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    1997_Wet oxidation of phenol by hydrogen peroxide -the key role of pH on the catalytic behaviour of Fe-ZSM-5_Fajerwerg

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    1997_Wet oxidation of phenol by hydrogen peroxide -the key role of pH on the catalytic behaviour of Fe-ZSM-5_Fajerwerg

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    1997 - Wet Oxidation of Phenol by Hydrogen Peroxide - The Key Role of PH On The Catalytic Behaviour of Fe-ZSM-5 - Fajerwerg

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    petru apopei
    1997_Wet oxidation of phenol by hydrogen peroxide -the key role of pH on the catalytic behaviour of Fe-ZSM-5_Fajerwerg

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    Pergamon Wat SciTech, Vol 38.No 4, pp, 103-110, 197 © 1997 1AWQ Published by Elsevier Science Lid Pinte in Great Bein (o-12HST 1700 +000 PIL: $0273-1223(97)00015-2 WET OXIDATION OF PHENOL BY HYDROGEN PEROXIDE: THE KEY ROLE OF pH ON THE CATALYTIC BEHAVIOUR OF Fe-ZSM-5 K. Fajerwerg*, J. N. Foussard*, A. Perrard** and H. Debellefontaine* * Laboratoire dIngénierie des Procédés de ! Environnement, Dép. de Génie des Procédés Industrels, Institut National des Sciences Appliquées, Complexe Scientifique de Rangueil. 31077 Toulouse Cedex 4, France + Centre National de la Recherche Scienifique, Institut de Recherches sur la Catalyse, 2, Avenue Albert Einstein, 69626 Villeurbanne Cedex, France ABSTRACT This poper presents an original approach to the treatment of phenolic aqueous wastes using HiOz with Fe-ZSM-S as a heterogeneous catalyst. The Fe-ZSM-5 zeolite with MFI structure allows a total elimination of phenol and a significant total organic carbon (TOC) removal at 90°C and atmospheric pressure in a batch reactor. The studies with this Fe-ZSM-5 catalyst deal mainly with the influence of external diffusion and pH on ‘the oxidation process. It appears that the phenol degradation and the toxicity reduction, on the one hand, and the Jeaching-off of Fe(III) ions in the solution, on the other hand, depend strongly on the pH . In these conditions, an optimum value exists at pH= 5. At higher pH values, the system becomes less effective. At lower values, a significant leaching-off will induce homogeneous catalysis and the degradation of the catalyst. Generally ‘speaking, when this heterogencous catalyst is used in the presence of H:O2, the reaction rates depend on the degree of hydroxylation of the aromatic compound in contact with the catalyst. So, a chain radical mechanism could be envisaged. © 1997 IAWQ. Published by Elsevier Science Lid KEYWORDS Fe-ZSM-5, Heterogeneous catalysis, Hydrogen peroxide, Oxidation, Phenol, Wastewater, Zeolite. INTRODUCTION Many wastewater streams originating in the chemical process industries contain high concentrations of organic ‘material which can be difficult to oxidise biologically. Phenol is one of the most common and important ofthese polhtants because itis extremely toxic to the environment even at very low concentrations. Owing to its stability and solubility in water, the degradation of this compound to a safe evel is usually very difficult (Keating et al, 1978). This required concentration fim i 0.1 mg/l in process effluent water for discharge. For years, engineers have relied on various processes to make industrial wastewater « acceptable» for the environment ‘(Debellefontaine et al, 1992 ; Sanger et al, 1992 ; Tukac and Hanika, 1994). Oxidation techniques, through which the contaminating substance is converted into carbon dioxide and water, are very suitable for the 103 108 K. FAJERWERG eral, treatment of wastewater containing such an organic pollutant. However, each method has its own drawbacks. “The wet sir oxidation process needs high temperature and high pressure conditions and is therefore very energy ‘consuming. The ozonation technique is also very energy intensive during operation. Recently, hydrogen peroxide treatment bas emerged as a viable alternative. It does not form any harmful or intrusive by-products and itis an ecologically « clean » and non-toxic chemical (Plant and Jef, 1994). However, the methods for treatment of phenolic wastewater with hydrogen peroxide are mostly based on ‘homogeneous catalysis by metal ions (Al Hayek and Doré, 1982,1985 ; Hocking and Intibar, 1985). In the usual Fenton-type reaction using hydrogen peroxide H:Oz, the key step isthe formation of hydroxyl radicals HO" from HAO; and Fe(II). These are known to be responsible for oxidising the organic material RH present in the wastewater, yielding Fe(III) and R’. But, the use of metalic salts as catalysts induces additional pollution. From this, it was anticipated that the use of heterogencous catalysis would be a good altemative. Earlier studies reported in the literature deal mainly with hydroxylation of phenol (Tuel et al, 1991 ; Allin et al, 1993 ;Clerici, 1993 ; Hari Prasad Reo and Ramaswamy, 1993), whereas complete wet oxidation of the