Membrane Contactors for

Textile Wastewater Ozonation

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


di Chimica e Chimica Industriale, Università 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

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
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 5–20% for acid dyes, 10% for disperse dyes, and
5–30% 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 æsthetic 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.
Ann. N.Y. Acad. Sci. 984: 29–38 (2003).

©2003 New York Academy of Sciences.

unsaturated bonds in the dyeing molecules. By properly controlling the pressure difference between the fluids. EXPERIMENTAL Membranes TABLE 1 lists the membranes used and their relevant properties.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.16–19 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. The effect of the membrane characteristic on the ozone mass transfer and decolorization yield is shown.6 flocculation. Membrane contactors are systems in which porous membranes are used to promote gas–liquid or liquid–liquid mass transfer without causing the dispersion of one phase into the other. However. such as micro-.14 The use of membrane-based ozonators in water treatment has not been fully developed. Wikol et al. these processes are still far from large-scale industrial application. A less expensive way to decolorize and reuse textile dyeing effluents has been found by inserting ozonation after an ærobic biological plant.9 Membrane processes. 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. such as bubble columns and packed beds. ultra-.12 Conventional methods of gas–liquid contact for the ozonation of wastewater. Details on membrane contactors and their advantages and benefits are reviewed by Gabelman and Hwang. These include activated carbon adsorption. This is accomplished by flowing the fluids on opposite sides of a porous membrane. because of the high costs involved.4 Other methods that were found to successfully evaluate the removal of color from textile effluents have been studied. the durability of the silicone membranes appeared to present a limiting factor. are limited by low mass transfer of ozone into the aqueous phase. acrylonitrile.7 and oxidation with hydrogen peroxide (Fenton’s reaction)8 even coupled with UV light. thus reducing the amount of pollutant present. Janknecht et al. a fluid–fluid interface is created in the pores. and nitrobenzene in wastewater. and nanofiltration and reverse osmosis have also been applied to dyehouse effluents with the main objective of recovering dyes and water.5 chemical precipitation. ozone consumption is reduced since the ozone serves only to break down the straight.10 Although effective.11 This process removes biodegradable matter from the water.30 ANNALS NEW YORK ACADEMY OF SCIENCES that 90% of the reactive dyes entering activated sludge sewage treatment plants will pass through unchanged. Therefore.13 tested a silicone capillary membrane-based ozonator for destroying phenol.15 Shanbhag et al. All membranes were 15 cm long but their porous permeable area was smaller since about 2cm at . Membrane-based equipment for bringing gas and liquid phases into contact could be suitable for industrial wastewater ozonation. used polytetrafluoroethylene membrane contactors to investigate the ozonization of tap water.

7 0. TAMI Industries (France) the ZrO2 represents the selective layer. 1 1 TAMI Industries (France) three channel 1 ATECH Innovations (Germany) 1.7 Outer Diameter Channel Diameter (cm) (cm) SCT (France) Configuration Manufacturer TABLE 1.1 single channel SCT (France) 200 nm 450 nm 140 nm 0.1 1.: TEXTILE WASTEWATER OZONATION 31 .a In the TAMI membrane b Hydraulic diameter. Membranes used and their main properties CIARDELLI et al.36b 0.36b 800 nm 200 nm Pore Size 16 α-Al2O3 ZrO2 α-Al2O3 40 39 22 ZrO2 α-Al2O3 21 α-Al2O3 Membrane Area (cm2) α-Al2O3 Materiala Selective Layer Properties 0.6 0.

traps. The gas pressure is regulated by a needle valve and read using a manometer. NV.32 ANNALS NEW YORK ACADEMY OF SCIENCES each end of the membrane was sealed using a vitrification process. 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. One membrane (TAMI. sampling valve. electromagnetic pump. FIGURE 1. gate valve.1m3/h) to the membrane lumen by means of an electromagnetic pump and then recirculated to the reactor. 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. . membrane and stainless steel vessel. ozone generator.20 Pilot Plant A schematic diagram of the membrane contactor laboratory scale plant is shown in FIGURE 1. A KI trap is also connected to the liquid reservoir in order to avoid any possible ozone discharge into the atmosphere. MM. 3 channels) among those listed was modified by coating a thin layer of inorganic oxides (TiO2 and γ-Al2O3) on the surface channels. needle valve. LR. manometers. 140 nm. The liquid is fed (at flow rate 0. OG. M. 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. liquid reservoir (2 L capacity). Schematic of the laboratory scale pilot plant used for the ozonation tests: GV. P. SV. T.

K L = ---------------------------A ( C L* – C L ) (1) The ozone flux NA through the gas–liquid interface was determined from the know amount of ozone transferred (at 25°C) to the liquid phase over time. The air pressure was gradually increased until reaching a value high enough to displace the water from the (largest) pore of the membrane pores.000mL solution (1.: TEXTILE WASTEWATER OZONATION 33 Membrane Characterization Membranes were characterized through bubble pressure and gas permeability measurements. Decolorization Experiments The simplified equation proposed by Chu and Ma21 D ln  ------0- = kt  D (2) was used to study the decolorization kinetics (T = 25°C) of model aqueous solution of Blue 19 reactive dye. was calculated using Henry’s law by assuming the ozone–air mixture to behave as an ideal gas. . This amount was evaluated by feeding the laboratory plant with a 2. Nitrogen permeability was determined at 20°C by measuring the pressure drop through the membrane due to the permeation of a controlled nitrogen flux. but employing deionized water as the liquid and air as the gas. with a solution of sodium thiosulphate.CIARDELLI et al. NA -. The interfacial area A was assumed to be equal to the membrane wet surface.750 mL potassium iodide and 250mL starch indicator) and titrating the iodine developed from the reaction between KI and O3. since the ozone was immediately consumed at the gas liquid interface. The concentration of ozone in the liquid phase CL was assumed to be zero. The former were carried on the same plant used for the textile wastewater treatment (FIG.20 Ozone Mass Transfer The well-known two-film theory was used to calculate the overall liquid phase mass transfer coefficients. The decolorization of exhausted dyebaths (untreated and after biological treatment) were also investigated at the same temperature. 1). The equilibrium concentration of ozone in the water phase C L* . 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. The initial dye concentration (D0) and at a given reaction time (D) were determined spectrophotometrically. A glass membrane vessel was also used to directly observe the air bubble stream passed through this pore.

