was used for the preparation of titanium dioxide modified polyvinylidene fluoride ultrafiltration membrane. Structure and properties of the membrane a

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1 ph - ph X 703 A Study on Treatment of Surfactant Wastewater by Coagulation and Membrane Separation Integrated Process WANG Jianming 1 WANG Hanbin 1 ZHONG Xiaoqing 2 SONG Hongchen 1 1 ( Guangdong Key Lab of Membrane Material and Membrane Separation, Guangzhou Institute of Advanced Technology, Chinese Academy of Sciences, Guangzhou , China ) 2 ( Water Science Research Center, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen , China ) Abstract Surfactants have complex compositions and low molecular weights, which usually leads to the eutrophication of waterbodies. For the treatment of wastewater that contains surfactants, the membrane separation technology is usually adopted. However, the membrane is easily polluted and the cleaning process is usually laborious. In this work, a new surfactants wastewater processing technology was investigated by combining the coagulation and membrane separation techniques. Firstly, the phase inversion technique B JCYJ hc.song@giat.ac.cn

2 was used for the preparation of titanium dioxide modified polyvinylidene fluoride ultrafiltration membrane. Structure and properties of the membrane are tested by several instrumentations, like the scanning electron microscopy, fourier transform infrared spectroscopy, and contact angle instrument. Secondly, using sodium dodecyl benzene sulfonate solution and polymerization aluminum chloride as surfactant wastewater and coagulant respectively, the treatment effect is evaluated with respect to ultraviolet light intensity, water flow rate and ph values. By observation, the modified membrane has dense-selective layer on the surface, and its cross-section is composed with finger holes and spongy structures. By the analysis of fourier transform infrared spectroscopy, polyethylene glycol and titanium dioxide in the modified membrane can cover apart of infrared absorption of polyvinylidene fluoride. The modified membrane has relative small contact angle and its performance is also insensitive to the change of ultraviolet light intensity and water flow rate. Moreover, the process can reach best performance while the wastewater with ph value of 4.5. The proposed surfactants wastewater process technique has distinct advantages of high efficiency and low-cost, which makes it with great potentials in the application of large scale industrial and domestic wastewater processing. Keywords coagulation; membrane separation; titanium dioxide; sodium dodecyl benzene sulfonate Linear Alklybezene Sulfonates LAS 72% 3 / ph ml/l 20 Sodium Dodecyl Benzene Sulfonate SDBS 96% 4 LAS LAS 65% 5 / mg/l 150 mg/l 80 m 3 /h 6 DK % 1 -

3 7-10 Polyaluminum Chloride PAC 11 Titanium Dioxide TiO 2 12 TiO 2 - SDBS ph TiO 2 5 Polyvinylidene Fluoride PVDF Polyethylene Glycol PEG Da80 4 TiO Table 1 Technologies and characters of surfactant waste water treatment 2 Table 2 Experiment reagents and instruments

4 4 cm cm 1 1 cm 2 3 μl MPa SDBS 224 nm 13 2 SDBS y x R (mg/l) 2 Fig. 2 Standard curve of sodium dodecyl benzene sulfonate solution 1 1 J L m 2 h 1 V m 3 A m 2 h 2 2 R C filtration g/l C bulk g/l 1 Fig. 1 The flow chart of cross-flow ultrafiltration experiment

2 796 cm 1 CH 2 975 cm 1 α 15 PEG TiO 2 β α 875 763 840 796 PVDF+TiO 2 +PEG PVDF+PEG PVDF 1 070

3 SEM picture of the membrane surface Fig. 5 Infrared spectra of the membrane 3.1.3 TiO 2 6 7 0.

5 Scanning Electron Microscope SEM 3 4 TiO 2 TiO 2 TiO 2 14 C C C 840 cm 1 CH 2 β 763 cm 1 CF cm 1 CH cm 1 α 15 PEG TiO 2 β α PVDF+TiO 2 +PEG PVDF+PEG PVDF (cm 1 ) SEM Fig. 3 SEM picture of the membrane surface Fig. 5 Infrared spectra of the membrane TiO wt% TiO TiO 2 PVDF TiO 2 4 SEM Fig. 4 SEM picture of the membrane cross-section PEG TiO cm 1 CH cm 1 CF cm TiO 2 Fig. 6 Contact angle of the membrane without TiO 2

6 1 wt% PVDF TiO 2 TiO TiO 2 Fig. 7 Contact angle of the membrane with TiO MPa SDBS 100 mg/l PAC 10 mg/l ph mg/l PAC 300 ml/min ph mw/cm mw/cm min 8 Fig. 8 Effect of different ultraviolet radiation intensity on the flux of membrane ultrafiltration % 1.0 mw/cm 2 TiO mw/cm mw/cm mw/cm 2 20 min 9 Fig. 9 Effect of different ultraviolet radiation intensity on the rejection rate of membrane ultrafiltration

7 300 ml/min 80% 300 ml/min ml/min ml/min 500 ml/min min 10 Fig. 10 Flux changes with different influent flow 100 ph SDBS SDBS ph 4.5 ph 2.5 ph 7 ph ph 4.5 ph ml/min 300 ml/min 500 ml/min ph 2.5 ph 4.5 ph 7 min 11 Fig. 11 Rejection changes with different influent flow ph ph 7 ph 4.5 ph ph 4.5 PAC 18 ph 2.5 PAC Al H 2 O 6 3+ ph 7 PAC min 12 ph Fig. 12 Flux changes with different ph ph 2.5 ph 4.5 ph 7 min 13 ph Fig. 13 Rejection changes with different ph

8 ph [19-26] Table 3 Characteristics of integrated membrane separation technology

9 4 1 PVDF TiO PEG TiO 2 β α TiO 2 /PVDF 2- SDBS PAC SDBS PAC 10 mg/l 300 ml/min ph 4.5 ph 3-TiO 2 1. SDBS D. :, ,. PAC PAM J., 2005, 24 3 : ,,,. UV/H 2 O 2 J., 2007, 32 2 : ,,,. J., 1998, 6 16 : ,. A 2 /O J., 2002, 22 7 : D. :, ,. - J., 2011, 37 4 : D. :, ,,,. J., 2014, 8 2 : D. :, ,,. J., 2010, 29 2 : Leong S, Razmjou A, Wang K, et al. TiO 2 based photocatalytic membranes: a review J. Journal of Membrane Science, 2014, 472: Zhao J, Oota H, Hidaka H, et al. Photodegradation of surfactants X. Comparison of the photooxidation of the aromatic moieties in sodium dodecylbenzene sulphonate and in sodium phenyldodecyl sulphonate at TiO 2 -H 2 O interfaces J. Journal of Photochemistty Photobiology A Chemistry, 1992, 69 2 : ,,. TiO 2 PVDF J., 2014, 41 6 : Wang QY, Wang ZW, Zhang J, et al. Antifouling behaviours of PVDF/nano-TiO 2 composite membranes revealed by surface energetics and quartz crystal microbalance monitoring J. RSC Advance, 2014, 4 82 : ,,,. - J.

10 , 2014, 34 6 : M. :, Zhang P, Wu Z, Zhang G, et al. Coagulation characteristics of polyaluminum chlorides PAC- Al30 on humic acid removal from water J. Separation and Purification Technology, 2008, 63 3 : ,,,. J., 2012, 43 5 : ,,,. - J., 2010, : ,,,. - J., 2009, 38 4 : ,,,. -- J., 2007, : ,,,. -- J., 2008, 34 3 : ,. - J., 2008, 14 1 : ,,,. J., 2008, : ,. J., 2006, 38 4 :

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