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\qj \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 \fs20\lang1040\langfe1040\cgrid\langnp1040\langfenp1040 {\b COMO, III. Workshop on Oxide Based Materials, 13-16. October 2004.}{
\par }\pard\plain \s15\qc \li567\ri565\widctlpar\tx567\aspalpha\aspnum\faauto\adjustright\rin565\lin567\itap0 \b\f4\fs24\lang1033\langfe1040\cgrid\langnp1033\langfenp1040 {\f0 
\par CATALYTIC WET PEROXIDE OXIDATION OF PHENOL OVER ZEOLITES CONTAINING COPPER
\par }\pard\plain \qc \li0\ri0\sb90\nowidctlpar\faauto\rin0\lin0\itap0 \fs20\lang1040\langfe1040\cgrid\langnp1040\langfenp1040 {\fs24\lang2057\langfe1040\langnp2057 K. Maduna}{\fs24\lang2057\langfe1040\super\langnp2057 1}{\fs24\lang2057\langfe1040\langnp2057 
, T. Granato}{\fs24\lang2057\langfe1040\super\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 , A. Katovic}{\fs24\lang2057\langfe1040\super\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 , G. Giordano}{\fs24\lang2057\langfe1040\super\langnp2057 2}{
\fs24\lang2057\langfe1040\langnp2057 
\par }\pard \qc \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\super\langnp2057 1}{\fs24\lang2057\langfe1040\langnp2057  Faculty of Chemical Engineering and Technology, University of Zagreb, Croatia
\par }{\fs24\lang2057\langfe1040\super\langnp2057 2}{\f34\fs24\lang2057\langfe1040\langnp2057  Dip. Ing. Chim. & Mat., Universit\'e0}{\fs24\lang2057\langfe1040\langnp2057  della Calabria, I-87036 Rende (CS), Italy
\par }\pard \qc \li0\ri0\sb90\nowidctlpar\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\langnp2057 
\par }\pard\plain \s1\qj \li0\ri0\keepn\widctlpar\aspalpha\aspnum\faauto\outlinelevel0\adjustright\rin0\lin0\itap0 \b\f4\fs24\lang1033\langfe1040\cgrid\langnp1033\langfenp1040 {\f0\lang2057\langfe1040\langnp2057 Introduction
\par }\pard\plain \ql \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 \fs20\lang1040\langfe1040\cgrid\langnp1040\langfenp1040 {\fs24\lang2057\langfe1040\langnp2057 
\par }\pard\plain \s16\qj \fi720\li0\ri0\widctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 \f4\fs24\lang1033\langfe1040\cgrid\langnp1033\langfenp1040 {\f0\lang2057\langfe1040\langnp2057 
One of the new emerging oxidation processes - catalytic wet peroxide oxidation (CWPO) is being studied for the use in the treatment of indus
trial wastewater. This method of waste treatment is specially appealing from the ecological standpoint due to its ability to eliminate pollutants as oppose to classical oxidation that results in turning the pollution from one form into another. The proces
s}{\f34\lang2057\langfe1040\langnp2057  is operated at mild conditions (0.1-0.5 MPa, T\u8804\'3d100 \'ba
C), and therefore with low energy requirements, with the addition of different types of catalysts. In the recent years, only a few studies dealing with the use of zeolites containing copper were reported}{\f0\lang2057\langfe1040\langnp2057 
, making this aspect of the process open for further investigations.}{\f0\lang2057\langfe1040\super\langnp2057 1,2}{\f0\lang2057\langfe1040\langnp2057 
\par }\pard \s16\qj \li0\ri0\widctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\lang2057\langfe1040\langnp2057 
It has been reported that metal bearing zeolites prepared using classical procedures show severe metal leaching, leading to side reactions catalyzed in homogeneous phase.}{\f0\lang2057\langfe1040\super\langnp2057 3}{\f0\lang2057\langfe1040\langnp2057 
 The aim of t
he present work is to study heterogeneous catalytic wet peroxide oxidation of phenol using copper bearing FAU and MFI zeolites prepared by direct hydrothermal synthesis. The effect of the presence of the inorganic cation in the zeolite structure, as well 
as leaching of the active metal component were also studied.