it obviously reduces the overall membrane porosity and consequently lowers the gas membrane permeability. thus increasing the bubble pressure. .5 bar. Coating the membrane surface with a thin layer of metal oxides eliminates the defects. connected to the presence of defects on the membrane surface. much lower than the theoretical value (P) that may be calculated by the Young–Laplace equation. when the bubble pressure is too low. Pliquid = 0. especially when long industrial membrane elements are employed..34 ANNALS NEW YORK ACADEMY OF SCIENCES 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. FIGURE 2. θ (3) P = 2σ cos --. to control the gas–liquid interface inside the membrane pores becomes more difficult. hence. The low KL value of the TAMI multichannel membrane is due to the fact that the gas–liquid transfer occurs almost entirely in the outer part of the channels that first come into contact with ozone. This is because the pressure of the liquid that flows through the lumen-side of the membrane progressively decreases due to friction loss. In fact. This fact. and r is the pore radius. r where σ is the surface tension (72dynes/cm for the air–water system).1 bar. The single channels SCT and ATECH uncoated membrane exhibits very high KL values due to their high pore size and gas permeability. However. may cause severe problems for the industrial implementation of an application using these types of membranes as contact devices. FIGURE 2 shows the mass transfer coefficients for various types of uncoated membranes. θ is the contact angle (usually assumed to be zero). Overall liquid phase mass transfer coefficient for various types of uncoated membranes. Pgas = 0.

CIARDELLI et al. Ozone transferred to the liquid phase (Pliquid = 0. hence. 2).5 () bar.5bar (FIG. The results of decolorization tests carried out on real solutions derived from untreated and biologically treated dyebaths are shown in TABLE 3. FIGURE 3. The importance of this finding is obvious in view of the need to have sufficiently high bubble pressures at the beginning of this section. 1 (). the higher the initial dyestuff concentration the lower the kinetic constant k.5 (). 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. and 0. Pg = 1.75 (). thus improving the ozone transfer (see FIGURE 3). The deposition on the membrane of a thin and less porous metal oxide (TiO2 and γ-Al2O3) layer allows for operations to occur at higher pressure. as TABLE 2 clearly indicates.1 bar) at various gas pressures for a TAMI 140 nm 3C membrane coated with a thin layer of metal oxides. . Decolorization Experiments Coated TAMI membranes were used for decolorization experiments because of the feasibility to better control the gas–liquid interface and. As can be seen the decolorization became much easier for the biologically treated dyebath. A straightforward relation is observed according to Equation (2) and.75 bar reaches a much higher value than that found for the uncoated membrane at 0. 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. the ozone transfer.5 bar) to avoid the liquid being forced out of the pores. Consequently (see FIGURE 4) KL at 1. 1.: TEXTILE WASTEWATER OZONATION 35 It is worth observing that the reported KL values are evaluated at a very low gas pressure (Pgas = 0.

36 ANNALS NEW YORK ACADEMY OF SCIENCES FIGURE 4. 0.036 (). D0 = 0.072 (). . Overall liquid phase mass transfer coefficient for a TAMI 140 nm 3C membrane coated with a thin layer of metal oxides. and 0.018 () mmol/L. Variation of ln(D0/D) versus operating time during decolorization of Blue 19 dye solutions of various initial concentrations. FIGURE 5.1 bar. Pliquid = 0.

Water Res. 3. CIANNARELLA.. A..2 × 10–2 0.H. G OMES.L. R.: TEXTILE WASTEWATER OZONATION 37 TABLE 2. 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. LOPEZ. Kinetic characteristics of textile wastewater ozonation in fluidized and fixed activated carbon beds. with a substantial improvement of the ozone transfer.04 65 52 90 37. 1999. G.936 83 75 60 25.8 × 10–4 3. A.03 × 10–4 TABLE 3. 34: 763–772. Water Sci. Dyers Colour 116: 393–397. BRAS. Soc.57 46 38 120 50.2 × 10–4 7. et al.C. I. 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 12.61 35 15 CONCLUSIONS It was demonstrated that ceramic membranes may be effectively used for textile wastewater ozonization. Kinetic constant k as a function of the initial dyestuff concentration Solution Concentration (mmol/L) k (sec–1) 1. J. Textile wastewater reuse: ozonation of membrane concentrated secondary effluent. Biological treatment of effluent containing textile dyes. . GONÇALVES. RICCO. 2. R. REFERENCES 1. et al. S. L AI. Prudente for ozone transfer and decolorization experiments. ACKNOWLEDGMENTS The authors wish to acknowledge Dr. Tech.M. 40: 99–105. 2000.CIARDELLI et al.6 × 10–2 1.8 × 10–2 1. & C. R. 2000. LIN.09 38 20 150 62.

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