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Highly concentrated phenolic wastewater
treatment by the Photo-Fenton reaction,
mechanism study by FTIR-ATR
Article in Chemosphere · September 2001
DOI: 10.1016/S0045-6535(00)00359-3 · Source: PubMed

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Usually a phenol±formaldehyde resin is * Corresponding author Tel. only 160 l of condensation water are removed from the ®nal mixture.M. previous to the tannin formation. Perez Pe~ na Departamento de Quõmica. Gonz alez Dõaz. Polymerization 1. FTIR. catechol and hydroquinone.: +34-928-45-44-37. catechol and hydroquinone have been monitored by total organic carbon (TOC) measurements along the reaction time span. the phenol±formaldehyde resins. Mechanism. Tello Rendo n. Keywords: Photo-Fenton reaction. E. including phenol. The possibility of a Fe3‡ -Pyrogallol complex formation. During the photodegradation of highly concentrated phenol solutions. Tannin formation inhibits the complete mineralization of phenol because  OH radicals attack will produce further condensation steps and the polymer size increase.M.ulpgc. cresol and other substituted phenolic compounds are the raw materials for one of the oldest synthetic resins used in industry.3 . prepared with formaldehyde 40% by volume. These observations have been proved from the identi®cation of primary degradation products. Spain Received 24 May 2000. Lower phenol concentrations (1±10 lg/l) in freshwater produce unpleasant odour/taste during the chlorinating process. has been proposed too. Phenols are very toxic. fax: +34928-45-29-22.Chemosphere 44 (2001) 1017±1023 www. The maximum inlet concentration for a biological water treatment plant (BWTP) is 1±2 mg/l. At present. when present at high concentrations. and reduction of the corresponding dissolved organic carbon.A. Other phenolic waste sources are summarized in Table 1. Consequently. Degradation process for phenol. a global mechanism for the Photo-Fenton degradation of phenol is proposed. mechanism study by FTIR-ATR ~a. These substances. These phenolic residues contain between 600±2000 mg/l of phenol and between 500±1300 mg/l of formaldehyde. O. PII: S 0 0 4 5 .6 5 3 5 ( 0 0 ) 0 0 3 5 9 . J. Then 750 l of water is removed for each ton of ®nal product. J. Don ~a Rodrõguez *. Do~ na Rodrõguez). The complex formation involving Fe3‡ ions could be related to the observed Photo-Fenton activity decrease. these residues are diluted before been discharged to a BWTP or are incinerated (cost: 167 $/ton).es (J. J. Ó 2001 Elsevier Science Ltd. Catechol is considered to be the ®rst step for the formation of tannins. When solid formaldehyde is used. E-mail address: jmd@cicei. Universidad de Las Palmas de Gran Canaria. the tannin precipitation allows its separation from the solution by conventional ®ltration. Photodegradation. E-35017 Gran Canaria.com/locate/chemosphere Highly concentrated phenolic wastewater treatment by the Photo-Fenton reaction. the formation of dissolved and precipitate tannin has been observed.see front matter Ó 2001 Elsevier Science Ltd. in the last few years many studies have been focused to reduce phenol 0045-6535/01/$ . However. All rights reserved. All rights reserved.elsevier. Campus de Ta®ra. Introduction Phenol and its derivatives are considered one group of dangerous and hard to eliminate organic pollutants. accepted 22 August 2000 Abstract Phenol degradation by Photo-Fenton reaction has been studied in highly concentrated wastewaters and most intermediate species have been identi®ed by Fourier Transform IR-Spectroscopy with ATR device. From these results. Aran an. Herrera Meli J. This fact limits the applicability of the process for highly concentrated phenolic wastes mineralization.

