Desalination 147 (2002) 43–48

Effect of ozonation for reducing membrane-fouling in the
UF membrane
Young G. Park
Department of Chemical Engineering, Daejin University, 11-1 Sundanri Pochuneup Pochungoon
Gyungkido 487-711 Korea
Tel. +82 (31) 533-1970; Fax +82 (31) 536-6676; email:
Received 30 January 2002; accepted 26 March 2002

The effect of ozonation on permeate flux was studied by using a polysulfone ultrafiltration membrane. The filtration
was carried out by permeating chemical wastewater treated by combined ozone and membrane filtration methods under
3 kgf/cm2 until steady-state flux was obtained. Then, the ozone of concentration range between 10 and 45 mg/l×min
was ozonated in water for reducing the fouling on the UF membrane. It was found that the ozonation made the
permeate flux enhance by 10%, and oxidation by ozone and hydrogen peroxide was more effective. Evidence was
presented that TMP decreased in more ozone-concentrated water and it was found that the ozone-mediated membrane
would have a limited role to prevent membrane fouling rather than to eliminate it fully.
Keywords: Membrane process; Ozone; Chemical wastewater

1. Introduction
The most important disadvantage of membrane filtration is the declination of permeate flux
due to membrane fouling, resulting from gel layer
formation on the membrane surface, adsorption of
solute on the membrane pores and blocking of
pores by rejected solutes. Serious problems in
performing efficient membrane operation are
encountered in both microfiltration and ultra-

filtration. A number of ways have been available
for reducing the extent of fouling and for
controlling fouling and concentration polarization. The improvement methods of membrane
performance are selected by one of four categories: pretreatment of feed solution, adjustment
of membrane material properties, membrane
cleaning and improvement by operating
conditions. Practically, what is most widely used

Presented at the International Congress on Membranes and Membrane Processes (ICOM), Toulouse, France,
July 7–12, 2002.
0011-9164/02/$– See front matter © 2002 Elsevier Science B.V. All rights reserved

TMP was measured at the front of membrane module and during the filtration. a surface area of 0.44 Y.000 MWCO. In this study.1. the overall dimension is N25 mm×320 mm. having a nominal pore size of 0.4 mm of OD and separation capacity of 10. As schematically illustrated in Fig. The purpose of this work is to conduct experimental studies of the combined ozonation. As will be shown later. 1 illustrates a schematic of the experimental apparatus.1 µm. the raw water was further treated in the membrane process. As a result. Thus the membrane-housing was pressurized to give a driving force to the filtration. 2. The solution was pumped into the membrane-housing. 1. elevating the water quality of the final effluent to a standard for safe discharge. A module of hollow fiber membrane. First of all. The raw chemical wastewater applied in the present study was also obtained from a large dyeing and finishing plant in the Gyungkido area.5 m2 and made of polysulfone material. and the excess amount of raw water was bypassed back into the mixing tank. The ozonation effect has been few studied for the enhancement of permeate flux in the membrane process. Membrane filtration by chemical oxidation was tried in the chemical wastewater after pretreatment by Fenton’s oxidation. an electric cleaning technique was developed. Park / Desalination 147 (2002) 43–48 in the membrane separation process is the cleaning technique by hydraulic. Consequently. Materials and methods 2. mechanical. Membrane Fig. Combination of both methods into a single process could offer an attractive alternative to remedy the inherent disadvantages of ozonation and membrane filtration. and filtration was continued for several hours. The purpose of ozone-use is to reduce membrane fouling in the process and to prolong the life-expectancy of the membrane as well as to enhance the water quality. the use of an ozonemediated membrane in the drinking water system has been utilized as an alternative method of prechlorination which should be avoided in order to reduce THMs in tap water. The water quality of wastewater fluctuated significantly over a wide range during the experimental period as shown in Table 1. The hollow fiber was 0. The raw wastewater was first treated using Fenton’s reagent to remove suspended particles as a pretreatment method.G. the charged particles fouled on the membrane were removed away from the membrane [1]. was installed in acrylic housing. chemical and electrical methods. More recently.1–9. Fenton’s oxidation and membrane process to address this point. this technique interrupts the continuous filtration process and cannot maintain the membrane operating at high permeate flux. the combined treatment process does offer considerable advantages unrealized by each of them.2 200–560 50–210 90–121 . The hydraulic cleaning including back-washing is the most important method for reducing membrane fouling. the filtration was performed after the ozonation.8 mm of ID. However. 1. the ozonation was integrated to the membrane process and studied the factors affecting an increase of permeated flux. The motivation of this investigation is first to explore the feasibility of using the ozonemediated membrane filtration method by ozonation. Table 1 Water quality of raw wastewater Item Range of measured values pH TOC (ppm) Turbidity (NTU) Color (CU) 5. which was applied by using a pulsed electric field to membrane filtration.

