Radioisotopic Study of Methanol Transformation over H- and Fe-Beta Zeolites; Influence of Si/Al Ratio on Distribution of Products

É. Sarkadi-Pribóczki, N. Kumar a) , D.Yu. Murzin a) and Z. Kovács The acid-basic properties of Beta zeolite can be modified by dealumination and/or ionexchange. The wide-pore H-Beta zeolite has strong Brønsted acid sites and other chemical environment which govern adsorption and conversion of methanol to dimethyl ether and hydrocarbons during catalysis [1-2]. Partly Fe-ion-exchanged Beta i.e. Fe-H-Beta zeolite keeps this behavior to a certain extent; however, the presence of Fe ions can modify the reaction pathway. In the present work, the methanol conversion was studied over H- and Fe-Beta zeolites at two different Si/Al ratios. 11 C-methanol was used to follow-up adsorption as well as desorption of methanol and its derivates. Therefore, a radioactivity detector was integrated to the gas chromatograph for exact identification of the labelled methanol and its derivates. H-Beta and Fe-Beta zeolites were applied at two different Si/Al ratios i.e. H-Beta(25) and H-Beta(300) and Fe-H-Beta(25) and FeH-Beta (300), respectively. A glass tube fixedbed reactor was used as a closed static reactor. The 11 C-radioisotope (T1/2 =20.4 min) was produced in 11 C-labelled carbon dioxide form by cyclotron. The 11 C-methanol tracer was produced by radiochemical process [3]. The mixture of 11 C-methanol and non-radioactive methanol was then introduced into zeolite by He gas flow. The volatile products of catalytic conversion of 11 C-methanol were analyzed by radio-gas chromatography (gas chromatograph with flame ionization detector (FID) coupled on-line with a radioactivity detector). The methanol conversion rate and product selectivities to dimethyl ether, hydrocarbons (methane, C2 -C6 olefins and paraffins), formaldehyde and carbon-oxides were measured and calculated over H- and Fe-Beta zeolites at two different Si/Al ratios at 250 and 350 ◦ C. Over H-Beta(25) C2 -C6 hydrocarbons (mostly as alkanes) with high conversion rate and some dimethyl ether were detected due to presence of strong Brønsted acid sites (∼270 µmol/g). Contrary, over H-Beta(300) a negligible amount of above gas products was detected at 250 ◦ C due to less Brønsted acid sites (∼82 µmol/g). At higher temperature (350 ◦ C) the methanol conversion rate increased resulting in higher selectivity to C1 -C2 and higher olefin/paraffin product ratio over H-Beta(300) compared to H-Beta(25). Over Fe-modified Beta zeolite as a bifunctional beta zeolite the methanol conversion rate was high with high selectivity to dimethyl ether and only small amount of hydrocarbons (irrespectively of Si/Al ratios) was formed at 250 ◦ C. Nevertheless, formaldehyde as an additional product was detected at 350 ◦ C besides lower amounts of ether and hydrocarbons due to the presence of Fe-ion and reduced acidity.
a) Laboratory of Industrial Chemistry, Process Chemistry Centre, Åbo Akademi University, FIN20500 Åbo / Turku, Finland [1] Hunger M. and Horvath T., Catalysis Letters 49 (1997) 95. [2] Tsoncheva T. and Dimitrova R., Applied Catalysis A: General 225 (2002) 101. [3] Sarkadi-Pribóczki É., Kumar N., Salmi T., Kovács Z. and Murzin D. Yu., Catalysis Letters 93 (2004) 101.


bulb matrix regions nor in the hair shaft (1000-2000 in all parts). The induction of catagen transformation essentially did not change the Ca concentrations in the dermal papilla. 1000-1500. 1000-2000. we observed a remarkable increase in the outer/ inner root sheath keratinocyte layers up to 4000-8000 µg/g Ca concentration.. led to the inhibition of proliferation of HF keratinocytes as well as the induction of HF apoptosis. In this study [1] we provided detailed quantitative elemental distribution of organcultured hair follicle in anagen and catagen growth phases using ion microscopy in order to reach a better understanding of the function. In capsaicin-treated catagen HFs. the receptor for capsaicin. Kertész. Kertész et al. in anagen (control) HFs. Telek b) and T. no data are available concerning the distribution of elements in human hair follicle with various growth and cycling phases. the following concentrations were measured (given in µg/g dry weight): dermal papilla. development. Slovenia. using combined STIM and PIXE ion beam analytical techniques.5 and 2 mm. P. ref. and cyclic activity of the hair follicle. J. our findings also show that ion microscopy may serve as a fine tool to detect changes in elemental distribution related to the human hair-cycle. matrix of the bulb. The microprobe analysis was carried out at the scanning ion microprobe facilities at the ATOMKI Debrecen. OMFB00427/2006) and the Hungarian Research Fund (contract no. outer/ inner root sheath keratinocyte layers. in turn. to the best of our knowledge. Simčič a) . Bíró b) Hair follicle (HF) is an appendage organ of the skin which is of importance to the survival of mammals and still maintains significance for the human race . in press. In contrast. Szikszai. a) Jožef Stefan Institute. University of Debrecen.7. Since TRPV1 functions as a Ca-permeable channel. K063153). Ljubljana. However data on the composition of hair follicles are scarce and mostly limited to the hair shaft. Slovenia b) Department of Physiology and Cell Physiology Research Group of the H. A. However. the Ca concentration was increased mostly in those layers which possess a significant expression of TRPV1.: NIMB 54339 63 . Moreover. Acknowledgements This work was supported by the Hungarian-Slovenian Intergovernmental S & T Cooperation programme (contract no. and at the Jožef Stefan Institute.2 Ion beam microanalysis of human hair follicles Zs. Human anagen hair follicles were isolated from skin obtained from females undergoing face-lift surgery. Medical and Health Science Center. 10002000. S. Pelicon a) . the elevated Ca in the TRPV1-expressing layers suggest that the activation of TRPV1 by capsaicin resulted in a prolonged elevation of intracellular Ca-concentration which. A. but also through cosmetic and commercial considerations. In addition. hair shaft. and 4 control (anagen) hair follicles. [1] Zs.. Concentrations for most of the elements were found to be the same in the corresponding parts of the anagen and the catagen hair follicles. With respect to the distribution of Ca. Elemental distributions and absolute concentrations were determined along 5 capsaicin treated (catagen). Average elemental concentration values of the whole sample and the different morphological parts were also determined. significant differences were observed in the Ca concentration between the anagen and catagen HFs. Z.not just biologically. Cultured anagen HFs were treated by either vehicle or by 10 µM capsaicin for 5 days. Research Center for Molecular Medicine. Nuclear Instruments and Methods B. Ljubljana. ∼500. The investigated length varied between 1.