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    1996_Wet oxidation of phenol by hydrogen peroxide using heterogeneous catalysis Fe-ZSM-5-a promising catalyst_Fajerwerg

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    1996_Wet oxidation of phenol by hydrogen peroxide using heterogeneous catalysis Fe-ZSM-5-a promising catalyst_Fajerwerg

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    1996 - Wet Oxidation of Phenol by Hydrogen Peroxide Using Heterogeneous Catalysis Fe-ZSM-5-a Promising Catalyst - Fajerwerg

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    1996_Wet oxidation of phenol by hydrogen peroxide using heterogeneous catalysis Fe-ZSM-5-a promising catalyst_Fajerwerg

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    APPLIED CATALYSIS, iv Applied Catalysis B: Environmental 10 (1996) L229-L235 Letter Wet oxidation of phenol by hydrogen peroxide using heterogeneous catalysis Fe-ZSM-S: a promising catalyst K. Fajerwerg, H. Debellefontaine * Laboratoire d'Ingénierie des Procédés de l'Environnement, Département de Génie des Procédés Industrials, Instrut National des Sciences Appliquées, Complexe Scientifique de Ranguell, 31077 Toulowse Cedex, France Received 24 November 1995; revised 13 March 1996; accepted 1 April 1996 Abstract This leter presents an original approach to the treatment of phenolic aqueous wastes using H,0, with heterogeneous catalysts. The experimental results indicate that the system using Fe-ZSM-S zeolite with MFI structure is promising since it allows total elimination of phenol and significant total organic carbon (TOC) removal under mild working conditions. Moreover, Fe-ZSM-S remains active after successive runs. Compared with processes using homogeneous catalysis, the possibilty of induced pollution caused by the metal ions in the solution is avoided Keywords: Wastewater; Oxidation; Hydrogen peroxide; Phenol; Heterogeneous catalysis; Fe-ZSM-5 1, Introduction Nowadays, phenol is one of the most prevalent chemical pollutants from industry. It has become a significant environmental contaminant, toxic and difficult to remove and the problems associated with phenolic wastewater treatment have become important [1]. Oxidation techniques, through which the contaminating substance is converted into carbon dioxide and water, are very suitable for the treatment of such wastewater containing organic pollutants. For years, engineers have relied on a number of processes to make industrial wastewater fit for discharge [2-4]. Recently, hydrogen peroxide treatment has emerged as a viable altemative. It does not form any harmful or intrusive by-products and it is an ecologically ‘clean’ and non-toxic chemical [5]. Corresponding author. Tel: (4-33-61) 35 97 61; fax: (+33-61) 55 97 60; e-mail: debelle @insotlse.insa- Used (0926-3373 /96 /$15.00 Copyright © 1996 Elsevier Science B.V. All rights reserved. PIT $0326-3373(96)00041-0 1230 K. Fajerwerg, H. Debellefontaine / Applied Catalysis B: Environmental 10 (1996) 1229-1235 However, the methods for phenolic wastewater treatment with hydrogen peroxide are mostly based on homogeneous catalysis by metal ions (Fe™ and others) [6-8]. In the usual Fenton-type reaction using hydrogen peroxide, the key step is the formation of hydroxyl radicals (HO*) from HO, and Fe". These are known to be responsible for oxidising the organic material RH present in the wastewater, yielding Fe™ and R’. But, the use of metallic salts as catalysts induces an additional pollution. From this, it was anticipated that the use of heterogeneous catalysis would be a good alternative. Earlier studies reported in the literature deal mainly with hydroxylation of phenol [9-11], whereas complete wet oxidation of the latter using a heterogeneous catalyst in the aqueous phase with HO, opens up a new field of investigations. ‘The aim of this study was double: firstly, to find a heterogeneous catalyst that will act efficiently for phenol degradation by promoting HO, decomposition to HO’ radicals without producing inactive molecular oxygen. Secondly, in order to avoid any additional pollution, to minimise the concentration of transition metal ions generated in the solution during the reaction. For this purpose, a series of screening tests was conducted during which concentrations of phenol, ‘TOC and metal ions in the solution were measured. 2, Experimental 2.1. Materials Table 1 presents the various heterogeneous catalysts used for the screening tests. The typical particle size was about 1 ym (powder catalysts). Samples from the laboratory were synthesised by classical impregnation or by ion-ex- change methods. The metal content of the various catalysts were taken as indicated, without specific determination during this study. 