The ozone generator was rated at 30 g/h as the maximum generation capacity. flowmeter. 3 ozone generator. The ozone gas was generated by a PCI ozone generator (PCI. At the bottom of the reactor. 1. P. pressure gauge. 6 permeate storage tank. But the actual ozone output was primarily controlled by the inlet air flow rate as regulated by a rotameter to . 2. 7 chemicals. a solution sampling port and an ozone gas input port were provided. Such a combined chemical oxidation and membrane treatment was found to be highly efficient and may offer an advantage in dealing with the high variability of pollutant content in the chemical wastewater. ozone oxidation and membrane process unit as shown in Fig. Three experimental runs were carried out to verify the effectiveness of ozonation on TMP in order to investigate the effect of ozonation on preventing membrane fouling. 9 acid. 8 base. In a combined sequential treatment test run. 5 UF membrane module.2. The three treatment units could be operated independently in a batchwise fashion or in combined sequence. 4 ozone contactor. 1 raw water.000 mm long. the wastewater was further treated in the membrane process.Y. The experimental apparatus of the present investigation consisted of three major parts: chemical coagulation by Fenton’s oxidation. Schematic diagram of pilot plant.G. the wastewater was first fed to the chemical coagulation tank for pretreatment. elevating the water quality of the final effluent of wastewater to a standard for safe discharge or even for reuse as non-portable water. The batchwise mode was adopted for determining the individual operating conditions. PA. The effluent from that unit was then oxidized in the set-up that consisted of a ozone contactor which was 360 mm in ID and 1. F. 2 pretreatment contactor (Fenton’s oxidation). the ozonation on UF was studied by using an experimental set-up of cross-flow filtration pressure-units made of acrylic tubing. USA) which was equipped with an air process unit (air compressor. Experimental apparatus After the ozone-Fenton’s oxidation. Park / Desalination 147 (2002) 43–48 45 Fig. air dehydrolyzer). 1.

This accounted for the highly effective color removal of ozonation. TMP in case of input ozone of 10. and 20. a color removal over 93% could be achieved by ozonation. could be effectively removed around 60% by Fenton’s oxidation only. the ring opening or side chains generated a large amount of small chemical molecules in the solution by the ozonation. The ozone was fed to attain a total transferred dose of ion 46 mg/l×min in the reactor for 30 min. the ozone concentrations in the ozone gas mixture entering and exiting the reactor were determined using the UV detecting method using Wedeco (PCI Co. This conclusively indicates that the more ozonation could make the permeate flux easier in the membrane process and would make . Japan. causing rapid decolorization of wastewater. In the chemical pretreatment. the slope proportionally increased 8. Park / Desalination 147 (2002) 43–48 within 1 to 6 L/min in the present study. 3.. the permeate flux increased in higher concentration of input ozone and became constant. As a result. was equipped with an external vessel to treat with Fenton’s reagent consisting of FeSO4 ×7H2O and H2O2.55×10!4. Methods and analysis Batch experiments were adopted in the present study in order to facilitate identification of the optimum operating conditions of the combined treatment process. 2.G.13×10!3. Finally the wastewater effluent was fed to the membrane process unit. as shown in Fig.5 kgf/cm2. Fig. Korea.0 mg/l× min in comparison with those of 45.0 mg/l×min to 10.6 mg/l×min and 20. 1. The color degree was measured using a HACH measuring device.6 mg/l×min. and such a ozone-supported color removal was increased from 60% to 84%. the reactor. The TOC concentration was measured by the TOC meter (5000A) (Shimadzu Co. 3..17×10!3 as the ozone concentrations decreased from 45. however. and the hydrogen peroxide was obtained from Junsei Chemicals Co. but considerably less efficient TOC removal.3. The ferrous sulfate was obtained from Daejung Chemicals Co. Alteration of dyestuff molecules regardless of the original dyestuffs or altered ones were then oxidized [3]. Hence even without membrane process. the color. This accounts for the highly effective color removal of ozonation. Results and discussion The dyestuffs in the wastewater used in the present study had structures with multiple rings and side chains of benzidine polyazo-dye and bromamine acid anthraquinon-dye. 1. 2 shows the results of input ozone concentrations of 10. they were severed by ozonation as manifested by rapid color disappearance over 50%. Then the organic substances were more degradable and generated small molecule organic compounds by the oxidation of an ozone. but considerably less effective in the removal of TOC. Many previous investigations have shown that the ozonation was highly effective in breaking down the straight.46 Y. When the structural rings were opened up or the side chains including a phenol compound. However.).6 mg/l×min reached 3. It is noted that during the Fenton treatment of the wastewater.6 mg/l×min. In the wastewater.). the dissolved iron in conjunction with the externally added hydrogen peroxide functions and thus the synergistic effects of the membrane process and the ozone oxidation will be elaborated later. but significantly decreased in lower ozone concentration and had increased values with increasing TMP as shown in Fig. unsaturated bonds in the dye molecules. As TMP increased. 9.6 mg/l× min. a certain amount of ferrous sulfate was continuously dissolved into the wastewater [2]. respectively. In addition. Small liquid samples were then taken periodically to deter-mine the color absorbance and TOC concen-tration of the wastewater.