\par }\pard\plain \qj \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 \fs20\lang1040\langfe1040\cgrid\langnp1040\langfenp1040 {\fs24\lang2057\langfe1040\langnp2057 
\par }\pard\plain \s2\qj \li0\ri0\keepn\widctlpar\aspalpha\aspnum\faauto\outlinelevel1\adjustright\rin0\lin0\itap0 \b\f4\fs24\lang1033\langfe1040\cgrid\langnp1033\langfenp1040 {\f0\lang2057\langfe1040\langnp2057 Experimental
\par }\pard\plain \ql \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 \fs20\lang1040\langfe1040\cgrid\langnp1040\langfenp1040 {\fs24\lang2057\langfe1040\langnp2057 
\par }\pard\plain \s16\qj \fi720\li0\ri0\widctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 \f4\fs24\lang1033\langfe1040\cgrid\langnp1033\langfenp1040 {\f0\lang2057\langfe1040\langnp2057 
The starting synthesis systems for the preparation of copper bearing zeolite catalysts Cu-FAU (I) and Cu-MFI (II) were:
\par 
\par {\listtext\pard\plain\lang2057\langfe1040\langnp2057\langfenp1040 \hich\af0\dbch\af0\loch\f0 (I)\tab}}\pard\plain \qc \fi-720\li720\ri0\nowidctlpar\jclisttab\tx720\faauto\ls2\rin0\lin720\itap0 \fs20\lang1040\langfe1040\cgrid\langnp1040\langfenp1040 {
\fs24\lang2057\langfe1040\langnp2057 6 Na}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 O \endash  0.35 Al}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 O}{
\fs24\lang2057\langfe1040\sub\langnp2057 3}{\fs24\lang2057\langfe1040\langnp2057  \endash  0.3 Cu(NO}{\fs24\lang2057\langfe1040\sub\langnp2057 3}{\fs24\lang2057\langfe1040\langnp2057 )}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{
\fs24\lang2057\langfe1040\langnp2057 /0.9 H}{\fs24\lang2057\langfe1040\sub\langnp2057 3}{\fs24\lang2057\langfe1040\langnp2057 PO}{\fs24\lang2057\langfe1040\sub\langnp2057 4}{\fs24\lang2057\langfe1040\langnp2057  \endash  1 SiO}{
\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057  \endash  240 H}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 O
\par {\listtext\pard\plain\lang2057\langfe1040\langnp2057\langfenp1040 \hich\af0\dbch\af0\loch\f0 (II)\tab}0.16Na}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 O \endash  0.08TPABr \endash  0.0075Al}{
\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 O}{\fs24\lang2057\langfe1040\sub\langnp2057 3}{\fs24\lang2057\langfe1040\langnp2057  \endash  0.015Cu(NO}{\fs24\lang2057\langfe1040\sub\langnp2057 3}{
\fs24\lang2057\langfe1040\langnp2057 )}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 /0.03H}{\fs24\lang2057\langfe1040\sub\langnp2057 3}{\fs24\lang2057\langfe1040\langnp2057 PO}{\fs24\lang2057\langfe1040\sub\langnp2057 
4}{\fs24\lang2057\langfe1040\langnp2057  \endash  1SiO}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057  \endash  20H}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 O
\par }\pard \ql \li0\ri0\nowidctlpar\jclisttab\tx709\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\langnp2057 
\par }\pard \qj \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\langnp2057 The sources of materials used were: precipitated or colloidal silica, sodium aluminate, copper nitrate, phosphoric acid, organic c
ompound and distilled water. In the (II) synthesis system TPABr stays for tetrapropylammonium bromide. The samples were characterized by: powder X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic absorption spectroscopy (AAS), while the a
dsorption techniques were used for the measurement of the specific surface area.
\par Cu-Na-FAU and Cu-Na-MFI samples were treated with 1M solution of NH}{\fs24\lang2057\langfe1040\sub\langnp2057 4}{\fs24\lang2057\langfe1040\langnp2057 Cl at 80 \'b0
C for 2 hours in order to exchange the metal cation and to prepare the zeolites in the protonic form: Cu-H-FAU and Cu-H-MFI, respectively.
\par The post synthesis thermal treatment consisted in the calcination of the samples at 550\'b0C for 5 hours.