has been proposed too (Sun and Pignatello. 1990.1% w/w of the total production diluted in 60 volumes of water Idem 2 and intermediate species participate. 1985a. and the Fe3‡ reduction by UV-light (Kim et al.5 N nitric acid solution. 1997. The possibility of aromatic compounds degradation mediated by carboxylic and hydroxylic groups. The global mechanism for the complete mineralization of phenol is very complex since many di€erent steps .. The dissolved organic carbon concentrations were over 0. Scheck and Frimmel.5 g/l in every experiment. Chemicals ‰ROH±FeŠ3‡ ‡ hm ! ‰RO Š ‡ H‡ ‡ Fe2‡ Other authors have indicated the possible participation of Fe3‡ by-product complexes in the Fe3‡ to Fe2‡ reduction. 1995.. ENCO) was employed as UV light source. piping Condensation water containing less than 2000 mg/l of phenols and formaldehyde Rinsing water containing less than 15. Experimental conditions for the degradation of those intermediates may not be the same for all of them. Equipments and analyses Fe2‡ ‡ H2 O2 ! OH ‡ Fe3‡ Experiments were carried out in 200 ml glass vessels. Peralta-Zamora et al. On the other hand. 1990. but its eciency is restricted to low concentrated solutions. a global mechanism for the degradation of phenol is proposed. Experimental section 2.. able to interact with a photon and generate electrons and holes that can give place to the formation of hydroxyl radicals. 1997). 1997). In this article. / Chemosphere 44 (2001) 1017±1023 Table 1 Phenolic waste sources No. lorries.1018 J. Chen et al. Sample solutions were continuously air bubbled. Ara~na et al. ships.000 mg/l 3 Phenols Phenols production Spills.. Fajerwerg et al. 1997. cleaning water concentration in wastewaters (Augugliaro et al. 1992): The reagents used were Aldrich products: phenol …99:0 ‡ %†. The reaction process has been monitored by FTIR spectroscopy.  OH (Serpone and Pelizzetti. Photocatalysis is nowadays one of the most ecient methods for unspeci®c and total mineralization of dissolved organic pollutants. without coupled dissolved organic compounds oxidation during the reduction step (Zepp et al. 1992). hydoquinone (99%)..b. the phenol degradation at high concentrations (1±5 g/l of C from phenol) by the Photo-Fenton reaction has been studied. Chemicals Process Waste description Quantity 1 Phenols and formaldehyde Phenol±formaldehyde resins 500 l/ton of phenolic resin 2 Phenols Storage tanks. Experimental conditions. equipped with an air and CO2 These complexes have been considered as possible process-accelerating species (Chen and Pignatello. This may be the reason why in many cases the complete elimination of total organic carbon (TOC) in not achieved. hydogen peroxide (33%) and dihydrated ferrous sulphate. considering the intermediates species. The pH control was maintained with 0. Mattews and McEvoy. It has been suggested that phenol is oxidized by  OH radicals. and most of the intermediate species have been identi®ed. These may be degraded to aliphatic acids and ®nally to CO2 (Okamoto et al. Many mechanisms for the phenol degradation by heterogeneous photocatalysis have been proposed. through the formation of complexes with Fe3‡ . catechol …99:0 ‡ %†. IR studies were made by a spectrophotometer FTIR model RS/1 (UNICAM). have been optimized in order to obtain a TOC reduction of about 100%. TOC was analyzed by a TOC Shimadzu 5000 A analyzer. Samples' pH was held at 3 during the whole experiment. and converted in catechol and hydroquinone.1. 1997). An 800 W UV-lamp (HPA 8068. because the FTIR technique is unable to follow the process evolution for lower concentrations due to the low signal intensity. Fe3‡ Ln ‡ hm ! Fe2‡ 2.. Tsong-Yang et al. in the Photo-Fenton reaction.2. The possibility of tannin precipitation makes this process able to detoxi®cate high phenol concentrated wastewaters by ®ltration and separation of the low toxic tannin solid waste. 1993): ‰RCO2 ±FeŠ2‡ ‡ hm ! ‰R Š ‡ CO2 ‡ Fe2‡ 0. 1989)... From these results. 2. Heterogeneous photocatalytic degradation consists of the use of semiconductors such as TiO2 or ZnO.  OH are generated by the reaction of Fe2‡ with H2 O2 .

