Chemosphere, Vol 38, No 10, pp. 23152325, 1909 © vow Resear et ance 0454653598 $= se fon mater PII: $0045-6535(98)00450-0 IMMOBILISATION OF IRON IONS ON NAFION® AND ITS APPLICABILITY TO THE PHOTO-FENTON METHOD, P. Maletzky and R. Bauer’ Institute of Physical Chemistry, Vienna University of Technology Getreidemarkt 9, A-1060 Wien, Austria J. Lahnsteiner and B. Pouresmael ‘Austrian Energy & Environment, SGP/Waagner Biro GMBH SiemensstraBe 89, A-1210 Wien, Austria (Received in Germany 25 June 1998; accepted 27 August 1998) Abstract Immobilisation of iron ions on Nafion® is a promising technique to perform the Photo-Fenton method in a neutral pH range. Nafion® fulfil the requests of being a good complexing agent for iron and it is stable under oxidative and aqueous conditions. The efficiency of this new photocatalyst has been demonstrated by degradation experiments of 4-chlorophenol. In addition the influence of thickness and area of the membrane ‘on the TOC reduction was tested. Reusing of the membrane after a specific treatment sequence described in this work is also possible and the photocatalyst showed resistance to ageing. © 1999 Elsevier Science Ltd Al ights reserved 1 Introduction ‘The Photo-Fenton reaction, an Advanced Oxidation Process (AOP) [1,2,3,4], is already well known in literature (5,6,7,8]. It is an efficient and cheap method for wastewater treatment [9,10,11]. Production of hydroxyl radicals in an homogenous reaction pathway out of hydrogen peroxide under photocatalytic conditions is the basis of this method. This radical with a standard reduction potential of 2,8 V vs. NHE (see Table 1) is able to oxidise almost all organic compounds to carbon dioxide and water. "To whom correspondence should addressed 23152316 Oxidant Standard reduction potential IV vs, NHE] Fluorine (F;) 3,03 Hydroxyl radical (HO") 2,80 Ozone (05) 2,07 Hydrogen peroxide (H,O, ) 178 Chlorine (Cl;) 1,36 Table 1 Standard reduction potentials of some oxidants [12]. Iron in its ferrous and ferric form acts as photocatalyst and requires a working pH below 4. At higher pH values iron precipitates as hydroxide, The reversible redox cycle of iron can be described as followed. In the first step ferrous ions react with hydrogen peroxide yielding to ferric ions, hydroxyl radicals and hydroxide anions (eq.1), well known as Fenton reaction (13). In the next step ferric irons are reduced by light (A < $80 nm), generating further hydroxyl radicals (eq.2). This "Ligand-to-Metal-Charge-Transfer" (LMCT) takes place via a complex with mainly hydroxo groups, water or simple carboxylic acids as ligands. HO, + Fe" > Fe” + HO + HO" @ Fe(OH)" + hv + Fe + HO" @ Considering the Photo-Fenton method as a preliminary step prior to a biological wastewater treatment, one has to adjust pH twice. First to an acidic pH below 4 to perform the Photo-Fenton method and then back to a neutral pH. Therefore immobilisation of iron is a possible way to avoid the disadvantage of this pH dependency. For this purpose, the supporting material has to fulfil some requests. On the one hand it should be a good complexing agent for two different iron species (Fe, Fe”) and it should also show a stable configuration in aqueous solutions and resistance to oxidative conditions. On the other hand it should be transparent for UV/VIS radiation. This means that the support should not absorb the incident light in the range necessary for the Photo-Fenton reaction. This work is about the immobilisation of iron ions on Nafion® and its use in the Photo-Fenton method.2317 2 Experimental section 21 Materials Ferrous sulphate, hydrogen peroxide (30%) and 4-chlorophenol (4CP) were all analytical grade and supplied from Merck. All reagents employed were not subjected to any further treatment. Water used throughout was distilled. Two different Nafion® membranes (0,18 mm thick = membrane A and 0,43 mm thick = membrane B) were used and purchased from Sigma-Aldrich. Both membrane types were employed in the acid form with an equivalent weight of 1100. Before application they were soaked in distilled water and then loaded with iron using an ion exchange method. On this purpose the membrane was stirred at room temperature over a period of 24 hours in a solution containing 10? moV/L ferrous sulphate. 