2.2, Reactor and procedure Experiments were carried out in a completely stirred glass reactor equipped with a condenser and a magnetic stirrer. This reactor has a usable volume of 150 cm’ (screening tests) or 350 cm? (further tests). Blank tests, conducted with H,,O, and phenol indicated that such a glass material eliminated catalytic effects of the wall surface, which would have occurred with a metallic reactor. The amount of HO, necessary for the reaction was continuously injected throughout the reaction period. The hydrogen peroxide stoichiomettic ratio is defined as the actual amount of peroxide used compared to the one theoretically necessary during stoichiometric oxidation of the organics to carbon dioxide and water. K, Fajerwerg, H. Debellefontaine / Applied Catalysis B: Environmental 10 (2996) 1229-1235 L231 ‘Table List of heterogeneous catalysts used Reference Usval name Nature of ‘Active Proportion number catalyst metal the active (vt) T Fe,(PO,)a, 84,0 Phosphate Fe 3 2 FePO, Phosphate re 371 3 RbFeP,O; Phosphate Fe 18 4 KFeP,O; Phosphate R 21 5 NagFe,Sig03(0M); Silieate Fe 32 6 H-Fe-silica Silica Be 09 7 Fe-aerosil 200 Silica * Fe Ls 8 FeCuMn-2erosi-200 Silica * FeCuMn — 125,2.5,1.25 9 Fe:CuMn-SiO,~Al,05 FeCuMn — 1.25,2.5,1.25 10 Ts. ti 1s nL Fe-ZSM-5 Fe 2 2 Cu-¥Nal cu 2 3 Cu-¥Na G 5 4 (CusMin-YNa Cu, Mr 462 Is Fo,0; Fe 0 * Ton-exchange method. * Imnpregnation method. © Hydrothermal method. 2.3. Analysis in solution The oxidation reaction involves a decrease in the total organic carbon (TOC) value. Total organic carbon was measured with a Bioritech-700 analyser. A sample is completely oxidised to carbon dioxide using a large excess of sodium persulphate, then the amount of carbon dioxide obtained is found by IR determination. The phenol titration was performed by HPLC using a Sarasep Car-H stainless column (30 cm 7.8 mm) packed with a cationic resin, A pre-column (Sarasep Car-H, 5 cm) was used to prevent clogging of the main column. The column was attached to a chromatograh (Spectra Physics 8800) fitted with a UV detector (UV SP 200) and used at 55°C. The eluent was 2 water solution of sulphuric acid (0.01 N). The concentration of the various metal ions in the solution were determined by Atomic Absorption Spectroscopy (Perkin Elmer-380 instrument). HO, remaining in the solution during the reaction was detected through titration with Na,SO, with an excess of KI in an acidic medium, 3, Results and discussion 3.1. Screening tests Table 2 presents the results of the degradation of a phenol solution (6.9 - 10~? M, corresponding to 5 g carbon/dm?) at 70°C using various catalysts (0.35 123K. Fajerwerg, H. Debellefontaine / Applied Catalysis B: Environmental 10 (1996) £229-L235 ‘Table 2 Oxidation of phenol by various heterogeneous catalysts, TOCipiraq, 69:10? M; catalyst, 035 g/dm?s hydrogen peroxide stoichiometric ratio, 1.5; initial pH = 5; P, 10° Pa; reaction time, 180 min; temperature, 0c Reference _‘% TOCremoval %H,0,decomposition Metal concentration in the solution (ppm) 180min 90 min 180 min 2 rn 2 EF a cu. B 19 29 37 “a cu) 4 o 70 88 99 Cu (16), Mn @) 8 a 2604 33 38 Fe(4), Cu(10), Mn (3.5) 9 SI a 4” 50 Fe G4), Cu (10), Mn (2.5) 7 35 a 30 46 Fe() 2 40, 3 R n Fe (32) i 45 SI 4 s4 Fe(27) n a 2 35 9 Fe) 6 0 a7 2 a Fe(i) 10 0 0 18 18 15 8 2 1s 19 Fe(2) 4 35 45 20 a Fe(<1) 5 25 w 4 3 Fe(<1) 3 5 u 10 10 Fe(<1) g/dm*), H,O, (stoichiometric ratio = 1.5) was continuously injected into the reactor over the reaction period. Initial pH values were close to 5. However, the pH was not controlled, the final values were usually between 1.5 and 3 because of the apparition of carboxylic acids as products of phenol degradation [2]. The results indicate that three categories of catalysts can be distinguished: in the first one, catalysts are efficient with respect to HO, decomposition and phenol degradation in TOC values. Unfortunately, for some of these catalysts (nos. 1, 2, 8, 9, 13 and 14) the amount of metallic cations leached can be important. The second one promotes HO, decomposition whereas TOC values do not decrease significantly. The third one has a weak catalytic activity both in H,O, decompo- sition and in TOC removal. So, only catalysts from the first category seem to be suitable for the removal of phenol from aqueous solutions. 3.2. Final selection tests High H,0, decomposition and decrease in TOC values are necessary, but not sufficient, for a catalyst to be considered as efficient. The presence of metallic cations in the solution, which will cause additional pollution, has to be avoided. For some catalysts of the first category (nos. 1, 2, 8, 9 and 14), a homogeneous K. Fajerwers, H. Debellefontaine / Applied Catalysis B: Enuironmental 10 (1996) 1229-1235 L233 of Fel fons, dependence on the pF, TOCipygane 69°10? Mi; catalyst, 0.35 g/ém*; reaction time, 180 min; temperature, 70°C: hydrogen peroxide stoichiometric ratio, 15; P, 10° Pa Caulyst %T0C -% HO; ‘ephenol_ ‘Metal concentration pit removal decomposition conversion __i the solution (ppm) 180 min 0 min min 180 min eros 200——«7 3 0 3 25 ZSM-5 21 28 7 7 25 Fe-aerosil 200 19 30 6 5 35 Fe-ZSM-5 0 7 81 <1 35 FeZSMS 85 20 64

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