Fig. Fig 2(a) shows the obtained spectra between 1000 and 1600 cm 1 . 3. Reference spectra for catechol and hydroquinone are also shown. after 3 h of reaction and after subtracting the initial phenol spectrum. However. 1696. respectively. The bands observed in this spectrum at 1717. 1530. An absorption shift to higher wavenumbers (1393 cm 1 ) due to O±H tension is observed. the solution became yellow±orange and the progressive appearance of a precipitate in the same color was observed. % Phenol-a degraded. Reference water was subtracted to every spectra shown in this article. 1308. indicating that it is the Fenton reaction. This solid sample showed the typical high solubility of phenolic polymers (tannin) in water. Ara~na et al.J. 1019 are only attributable to catechol and hydroquinone. Photo-Fenton reaction for phenol was studied in two samples containing 1 g/l of the pollutant. which was taking place as the initial step for the process (Peral et al. The reaction with Fe3‡ and the corresponding free Fe3‡ concentration decrease may explain the low activity observed for the photo-induced reaction. pyrogallol. 2 and 4 h. On the other hand. Initially. 0. (a) IR spectrum phenol-a sample after 3 h Photo-Fenton reaction. 1480. 3(b)). . / Chemosphere 44 (2001) 1017±1023 purge unit. This spectrum is quite similar to the tannic acid one (Fig. 1). 1557. the reaction monitoring by FTIR measurements con®rmed the progressive transformation of phenol into catechol and hydroquinone.1. This band shift may be due to the presence of other species in the solution. independent on irradiation.02 g/l of Fe2‡ and three doses of 2 g/l of H2 O2 each. 1. Spectra-tech) has been employed for the determination of water-dissolved substances. as TOC reduction. 1436. 1287 and 1229 cm 1 may be observed. were added after 0. alcohol and ketone. no important degradation. Kubelka±Munk units have been employed. 1450.. 1573. 1310. Results and discussion 3. In fact. and its low solubility in ether. (b) and (c) IR spectra reference samples ± catechol and hydroquinone. Phenol In the ®rst assay (phenol-a) a 5 g/l test solution (200 ml) was employed for the Photo-Fenton reaction. 1385 and 1100 cm 1 may be attributable to both catechol and hydroquinone. 1334. a sudden organic carbon mineralization took place. 1388. 1988). 1270 and 1020 cm 1 and those at 1230 and 1210 cm 1 Fig. The ®rst Fig. 2. 3(c) and (d)). was noticed (Fig. Four hours after the reaction started. 1986). After every H2 O2 dose addition. The literature con®rms the high reactivity of this substance with Fe3‡ (Bruneton. 3(a) shows the spectrum acquired from the precipitate obtained during the phenol degradation. An internal re¯ection device (Standard Circle Liquid Analyzer. once the catechol and hydroquinone reference spectra have been subtracted from this spectrum. remaining bands at 1393. the phenol IR bands evolution with reaction time showed the phenol degradation to other products. H2 O2 and Fe3‡ mixtures (Figs. but it did not progress with time. IR spectra were made with 128 scans using a 4 cm 1 resolution. 1196 and 1077 cm 1 have been observed in experiments made with catechol. Absorption bands at 1519. but bands at 1289. when phenol-started reaction promoted by Fe2‡ and H2 O2 .

It can be observed that ®ltering enhances TOC reduction.b): Fe2‡ ‡ H2 O2 ! Fe3‡ ‡  OH ‡ OH Since catechol and hydroquinone are primary products observed in this study for the degradation of phenol. This shows the e€ect of Fenton reaction as an initiating step (Okamoto et al. only just after H2 O2 addition at t ˆ 0 and t ˆ 2 h. The procedure for these studies is schematically shown in Tables 2 and 3.1 g/l of the compound. Ara~na et al. 3.5 g/l a precipitate showing similar chemical and spectroscopic features to that observed in phenol samples was obtained. (d) solid sample got after reaction of pyrogallol with Fe3‡ and H2 O2 .03 ± 0. sample (phenol-b) was ®ltered several times and di€erent additions of H2 O2 were made during the reaction. Time (h) ‰Fe2‡ Š …g=l† H2 O2 …g=l† 0 3 …f1c † 6 0. a strong catechol degradation may be observed.2.5.5. This can be explained by the presence of dis- Table 2 Filtering and Fe2‡ +H2 O2 successive additions treatments applied to phenol-b (1 g/l) samplea a Time (h) ‰Fe2‡ Š …g=l† H2 O2 …g=l† 0 0. IR spectrum: (a) solid sample got after Photo-Fenton study with phenol-a. 1985a. 3 h after the reaction start. it was considered interesting to carry out degradation experiments of these products. In samples with 2. 1. Fig. 0. The other sample (phenol-c) was ®ltered only once. 4.5 …f1 † 1 …f2 † 2 …f3 † 0. Fe2‡ concentration was 0.5 ± 1 1 …fn ) Solution ®ltered. As for the phenol degradation studies. (c) solid sample got after reaction of catechol with Fe3‡ and H2 O2 .01 0. Fig. / Chemosphere 44 (2001) 1017±1023 Table 3 Filtering and Fe2‡ + H2 O2 successive additions treatments applied to phenol-c (1 g/l) samplea a Fig.2 and 2 g/l of H2 O2 were added. 3. TOC degraded (%) during Photo-Fenton reaction with phenol-b …N) and phenol-c …j). 5 . 4 shows TOC reduction during these studies for samples phenol-b and phenol-c. The existence of an initial degradation …t ˆ 0†. Fig.1020 J.5 and 0. that have not been removed from the sample after successive ®ltering. before the sample irradiation is also remarkable. (b) reference tannic acid.01 ± 0. but when a degradation of about 90±95% is achieved. the process becomes slower.. 1 and 0. solved polymers.01 0. This may reveal the possible formation of polymers in catechol samples.02 2 1 1 (f1c ) Solution ®ltered. Catechol Catechol degradation experiments have been performed for solutions containing 2.