latter using a ‘heterogeneous catalyst in the aqueous phase with H:O; opens up a new field of investigation, Previous studies based on a screening test including about 25 catalysts synthesised using transition metal ions. evidenced the catalytic activity of Fe-ZSM-5 for phenol elimination by HO; (Fajerwerg and Debellefontaine, 1996) in an aqueous medium. Under the operating conditions used, the Fe-ZSM-S allows total degradation of ‘Phenol and a significant TOC removal without producing an additional pollution generated by the Fe ions in the solution. Moreover, the catalyst can be reused for successive runs. The aim of the present paper is to go deeper into the study of this catalytic process. In order to check the absence of extemal mass transfer imitations, the effect of the stirring speed and the amount of catalyst on the intial rate over Fe-ZSM-5 was tested. The selection ‘ofa suitable pH value leading to the best removal of the toxicity of the final effluent without leaching-off Fe(III) ions in the solution is discussed. METHODS Materials and catalysts Phenol (Fluka p.a. > 99%) was used without further purification. Hydrogen peroxide was 35% commercial grade. The Fe-ZSM-5 (Ratnasamy, 1983) zeolite with a MFI structure used during this study is presented in Figure 1. Figure | : Structure of the Fe-ZSM-5 zeolite. (Q) Plane representation of the structure. @) Structure of the channels. ‘Wet oxidation of phenol by hydrogen peroxide 10s Characterisation of Fe-ZSM-S5 calcined catalyst Induced coupled plasma (ICP) with a Perkin Elmer 1100 was used during the chemical analysis to determinate the Fe content. The specific area was measured by the BET method. The particle size distribution was determined by Scanning electron microscopy (SEM) with a Hitachi S800 microscope. The main characteristics are listed in Table 1. ‘Table 1 : Main characteristics of Fe-ZSM-5 catalyst. ‘Specific area (antl) 350 Fe content ‘Sie ratio (%) 2 100 Reactor and procedure Batch reactor : Oxidation tests were carried out in a glass reactor (usable volume 850 cm") equipped with ‘mechanical stirring and baffles. The use of such equipment eliminates the catalytic effects of the wall surfaces ‘which occur when a metallic reactor is used. In the course of the tests, samples of liquid were drawn off for analysis. Procedure : After beating the solution (water and phenol) up to the rated temperature, the amount of HzO2 necessary for the reaction was added instantaneously. The pH was set and controlled at the set-point value (pH + 0.1) by injecting KOH (1 M) or H,SO, (0.5 M) with peristaltic pumps connected to a pH controller. The volumes of these two reagents did not induce dilution of the reaction mixture. At the same time, the catalyst was added and thus the run was started. Oxidant ratio : The hydrogen peroxide stoichiometric ratio is defined as the actual amount of peroxide used, ‘compared to the amount necessary during a theoretical stoichiometric oxidation of the organic molecules to carbon dioxide and water. The typical value is 1.5. Analytical section Total organic carbon : 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. Phenol: The titration was performed by HPLC (Spectra Physics SP 8800) with a Zorbax C18 coburn (25cm 4 mm). The UV detector (UV SP 200) wavelength was 254 nm. The eluent was a mixture of water ‘and acetonitrile (80/20 v/v). A pre-column having the same characteristics (C18, 1 em) was used. Oxidation by-products : The titration was also performed by HPLC, with a Hamilton PRP-X 300 column (25cm x 4mm), The detector wavelength was 210 nm. A pre-cohumn having the same characteristics (Hamilton PRP-X 300, 3 cm) was used. Analyses were performed with a gradient of the mobile phase. The eluent was a mixture of acidic water (sulphuric 0.1 N) and methanol (chromatographic grade). The eluent, which had a high concentration of sulphuric acid at the beginning of the analysis, achieved the separation of carboxylic acids in the first 10 minutes ; thereafter, the increase of the proportion of methanol in the solvent allowed the aromatics to be separated. 106 K. FAIERWERG er al, ron : The concentration of Fe ions in the solution was determined by atomic absorption spectroscopy (Perkin Elmer 380). Hydrogen peraxide : The hydrogen peroxide remaining in the solution during the reaction was detected by colorimetric titration using the TiCl, method. RESULTS AND DISCUSSION Kinetics of the chemical reaction. Diffusion Vo (mmotiey*40? nok ° 200 400 © 600-800» 1000 ‘Stirring (rpm) Figure 2 : Extemal moss transfer limitation. Influence of the stirring speed. (Catalyst : 0.10 gfttre ; Temperature = 90°C). Vo (mmovisy"10* 388 8 ° on 02 08 04 Mass of catalyst (g) Figure 3: External mass transfer limitation. Dependency of the mass of catalyst on the initial rate. (Temperature : 90°C ; Stirring speed : 800 rpm) In order to observe the true chemical rate of oxidation of phenol with the Fe-ZSM-5 / H,O; system, any

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