 984: 2938 (2003).

2003 New York Academy of Sciences.

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ANNALS NEW YORK ACADEMY OF SCIENCES

that 90% of the reactive dyes entering activated sludge sewage treatment plants will
pass through unchanged.4 Other methods that were found to successfully evaluate
the removal of color from textile effluents have been studied. These include activated
carbon adsorption,5 chemical precipitation,6 flocculation,7 and oxidation with
hydrogen peroxide (Fentons reaction)8 even coupled with UV light.9 Membrane
processes, such as micro-, ultra-, and nanofiltration and reverse osmosis have also
been applied to dyehouse effluents with the main objective of recovering dyes and
water.10 Although effective, these processes are still far from large-scale industrial
application, because of the high costs involved.
A less expensive way to decolorize and reuse textile dyeing effluents has been
found by inserting ozonation after an robic biological plant.11 This process
removes biodegradable matter from the water, thus reducing the amount of pollutant
present. Therefore, ozone consumption is reduced since the ozone serves only to
break down the straight, unsaturated bonds in the dyeing molecules.12
Conventional methods of gasliquid contact for the ozonation of wastewater,
such as bubble columns and packed beds, are limited by low mass transfer of ozone
into the aqueous phase.13 In order to increase the number of industrial sites performing wastewater purification by ozonation it is important to attain a high degree of
ozone utilization in the contactors and to minimize the costs related to ozone production and ozone destruction in the outlet gas.
Membrane-based equipment for bringing gas and liquid phases into contact could
be suitable for industrial wastewater ozonation. Membrane contactors are systems in
which porous membranes are used to promote gasliquid or liquidliquid mass
transfer without causing the dispersion of one phase into the other. This is accomplished by flowing the fluids on opposite sides of a porous membrane. By properly
controlling the pressure difference between the fluids, a fluidfluid interface is created in the pores. Details on membrane contactors and their advantages and benefits
are reviewed by Gabelman and Hwang.14
The use of membrane-based ozonators in water treatment has not been fully
developed. Wikol et al. used polytetrafluoroethylene membrane contactors to investigate the ozonization of tap water.15 Shanbhag et al.13 tested a silicone capillary
membrane-based ozonator for destroying phenol, acrylonitrile, and nitrobenzene in
wastewater. However, the durability of the silicone membranes appeared to present
a limiting factor. Janknecht et al.1619 studied the more inert ceramic membranes for
ozonization in a wet-oxidative treatment and investigated the effect of a hydrophobic
coating of their surface on the ozone mass transfer.
In this paper a variety of ceramic membranes with various pore sizes and configurations are examined as membrane contactors for the treatment of textile wastewater. The effect of the membrane characteristic on the ozone mass transfer and
decolorization yield is shown.

EXPERIMENTAL
Membranes
TABLE 1 lists the membranes used and their relevant properties. All membranes
were 15 cm long but their porous permeable area was smaller since about 2cm at

a In the TAMI membrane

b Hydraulic diameter.

TAMI Industries
(France)

the ZrO2 represents the selective layer.

TAMI Industries
(France)

three channel

ATECH Innovations
(Germany)

1.1
1.1

single channel

SCT (France)
200 nm

450 nm
140 nm

0.36b
0.36b

800 nm

200 nm

Pore Size

16

-Al2O3

ZrO2
-Al2O3

40

39

22

ZrO2
-Al2O3

21

-Al2O3

Membrane Area
(cm2)

-Al2O3

Materiala

Selective Layer Properties

0.6

0.7

0.7

Outer Diameter Channel Diameter

(cm)
(cm)

SCT (France)