\par The catalytic tests were carried out in a 500 cm}{\fs24\lang2057\langfe1040\super\langnp2057 3 }{\fs24\lang2057\langfe1040\langnp2057 thermostated stirred batch reactor. The catalyst was introduced in the phenol aqueous solution (1 g/L) at 70 \'b0
C followed by the addition of the required amount of the hydrogen peroxide solution. The change of phenol concentration during the reaction was monitored with an UV-VIS spectrophotometer, while the concentration of the remaining H}{
\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 O}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057 
 was determined by a modified iodometric titration method. The leaching of copper during the oxidation process was determined by AAS.
\par 
\par }\pard\plain \s2\qj \li0\ri0\keepn\widctlpar\aspalpha\aspnum\faauto\outlinelevel1\adjustright\rin0\lin0\itap0 \b\f4\fs24\lang1033\langfe1040\cgrid\langnp1033\langfenp1040 {\f0\lang2057\langfe1040\langnp2057 Results and Discussion
\par }\pard\plain \ql \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 \fs20\lang1040\langfe1040\cgrid\langnp1040\langfenp1040 {\fs24\lang2057\langfe1040\langnp2057 
\par }\pard \qj \fi720\li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\langnp2057 The screening tests were performed in order to optimize the following reaction parameters: catalyst amount, H}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{
\fs24\lang2057\langfe1040\langnp2057 O}{\fs24\lang2057\langfe1040\sub\langnp2057 2}{\fs24\lang2057\langfe1040\langnp2057  concentration and reaction temperature. 
\par }\pard \qj \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\langnp2057 The obtained results put in evidence that the samples prepared by direct hydrothermal synthesis show p
romising catalytic performances. Furthermore, it was observed that the H- form of the Cu-MFI catalyst showed no catalytic activity (Fig.1) as opposed to the H- form of the Cu-FAU catalyst that exhibited higher phenol conversions (Fig.2).
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\par }}\dpx-120\dpy252\dpxsize4830\dpysize4170\dpfillfgcr255\dpfillfgcg255\dpfillfgcb255\dpfillbgcr255\dpfillbgcg255\dpfillbgcb255\dpfillpat0\dplinehollow}}}}{\fs24\lang2057\langfe1040\langnp2057 
\par 
\par 
\par 
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\par 
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\par 
\par 
\par 
\par 
\par }\pard \qc \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\langnp2057 
\par }\pard \qj \li0\ri0\sl360\slmult1\nowidctlpar\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\langnp2057 
\par 
\par Figure 1. Catalytic activity of MFI samples\tab \tab Figure 2. Catalytic activity of FAU samples
\par 
\par }\pard \qj \li0\ri0\nowidctlpar\faauto\rin0\lin0\itap0 {\fs24\lang2057\langfe1040\langnp2057 
The copper bearing zeolites prepared following the metal complex method allows preparation of materials with controlled metal loading and stable active copper species.
\par 
\par }\pard\plain \s2\qj \li0\ri0\keepn\widctlpar\aspalpha\aspnum\faauto\outlinelevel1\adjustright\rin0\lin0\itap0 \b\f4\fs24\lang1033\langfe1040\cgrid\langnp1033\langfenp1040 {\f0\lang2057\langfe1040\langnp2057 References:
\par {\listtext\pard\plain\lang2057\langfe1040\langnp2057\langfenp1040 \hich\af0\dbch\af0\loch\f0 1.\tab}}\pard\plain \qj \fi-360\li720\ri0\nowidctlpar\jclisttab\tx720\faauto\ls1\rin0\lin720\itap0 \fs20\lang1040\langfe1040\cgrid\langnp1040\langfenp1040 {
\fs24\lang2057\langfe1040\langnp2057 H. Debellefontaine, M. Chakchouk, J.N. Foussard, D. Tissot, P. Stirolo, Environmental Pollution 92 (1996) 155-164
\par {\listtext\pard\plain\lang2057\langfe1040\langnp2057\langfenp1040 \hich\af0\dbch\af0\loch\f0 2.\tab}G. Ovejero, J.L. Sotelo, F. Martinez, L. Gordo, Water Science and Technology, 44 (2001) 153-160
\par }}