5% in case of 20. Acknowledgement This work was supported by the research fund of the Consortium of the Industry-AcademyResearch Institute in 2001. The higher removal efficiency in the membrane process in comparison with Fenton’s oxidation/ozonation indicates that better removal efficiency of TOC might occur due to the higher rejections in the porous membrane by alterations of chemicals in higher ozone concentration. 2. 4. the membrane prolong the period to reach the membrane-fouling rather than having a significant role to prevent the membrane fouling completely. 2. But the removal efficiencies of TOC were increased by 95. 3. TMP in two different input ozone concentrations of 10.1% and 97. In fact.0 mg/l×min and 45. it was observed in all 47 experimental runs at 4 L/min of ozone gas.6 mg/l×min of input ozone. removal efficiency over 91% could be achieved. Results from all experimental runs revealed that: 1.6 mg/l×min in the wastewater treatment.6 mg/l×min of input ozone.6 mg/l×min and 45. Conclusions Experiments were conducted to investigate the treatment by ozonation in the membrane process.6 mg/l× min. the overall treatment efficiency of TOC had a result of 98%.8% in case of the wastewater treated by 10. Emphases were placed on examining the performance characteristics of the combined treatment process.6 mg/l×min. it was found that the permeate flux increased in higher concentration of input ozone and slightly decreased in lower ozone concentration over time. Based on Fenton’s oxidation/ozonation membrane filtration mechanism. In fact. Effects of TMP in the different ozone concentrations of between 10. Ozonation did not have a significant role to prevent membrane fouling. 4. The addition of a membrane process did little to improve color removal over that by ozonation. The removal efficiencies of TOC in the membrane process was overall 93.6 mg/l×min and 45. Park / Desalination 147 (2002) 43–48 Fig. Permeate flux vs. The corresponding TOC removal by an ozonemediated membrane shows that those chemical compounds could be removed and considerably improved as the input amount of ozone increased. The most significant improvement in the TOC removal appeared to occur in high ozone concentration.6 mg/l× min to 45. .Y. As TMP increased.G. Fig. The flux rate increased about 12% as the input amount of ozone increased from 10. 3.

M. 34 (2000) 2786–2790. Hwang.. Beszedits. Am. Res.A. Kang and K. [3] S. Water Res.. Eng.48 Y. Sabuni. . Pulsed electrokinetic cleaning of cellulose nitrate microfiltration membrane. Ind. Effects of reaction conditions on the oxidation efficiency in the Fenton process.. Dyestuff Rept.G. Park / Desalination 147 (2002) 43–48 References [1] W. 69 (1980) 38–46. Chem. [2] Y. Ozonation to decolor textile effluents. Bowen and H.R. 31 (1992) 515– 523.