Você está na página 1de 2

Modified Beta Zeolites for Alkylation of Benzene Using Batch and Continuous Fixed-bed Reactors Genoveva Buelna 1, Tina

M. Nenoff 1, Mutlu Kartin1, Steven M. Thornberg 2, Ion C. Abraham 2, Deborah E. Hunka 2 1 Chem and Bio Technologies Department; 2 Chemical and Biological Sensing, Imaging and Analysis Department. Sandia National Laboratories, Albuquerque, NM 87185 USA. Introduction Alkylation reactions are significant in industry as many important commercial alkyl aromatics are produced worldwide. Among these alkylation reactions is the alkylation of benzene with propylene, which produces cumene, a petrochemical commodity produced in large quantities for use in the manufacture of phenol and acetone [1, 2]. Conventionally, cumene is manufactured using AlCl3 or phosphoric acid catalysts. However, corrosion and environmental problems arising from these conventional catalysts have impelled the use of solid acids such as zeolite-based catalysts [3, 4]. Several medium to large pore zeolites are highly effective catalysts for the reaction of alkylation of benzene to produce cumene, but suffer from rapid deactivation of the zeolite catalysts [5, 6]. In the present work, the activity of several modified H+-beta zeolites was studied in a batch reactor and the life span of the catalyst was tested in a fixed-bed reactor. Results and Discussion Benzene alkylation reactions were tested in a batch reactor at 175-250C, with 7:1 benzene:propylene molar ratio, using modified H+-beta catalysts. Baseline H+-beta catalysts (Si/Al2=25) were loaded with 1 wt.% of either Pt, La, Ga, or Ce. Platinumimpregnated beta zeolite was prepared by mixing beta zeolite with a solution of hexachloroplatinic acid. The other catalysts were prepared by ion exchange of the beta zeolite with aqueous solutions of lanthanum chloride, gallium nitrate and cerium chloride, respectively. In addition, carbonized samples were prepared by exposing (at temperature) the beta zeolite to a gaseous mixture of hydrocarbons. The catalytic activity of the modified catalysts was tested and compared with that of the unmodified H+-beta zeolite. Our early results in the batch reactor indicated that catalysts modified with Pt, Ga, and n-pentane were the most promising. These samples showed high selectivity on par with the unmodified baseline sample. The lifespan of these three catalysts in the cumene reaction was tested over extended periods of time (8 h continuous operation) using a stainless steel fixed-bed reactor at 225C, with 7:1 benzene:propylene molar ratio and WHSVpropylene = 1.6/h.

Preliminary results on the cumene yield and relative selectivity of the samples showed that all the samples deactivate with time (i.e. the unmodified beta catalyst reached a plateau at about 25% of the initial conversion after 6 h). Initial cumene yield of the studied samples, measured after 1 h of reaction, ranked in an order as follows: beta-Ga > beta unmodified > beta carbonized > beta-Pt. This order was kept for the first three hours of reaction. Following this initial period, catalysts decayed at different rates, and after 7 hrs of reaction, the cumene conversion reached a plateau in all the samples with cumene yields in the order: beta-Ga > beta-Pt > beta unmodified > beta carbonized. The strong loss in catalytic activity with increasing reaction time results from blocking of the zeolite pores by coke formation, which is affected by the introduction of metals [6-8]. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the US DOE under Contract DE-AC04-94AL85000.
References 1. U. Sridevi, B.K.B. Rao, N.C. Pradhan, S.S. Tambe, C.V. Satyanarayana and B.S. Rao, Ind. Eng. Chem. Res., 40 (2001) 3133-3138. 2. A. de Angelis, S. Amarilli, D. Berti, L. Montanari and C. Perego, J. Molec. Catal A: Chemical, 146 (1999) 37-44. 3. A. Corma, V. Martinez-soria and E. Schnoeveld, J. Catal., 192 (2000) 163-173. 4. B. Wichterlova, J. Cejka and N. Zilkova, Microporous Materials, 6 (1996) 405-414. 5. J. Ma, J.P. Shen, T. Sue and D.Z. Jiang, Chem. Res. Chin. Univ., 11 (1995)39-44. 6. S. Siffert and B.L. Su, React. Kinet. Catal. Lett., 68 (1999) 191-195. 7. S. Siffert, L. Gaillard and B.L. Su, J. Molec. Catal. A: Chemical, 153 (2000) 267-279. 8. A.R. Prandhan and B.S. Rao, Appl. Catal. A:General, 106 (1993) 143-153.