2.2 Photodegradation procedure An aqueous solution containing 4CP (1,4*10° moV/L; volume = 1 L; pH = 7,5 +/- 0,5), ferrous ion loaded Nafion® membrane (see Table 2) and hydrogen peroxide (2,3*10? moV/L) was illuminated under continuous magnetic agitation with a 400 W mercury lamp (Osram Ultramed 400) delivering 97 mW/em? (Kipp and Zonen CC20 radiation indicator with pyranometer CM3). The lamphousing (Polytec GmbH, LH- 151/3, including a condensing system LHC-151/3) was equipped with a 90° light tube (LHA-154/3). Experiments were carried out in unbuffered solutions over an irradiation time of 300 minutes and without temperature compensation. The temperature increased from about 20°C to approximately 30°C. All analytical methods were performed with unfiltered solutions. 23 Analytical methods Concentration changes of 4CP were monitored with a TOC-Analyzer 5000 (Shimadzu) equipped with an auto sampler (ASI 5000). The determination of iron was performed with the spectrometric method using 1,10-phenanthroline (UV-160A, Shimadzu, [14]). UV/VIS spectra were measured with a spectrophotometer (UV-160A, Shimadzu) in 10 mm quartz glass cells. The pH was measured by means of a WTW pH-Meter 537 equipped with a pH combination electrode E56, the oxygen was determined by means of a WTW microprocessor OXI-Meter OXI96 equipped with an oxygen electrode EO96 and the chloride content was measured by means of a WIW pH-Meter 523 equipped with a chloride combination electrode 9617BN (Orion). Hydrogen peroxide was determined iodomettically. 3. Results and Discussion 3.1 Studies on the membrane In Figures 1 and 2 changes in the absorption spectra of the used membranes are shown. One can see that the absorption decreased when the membrane was soaked in distilled water. This effect appears stronger with2318 membrane B. A reason for the lower transparency of the dry membrane B is the Teflon®grid used as reinforcing agent. + +dry membrane (0,18 mm) —+— membrane (0,18 mm) soaked in distilled water Fe(II) loaded membrane (0,18 mm) 200 300 400 500 600 700 800 Wavelength [nm] Figure 1 Changes in the absorption spectra of membrane A. = dry membrane (0,43 mm) 1s + —+— membrane (0,43 mm) soaked in distilled water | ——Fe(I1) loaded membrane (0,43 mm) Absorption [-] Wavelength [nm] Figure2 Changes in the absorption spectra of membrane B. ‘This reinforcement of membrane B also cause a continuous absorption of about 0,2 in the range of 200 to 800 nm in the case of soaked and loaded membrane. In the case of membrane A, there is also a continuous2319 absorption but it is negligibly low (below approximately 0,01). In both cases the loading with ferrous sulphate caused a significant increase of the absorption at wavelengths lower than 300 nm. ‘The changes in the absorption of the membrane B occurring during a 4CP degradation experiment are depicted in Figure 3. After the first 5 minutes the greatest change in the absorption curve took place. The absorption maximum at 240 nm increased to a value > 2,5 and changed into a broad band absorption. In addition a second maximum at 370 nm appeared. In the next 175 minutes this second maximum broadened and was red-shifted. During the last 120 minutes of degradation procedure the spectra did not show any changes. At the end of a run a change in colour from colourless to reddish-brown was observed. The course of the absorption spectra in case of membrane A showed the same trend (data not shown). Absorption [-] Wavelength [nm] Figure 3 Changes of membrane B during a 4CP degradation experiment performed as described in Section 2.2. 