. (b) 30 min. / Chemosphere 44 (2001) 1017±1023 Fig. IR spectra from catechol sample (2. Ara~na et al. These intermediates have been identi®ed by IR spectroscopy when present at high concentrations. 0. as it has been observed in this work. 1335. In contrast with the sample of 1 g/l of TOC from catechol. 1194. as TOC reductions. 5. Fig.. These two compounds have been proposed as intermediates in studies on phenol/TiO2 -photocatalytic degradation (Okamoto et al. 1227. 1510.J. 1 g/l N) and 1 g/l hydroquinone …j†. could react with Fe3‡ giving place to a complex species. On other hand. catechol may be degraded to pyrogallol and 1. total hydroquinone degradation was achieved after 2 h. An important increment in band width and intensity is observed between 1715 and 1680 cm 1 after 30 min in reaction. (c) 2 h. 0.5 g/l) after PhotoFenton reaction: (a) 15 min. 4. 1467. for samples with 1. 1390. and 1098 cm 1 are progressively enhanced. in aqueous solutions of hydroquinone containing 2. From the previously exposed results. This set of bands can be attributable to the presence of dissolved Fe3‡ ±pyrogallol or Fe3‡ ±catechol complexes.5 g/l ppm d. 1273. Precipitates were only observed in solutions containing 2. 1021 In fact. Conclusions Fig. Hydroquinone The Photo-Fenton degradation of hydroquinone was attempted under the same conditions.1 g/l.1 g/l r.1 g/l) degradation occurs without the formation of polymers. Fig.5 g/l at di€erent reaction times. producing a diminution of the UV light penetration.5 and 1 g/l of the compound.2. From this graphic it is apparent that absorptions at 1618.5 and 0.5 g/l almost did not show any degradation. due to its resemblance to the spectra showed in Figs.4 benzenetriol. TOC degraded (%) during Photo-Fenton reaction with di€erent catechol concentrations (0. 1985a. In these conditions. 5 shows the results for the sample with 1 g/l. 3(c) and (d). 6 shows the spectrum for the sample with 2. 6. This could be due to tensions in carboxylic groups when joined to an aromatic ring or to an aliphatic group with double bonds in a positions. producing the correspondent Fe3‡ free concentration decrease and the consequent Photo-Fenton reaction activity decrease. In catechol solutions at low concentration (0. Phenol degradation by Photo-Fenton reaction begins with the formation of catechol and hydroquinone. 1573.b). 1536. high concentration of catechol and pyrogallol may produce tannin-like polymers. Catechol and pyrogallol. 1557. It may be observed that when catechol concentration is increased degradation is more dicult.5 g/l and showed the same features of those obtained for phenol and catechol. 3.3. shows degradation. The observed Photo-Fenton activity decrease for high phenol and catechol concentrations may be due to: (a) The scattering e€ect of the precipitated solid which gives place to a sharp solution darkness. the sample with 2. a global mechanism for highly concentrated phenol degradation by a Photo-Fenton reaction is proposed (Scheme 1).

