ent 8a ADE Save, SON 86-7522 Gas phase partial oxidation of toluene on a vanadium/AI,0,-TiO, catalyst A. Bottino', G. Capannelli', A. Comite!, R. Di Felice? "Dipartimento di Chimica ¢ Chimica Industriale, Universita di Genova Via Dodecaneso 31, I-16146 Genova 2 Dipartimento di Ingegneria Chimica e di Processo "G. Bonino", Universita di Genova, Via Opera Pia 15, I-16145 Genova ‘The gas phase partial oxidation of toluene was investigated on a V/AhOs-TiQ} catalyst The AlOy-TiO; support was prepared using the sol-gel technique. The vanadium deposition influenced the porosimetric properties ofthe support. The developed catalyst ives a high toluene conversion and a high selectivity to benzoic acid. 1. Introduction Benzoic acid and benzaldehyde are chemical intermediates of great relevance in the chemical industry, for example benzoic acid can be used to prepare ecaprolactam. Benzaldehydeis used as intermediate in the dye and perfume industry and asa solvent in resins and oils. The main industrial route to produce these compounds isthe Tigsid phase oxidation of toluene, but many other compounds are formed during the process and the successive separation operations significantly contribute tothe total cost ofthe final products (Maki and Suzuki, 1985, pp 555-559). ‘Another way 10 oblain benzoic acid and benzaldehyde is through the gas phase oxidation of tole. Using a gas phase process the separation of the products is simpler fac example by a cooling because some products are solid (i.e. benzoie acd), others liquid encaldheyde) and others gascous (iert gas and combustion products), Gas phase oxidation as not received attention since ealy patents were passed, since the presence of combustion reactions lead to unsatisfactory yields of intermediate products {Dunker, 1966, p 420-430), The 8s phase oxidation of toluene has been recently e- considered with renewed interest Greybowska-Swieskos (1997) reviewing the Vania catalyst inthe partial oxidation of alkylaromatcs reports this kind of catalysis effective forthe conversion of xylenes, but inthe case of toluene gives low selectivity to benzoic acid. Bulushev et al. (2001) indicates thatthe Viana eatalyst can suffer frm a deactivation problem due the deposition of coke. Isis well-known that vanadium on titania can be present as stable monolayer (Bond, 1997) Nevertheless commeril titania has a very low specific surface area (10-7Onf/g). Indeed, alumina can be obtained with elevated specific surface areas and it has excellent mechanical properties nevertheless vanadium on alumina bas low activity inthe para oxidation of toluene. We tested the partial oxidation of toluene on a V/AKOs-TiO, catalyst, The ALOy-TiOs support was obtained by the sol gel technique and vanadium was deposited on it through the adsorption teeaniqu inorder to limit the formation of bulk Vs0s,2, Experimental 2.1 Catalyst preparation ‘The AhOy-T10; support was prepared using the sol-gel technique, Figure 1 shows the sequence of the principal operations involved. The bobemite and the titanium based sols ‘were independently prepared and then mixed in order to have singe sol with equimolar concentrations of titanium and aluminium. The AlO-TiO, powders were obtained by 2 0 ° i 1203 4 56 6 EDX spot Figure 2. Catalytic powder composition by EDX semi-quantitative analysis on randomly chosen points. From the porosimetric determinations, the specific surface area (BET) of the support was 257 nf/g, After the deposition of vanadium the specific surface area of the catalyst was 211 nf/g, This decrease of 17% in the specific surface area is related to a change in the pore dimension distribution as can be seen in Figure 3. For both the support and catalyst, two partially overlapped families of pore are visible. The pore distribution in the final catalyst is wider than in the support 281282 dVidlogV (crr*/g) e 92 8 83 g ° a 5 10 15 20 Pore Diameter (nm) Figure 3. Pore diameter distribution for the Al;Os-TiO; support (©) and for the catalyst (©) after the deposition of vanadium A similar effact was also observed by other authors for the deposition of vanadium on titania supports (Matralis et al., 1995). Generally the employed technique of vanadium deposition didn't have the same effect on the alumina support. At the moment we can suppose that vanadium strongly interacts with the TiO; present in the AlOs-TiO; support changing the texture of the catalyst. 3.2 Catalytic results In the operating conditions used an apparent activation energy of about 34 ki/mol was found indicating that mass transfer limitation should be negligible. ‘As can be seen from Figure 4, benzoic acid is the main product of the process. The selectivity to benzoic acid is very high at low temperature where the formation of ‘carbon oxides is negligible. Selectivity to benzaldheyde is less than 18%. By increasing the process temperature the selectivity to benzoic acid decreases and the formation of (CO; increases. At temperatures above 370°C the formation of CO becomes more {important than the formation of CO In Figure 5 the selectvity-conversion rend is reported. The selectivity to benzaldehyde passes through a maximum. The process invoives both consecutive and parallel reactions as indicated by Andersson (1986) and Bulushev et al. (2000). Selectivity to benzoic acid and conversion of toluene is very interesting when compared with those reported in literature. The V/TiO, catalyst is reported to give a selectivity to benzoic acid between 25-50% in similar condition with a similar vanadium loading (Bulushev, 2000). Moreover, some authors (Elguezabal and Cortes-Corberan, 1996) have studied the performance ofa promoted V/TiO;-SiO; catalyst forthe partial oxidation of toluene and they obtained a high selectivity to benzaldehyde, Our results suggest the bulk of titania as a support is detrimental to the selectivity, but when titania is present in the structure of another support or as a coating over another oxide the selectivity toward283, intermediate product can be enhanced. In other words, the performance of the catalyst could be due to the heterogeneous structure on nanoscale of the support. » » m0 mM) om mm Oem ° © © “erponase C0) eae) Figure 4, Selectivity to benzoic acid @), Figure 5. Selectivity to benzole acid benzaldhyde (@), CO (O) and CO; (©) ——_W), benzaldehyde (@), CO (C) and versus temperature, Total flow rate 60 CO; (O) versus toluene conversion. ml/min; Otoluene molar ratio 12 4. Conclusions The prepared catalyst is effective in the partial oxidation of toluene to benzoic acid. Benzoic acid is obtained with high selectivity and also toluene conversion was high. ‘The prepared catalyst combines the advantages of alumina (high surface area, ‘mechanical strength) with that of titania (affinity for vanadium). The presence of TiO; allows for the deposition of vanadium in high amounts without the formation of bulk ‘Vi0s which is detrimental for the selectivity. Further investigation is needed to better larfy the role of the titanium content on the catalyst performance. 5. References Andersson, S.L-T., 1986, J. Catal. 98, 138. Bond, G.C,, 1997, Appl. Catal. A, 157, 91. Bulushev, D.A., Reshetnikov, S.L., Kiwi-Minsker, L, Renken, A.,2001, Appl. Catal. A 220, 31 Bulushev, D. A., Kiwi-Minsker, L., Renken, A., 2000, Catal. Today. 57, 231 Dunker, C., 1964, Benzoic Acid, in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 3, John Wiley e Sons, New York Elguezabal, A.A., Cortes-Corberan, V., 1996, Catal. Today. 32, 268. Grzybowska-Swierkosz, B., 1997, Appl. Catal. 157, 263. Maki, T, Suzuki, Y., 1985, Benzoic Acid and Derivatives, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A3, Wiley-VCH, New York Matralis, H.K., Papadopoulou, C., Kordulis, C., Elguezabs, Cortes-Corberan, V., 1995, ‘Appl. Catal. A. 126, 365.