3.2 Results of 4CP degradation experiments ‘To examine if an increase of membrane area improves the degree of degradation, run7 (70 cm*), run8 (100 cm?) and run9 (2*100 cm) were performed using ferrous ion loaded membrane B. The results are shown graphically in Figure 4 and in Table 2. The increase of area in case of run7/run8 was in the order of 45% (one layer system) and in case of run8/run9 in the order of 100% (two layer system). Considering the blank experiment (runl2, unloaded membrane B, 70 cm*) TOC reduction increased by 13% and 71%, respectively. Determination of iron yielded values below 1 ppm Fe and the chloride content increased continuously over a period of 240 minutes to 100% of stoichiometry.2320 TOC /TOCO [-} =run 7 (70cm) —— = un 8 (100em*) run 9 (2*100cm?) ——u 12 (blank, 70cm?) 7 —= ° 60 120 130 240 300 Time of irradiation [min] ——$—____,__ Figure 4 Comparison of different areas and different loadings (see Table 2) with respect to TOC reduction performed with membrane B (Cyacp = 1,4*10° moV/L; Cano = 2,3*107 moV/L). ‘number | used area | thickness of membrane | TOC reduction in 300 Toading ofrun | [cm?] {mmj ‘minutes [%] [g iron/g membrane] T 200 O18 a2 0014 2 200 0,18 2 0.015 3 200 0,18 50,3 0,018 4 230 0,18 32,9 0,014 5 230 0418 83 0,014 6 230 0,18 28,7 0,014 7 70 0,43 18,5 0,012 8 100 043 20,1 0,010 9 | 2*100 0,43 29,9 0.011 10 | 2*100 0,43 26,3 0,006 ne | 2#100 0,43 230 0,009 2 70 0.43 63 . 13 _ 0,18 52 : ‘Table 2- Comparison of the TOC reduction achieved in 300 min irradiation time using different membranes (0,18 mm thick = membrane A and 0,43 mm thick = membrane B) with respect to area and loading (* .. blank experiment: performed with unloaded membrane B, all other experimental parameters were the same as described in Section 2.2).2321 The effect of different loadings with respect to TOC reduction are presented in Figure 5 and Table 2. The area was 24100 cm? (two layer system) in ran9, run10 and run11 and the loadings were 0,011, 0,006 and 0,009 g iron/g membrane, respectively. The decrease in loading caused a decrease in TOC reduction after an imradiation of 300 minutes. The achieved results are of good reproducibility with the deviation of +/- 2% in the first 240 minutes of irradiation increasing to a value of 5% in the last hour. In these experiments a continuous increase in chloride concentration took place. After 180 minutes of irradiation 100% of the stoichiometric chloride content was measured in solution. The dissolved oxygen curves are similar, too. Beginning with 8 mg/L at the start of irradiation followed by a continuous increase to a maximum of about 25 mg/L after 120 minutes and then a decrease of oxygen was measured. The iron determination in solution ‘was in all cases below Ippm Fe. 08 TOC /TOCO |-| ol {tt ° 60 120 180 240 300 Time of irradiation [min] Figure 5 Influence of different loadings (see Table 2) on the degradation results using membrane B (Cy4cp = 1,4#10* moV/L; Cano: = 2,3*107 moU/L; areas were in all cases 2*100 cm?) 3.3 Reuse of membranes The treatment sequence for the reuse of membranes can be described as following. First membrane A with an area of 200 cm* was prepared as described in Section 2.1 and used for a degradation experiment with an irradiation time of 300 minutes (= runl). After run] the membrane was rinsed with distilled water and then stored in distilled water (pH 6,5 +/- 0,5) over a period of 18 hours. This stored membrane was used without further treatment in the next run (= run2). After 300 minutes irradiation time the membrane was rinsed with distilled water and stirred in distilled water (pH 1,5 - 2,0) for 3 hours. This reactivation discoloured the membrane so that it was colourless as it was before runl. The next step was a reloading of the reactivated2322 ‘membrane. On this purpose the ion exchange procedure was performed once again, This reloaded membrane was used in run3. The reached loadings