W.M. Elementos de Fitoquõmica y de Farmacognosia. Pignatello. Water Sci. 1997. K. 1990. through its condensation as polymers. 231±246... Kim... Light-induced oxidation of phenol over ZnO powder. . the pretreatment of these waste produces no TOC reduction but its transformation to biodegradable substances as tannins. the formation of these tannin-like polyphenolic compounds. Once the sample dissolved TOC has been diminished long enough. this kind of substances are intermediate compounds in the pathway of the natural biodegradation of biomass wastes. 1985b. Okamoto... as the subproducts of the olive industries are not biodegradable. A. Tech. V. Global mechanism proposed for phenol high concentrated aqueous solutions degradation by the Photo-Fenton reaction. J. Tanaka. when the H2 O2 dose is increased.. during the initial times of the process. which favors complex and intermediate species degradation and the corresponding progressive generated solids disappearance. A. Chem. Yamamoto.. Water Sci.. Ara~na et al. Land®ll leachate treatment by a photoassited Fenton reaction. 35. S. 103±110. Tanaka.. A. J. 58.. the polymers formation is avoided and the process continues until the complete mineralization of the remaining toxic dissolved phenol derivatives. Heterogeneous photocatalytic decomposition of phenol over TiO2 powder. Tanaka..H.. Okamoto. H. McEvoy. J. Perrard. / Chemosphere 44 (2001) 1017±1023 Scheme 1. 1997. Foussard. The solution ®ltration eliminates the suspended solid diminishing the scattering e€ect and increasing the UV source penetration and ecacy. Role of quinone intermediates as electron shuttles in Fenton and Photoassisted Fenton oxidations of aromatic compounds. Technol.. In fact. Photochem. A. 35. without ®ltration treatment. Sikimatos.. Palmisano. Y. H. by means of this method. Mattews. J. 1997. K. Kinetics of heterogeneous photocatalytic decomposition of phenol over anatase TiO2 powder. Bruning. S. References Augugliaro. Bull. highly concentrated phenolic derivatives wastewater. Chen. 2023±2028.. Vogelpohl.. W. Wet oxidation of phenol by hydrogen peroxide: the key role of pH on the catalytic behaviour or Fe±ZSM±5.. may be interesting as part of a pretreatment wastewater treatment. Catal. Schiavello. relatively nontoxic and easily removable from the solution by simple ®ltration. 58. Soc.M. 1985a. K. 64. Bull. Tech. Yamamoto.U. (b) The Fe3‡ free concentration decrease due to complex species formation produces its relative red-ox potential variation.. H..M.. Peral. 44. 101±116. Y. R. A: Chem. A. Photocatalytic degradation of phenol in the presence of near-UV illuminated titanium dioxide. J. H2 O2 successive additions promote the  OH generation increase. Domenech... E. Itaya. 2015±2022.. Acknowledgements This work has been supported by the Consejerõa de Educaci on y Cultura del Gobierno de Canarias (Proy- ecto de Investigaci on PI1998-071A). Geissen. Tech. J.. Bruneton. the Ministerio de Educaci on y Cultura de Espa~ na (Proyecto de Investigaci on PB98-0739). Photobiol. Jpn. Zaragoza.. Debellefontaine. M. L. Environ. Rulkens. J. Itaya. Tanaka. Photobiol.. Spain. Fajerwerg.1022 J. On the other hand. Chen. J..N. 35. A: Chem. H. J. Photochem.J. 239±248. Davi.. Soc. 209±217. The proposed phenol degradation pathway by the Photo-Fenton process indicates that dissolved phenol and its toxic derivatives could be eliminated this way. 65. However.. Casado.. R. M. Sclafani. 1997. Photochemical elimination of phenol and cod in industrial waste waters. Acribia. 31. As it is well known.. 231±238. Appl. Water Sci. 1988. 1992. Furthermore. 1986. 2399±2406. S. Chem. M. These e€ects have been found to be reversible when the solution is ®ltered or. Sci. the Spanish Agency for International Cooperation (AECI) and by the Fundaci on Universitaria de Las Palmas. Jpn..R.

Serpone. 304±310. Photochem. W.J. Ara~na et al. 26. Hoigne.4-D by Fe3‡ =H2 O2 / UV. Pignatello. N. C. Chi-Chao. 27. De Moraes. Technol. Photobiol. Pelizzetti.. 1990. Zepp.H. Environ. fundamentals and applications... / Chemosphere 44 (2001) 1017±1023 Peralta-Zamora. Hydroxyl radical formation in aqueous reactions (pH 3±8) of iron (II) with hydrogen peroxide: the Photo-Fenton reaction...G. N. J. Faust.. 1993. 1992. B. Yung-Yun. 1023 Sun. 115±126.. Removal of organic pollutants by coprecipitation with metallic hydroxides and photochemical treatment. Y. Degradation of phenol and salicylic acid by ultraviolet radiation/hydrogen peroxide/ oxygen. Reyes. S. W. J. R... Scheck. 2346±2352. USA. F.K. J.. Water Res. Technol. 1989. Tsong-Yang. 1995. 29. Duran.J. A: Chem. P. W. Photocatalysis. Frimmel.. Sci. J. Environ.. 18. 55.. Sci. Technol. Wiley. Environ.. Photochemical reactions involved in the total mineralization of 2.G. 313±319.. . 461±466. 1997.