Configuration

Manufacturer

TABLE 1. Membranes used and their main properties

CIARDELLI et al.: TEXTILE WASTEWATER OZONATION

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ANNALS NEW YORK ACADEMY OF SCIENCES

each end of the membrane was sealed using a vitrification process. For this reason
the values of the membrane area reported in TABLE 1 are lower than those that can
be calculated from channel diameter and membrane length. One membrane (TAMI,
140 nm, 3 channels) among those listed was modified by coating a thin layer of inorganic oxides (TiO2 and -Al2O3) on the surface channels.20
Pilot Plant
A schematic diagram of the membrane contactor laboratory scale plant is shown
in FIGURE 1. The liquid is fed (at flow rate 0.1m3/h) to the membrane lumen by
means of an electromagnetic pump and then recirculated to the reactor. The liquid
pressure is regulated by a gate valve and is read on a manometer placed at the outlet
of the stainless steel membrane module. The gas (a mixture of air and pure ozone
generated by the ozonizer) flows first along the shell side of the membrane module
and then through the KI solution contained in the trap prior to being discharged. A
KI trap is also connected to the liquid reservoir in order to avoid any possible ozone
discharge into the atmosphere. The gas pressure is regulated by a needle valve and
read using a manometer.

FIGURE 1. Schematic of the laboratory scale pilot plant used for the ozonation tests:
GV, gate valve; LR, liquid reservoir (2 L capacity); M, manometers; MM, membrane and
stainless steel vessel; NV, needle valve; OG, ozone generator; P, electromagnetic pump; T,
traps; SV, sampling valve.

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33

Membrane Characterization
Membranes were characterized through bubble pressure and gas permeability
measurements. The former were carried on the same plant used for the textile wastewater treatment (FIG. 1), but employing deionized water as the liquid and air as the
gas. The air pressure was gradually increased until reaching a value high enough to
displace the water from the (largest) pore of the membrane pores. A glass membrane
vessel was also used to directly observe the air bubble stream passed through this
pore.
Nitrogen permeability was determined at 20C by measuring the pressure drop
through the membrane due to the permeation of a controlled nitrogen flux.20
Ozone Mass Transfer
The well-known two-film theory was used to calculate the overall liquid phase
mass transfer coefficients,
NA
-.
K L = ---------------------------A ( C L* C L )

(1)

The ozone flux NA through the gasliquid interface was determined from the
know amount of ozone transferred (at 25C) to the liquid phase over time. This
amount was evaluated by feeding the laboratory plant with a 2,000mL solution
(1,750 mL potassium iodide and 250mL starch indicator) and titrating the iodine
developed from the reaction between KI and O3, with a solution of sodium thiosulphate. The interfacial area A was assumed to be equal to the membrane wet surface.
The concentration of ozone in the liquid phase CL was assumed to be zero, since the
ozone was immediately consumed at the gas liquid interface. The equilibrium concentration of ozone in the water phase C L* , was calculated using Henrys law by
assuming the ozoneair mixture to behave as an ideal gas.
Decolorization Experiments
The simplified equation proposed by Chu and Ma21
D
ln ------0- = kt
D

(2)

was used to study the decolorization kinetics (T = 25C) of model aqueous solution
of Blue 19 reactive dye. The initial dye concentration (D0) and at a given reaction
time (D) were determined spectrophotometrically. The decolorization of exhausted
dyebaths (untreated and after biological treatment) were also investigated at the
same temperature. Color was determined by measuring the absorbance at 420nm.
The decolorization percentage was calculated from the ratio between the absorbance
after a given reaction time and the initial absorbance of the exhausted solution.

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RESULTS AND DISCUSSION

The bubble pressure of all the membranes listed in TABLE 1 was found to be on
the order of 1bar or less and, hence, much lower than the theoretical value (P) that
may be calculated by the YoungLaplace equation,

(3)
P = 2 cos --- ,
r
where is the surface tension (72dynes/cm for the airwater system), is the contact angle (usually assumed to be zero), and r is the pore radius.
This fact, connected to the presence of defects on the membrane surface, may
cause severe problems for the industrial implementation of an application using
these types of membranes as contact devices. In fact, when the bubble pressure is too
low, to control the gasliquid interface inside the membrane pores becomes more
difficult, especially when long industrial membrane elements are employed. This is
because the pressure of the liquid that flows through the lumen-side of the membrane
progressively decreases due to friction loss. Coating the membrane surface with a
thin layer of metal oxides eliminates the defects, thus increasing the bubble pressure.
However, it obviously reduces the overall membrane porosity and consequently lowers the gas membrane permeability.
FIGURE 2 shows the mass transfer coefficients for various types of uncoated membranes. The single channels SCT and ATECH uncoated membrane exhibits very high
KL values due to their high pore size and gas permeability. The low KL value of the
TAMI multichannel membrane is due to the fact that the gasliquid transfer occurs
almost entirely in the outer part of the channels that first come into contact with
ozone.