are listed in Table 2. In Figure 6 the achieved TOC reductions of run1, run2, run3 and run13 (blank experiment, unloaded membrane A, 70 cm?) are shown. In the course of the treatment sequence some interesting results were observed. The degree of photodegradation in runl was 42,2% and in run2 the degree deteriorated to 11,2%. In run3 a significant increase in the decomposition rate was observed. With a TOC reduction of 50,3% in run3 the result could be improved compared to run1. The experiments were performed at a pH value of 7,5 ++1- 0,5. In this pH region hydrogen carbonate is with about 90% the main species present in the equilibrium between carbon dioxide and hydrogen carbonate (eq.3). On the one hand hydrogen carbonate is stripped out only in small amounts and therefore enriched in the reaction volume and also adsorbed on the membrane surface. On the other hand it is an efficient scavenger for hydroxyl radicals in solution [15,16]. With this, treatment sequence we demonstrated that the membrane could be reused and that it is resistant to ageing. In all cases the measured iron concentration was below 2 ppm Fe and within 120 minutes of irradiation time the stoichiometric amount of chloride was detected. CO, + HO © (i,CO,) © HCO; + HY @) TOC /TOCOF-] Time of irradiation [min] Figure 6 Regeneration cycle performed with experiments done with membrane A aace = 1.4#10° moVL; Coynon = 2,3*107 moV/L; areas were 200 em? for runt, run? and run3, in case of run13 the area was 70 cm’).2323 4 Conclusion Combination of an AOP with biological treatment is a promising altemative because one can take the advantages of both methods and get as result a potent wastewater purification method. The advantages of the Photo-Fenton method as the oxidative pre-treatment step are cheapness, efficiency especially if aromatic compounds should be destroyed, low investment costs, solar light driven reaction and only harmless process products. The advantages of the biological treatment are the well know cheapness and efficiency if aliphatic compounds should be oxidised. Before its application to a wide range of industrial effluents, the disadvantage of the Photo-Fenton method, the need for acidification, has to be solved. The change in the working pH value from about 3 to a neutral pH cause a precipitation of iron as hydroxide. Due to this shift of the reaction mechanism from homogenous to heterogeneous a loss of efficiency within the Photo-Fenton reaction occurs. In the literature different possibilities for heterogeneous Photo-Fenton treatment of wastewater by using zero valent iron [17], iron oxide [18,19,11,20} and iron loaded zeolith [21,22,23] are mentioned. In this work immobilisation of iron ions on Nafion® membrane has been tested. This new photocatalyst used in the Photo-Fenton method showed a high efficiency. In addition it was demonstrated that the thickness of the membrane has no great effect on the achieved degradation results but increasing the area improves the TOC reduction. Reusing of the membrane after a treatment sequence described in this ‘work is also possible. Optimisation of this novel method is currently under work. 5 Acknowledgement The authors wish to thank the Austrian Energy & Environment, the Hochschuljubilaumsstiftung der Stadt Wien and the Forschungsférderungsfond der gewerblichen Wirtschaft for their support. 6 References [1] J. H. Carey, An introduction to AOP’s for destruction of organics in wastewater, Proc. Symp. Adv. Paper No 1, 13 pp. Oxid. Processes Treat. Contam. Water Air, Wastewater Technol. Cent. Burlington, Ontario (1990) [2] ©. Legrini, E. Oliveros, A. M. Braun, Photochemical processes for water treatment, Chem. Rev. 93, 671-689 (1993), 13] _J. Prousek, Advanced oxidation processes for water treatment. Chemical processes, Chem. Listy 90(4), 229-237 (1996). [4] J. Bandara, V. Nadtochenko, J. Kiwi, C. 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