FIGURE 2. Overall liquid phase mass transfer coefficient for various types of uncoated membranes. Pgas = 0.5 bar; Pliquid = 0.1 bar.

CIARDELLI et al.: TEXTILE WASTEWATER OZONATION

35

It is worth observing that the reported KL values are evaluated at a very low gas
pressure (Pgas = 0.5 bar) to avoid the liquid being forced out of the pores. The deposition on the membrane of a thin and less porous metal oxide (TiO2 and -Al2O3) layer allows for operations to occur at higher pressure, thus improving the ozone
transfer (see FIGURE 3). Consequently (see FIGURE 4) KL at 1.75 bar reaches a much
higher value than that found for the uncoated membrane at 0.5bar (FIG. 2). The
importance of this finding is obvious in view of the need to have sufficiently high
bubble pressures at the beginning of this section.
Decolorization Experiments
Coated TAMI membranes were used for decolorization experiments because of
the feasibility to better control the gasliquid interface and, hence, the ozone transfer. The results of decolorization kinetics studies carried out on three types of model
solutions with different initial dye (Blue 19) concentrations are shown in FIGURE 5.
A straightforward relation is observed according to Equation (2) and, as TABLE 2
clearly indicates, the higher the initial dyestuff concentration the lower the kinetic
constant k.
The results of decolorization tests carried out on real solutions derived from
untreated and biologically treated dyebaths are shown in TABLE 3. As can be seen the
decolorization became much easier for the biologically treated dyebath. After two
hours operating time the amount of dissolved ozone is about 50mg and the decolorization percentage is high enough to allow the reuse of the treated stream in textile
technological processes.

FIGURE 3. Ozone transferred to the liquid phase (Pliquid = 0.1 bar) at various gas pressures for a TAMI 140 nm 3C membrane coated with a thin layer of metal oxides. Pg = 1.75
(
), 1.5 (), 1 (), and 0.5 () bar.

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FIGURE 4. Overall liquid phase mass transfer coefficient for a TAMI 140 nm 3C
membrane coated with a thin layer of metal oxides. Pliquid = 0.1 bar.

FIGURE 5. Variation of ln(D0/D) versus operating time during decolorization of Blue

19 dye solutions of various initial concentrations. D0 = 0.072 (
), 0.036 (), and 0.018 ()
mmol/L.

CIARDELLI et al.: TEXTILE WASTEWATER OZONATION

37

TABLE 2. Kinetic constant k as a function of the initial dyestuff concentration

Solution Concentration (mmol/L)

k (sec1)

1.8 102

1.8 104

3.6 102

1.2 104

7.2 102

0.03 104

TABLE 3. Amount of dissolved ozone and decolorization percentage (see EXPERIMENTAL

section) over the operating time
Time
(min)

Dissolved Ozone
(mg)

Decolorization
(%)
Untreated
Dyebath

Biologically Treated
Dyebath

30

12.936

83

75

60

25.04

65

52

90

37.57

46

38

120

50.09

38

20

150

62.61

35

15

CONCLUSIONS
It was demonstrated that ceramic membranes may be effectively used for textile
wastewater ozonization. Coating the membrane surface with thin metal oxides layers
eliminates defects and the resulting increase of the bubble pressure permits operation at higher gas pressure, with a substantial improvement of the ozone transfer.

ACKNOWLEDGMENTS
The authors wish to acknowledge Dr. R. Prudente for ozone transfer and decolorization experiments.

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