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Vanadium-titanium oxides are well-known catalytic systems for the selective oxidation of different substrates, such as NH3 with NOx. Vanadia species strongly interacting with the Ti 02 and soluble bulk vanadium oxide are formed on these catalysts. Different kinds of active sites are suggested as being responsible for toluene activation and ammonia combustion.
Vanadium-titanium oxides are well-known catalytic systems for the selective oxidation of different substrates, such as NH3 with NOx. Vanadia species strongly interacting with the Ti 02 and soluble bulk vanadium oxide are formed on these catalysts. Different kinds of active sites are suggested as being responsible for toluene activation and ammonia combustion.
Vanadium-titanium oxides are well-known catalytic systems for the selective oxidation of different substrates, such as NH3 with NOx. Vanadia species strongly interacting with the Ti 02 and soluble bulk vanadium oxide are formed on these catalysts. Different kinds of active sites are suggested as being responsible for toluene activation and ammonia combustion.
Ammoxidation of Toluene to Benzonitrile on Vanadium-Titanium Oxides Catalysts Prepared by Precipitation. The Role of Catalyst Composition Patrizia Cavalli, Fabrizio Cavani, Italo Manenti, and Ferruccio Trifirb* Zst i t ut o di Tecnologie Chi mi che Speci al i , 40136 Bologna, I t al y The catalytic behavior of V205/Ti 02 catalysts prepared by the contemporaneous precipitation of vanadium and titanium oxides was tested in the reaction of toluene ammoxidation to benzonitrile. Generally, two kinds of vanadia species are formed on these catalysts: a vanadia species strongly interacting with the Ti 02 (insoluble in a basic medium) and soluble bulk vanadium oxide, which does not interact with the support. The relative amounts of the two species depend on the crystalline structure of the Ti 02. I n particular, the latter species is prevalent in V205/Ti 02 (rutile) catalysts, while the former predominates in V205/Ti 02 (anatase) catalysts. However, during reaction a re- distribution of the two species occurs, and the samples become more similar. Different kinds of active sites are suggested as being responsible for toluene activation and ammonia combustion. For a vanadia content corresponding approximately to the amount necessary for the monolayer coverage of Ti 02, higher yields in benzonitrile were obtained. The formation of an upper layer of vanadia over the Ti 02 surface causes a strong increase in ammonia combustion and therefore a decrease in the yield of benzonitrile. Vanadium-titanium oxides (V-Ti-0) are well-known catalytic systems for the selective oxidation of different substrates, both inorganic, such as NH3 with NOx (Inge- mar Odenbrand et al., 1985; Wongard and Nobe, 1984), and organic, such as toluene (van der Berg et al., 1984; van Hengstum et al., 1983a), xylenes (Cole et al., 1978; Saleh et al., 1986; Wachs et al., 1985; Wainwright and Foster, 1979), butene (Ai, 1976), and butadiene (Bond et al., 1979). Their catalytic properties in the ammoxidation of or- ganic substrates also have been investigated, especially as regards the conversion of picoline to nicotinonitrile (An- demon, 1982; Andersson and Andersson, 1985), while very little attention has been devoted to the characterization of these catalysts for the ammoxidation of alkylaromatics such as toluene or xylenes (Suvorov et al., 1972). For this kind of reaction, more suitable catalysts seem to be pure V205 or V205 supported on Al,03 (Ito and Sano, 1967; Niwa et al., 1977; Niwa and Murakami, 1982) and they have received more attention. In our opinion, V-Ti-0 catalysts should be studied in more detail in regard to the reaction of ammoxidation for the following reasons: (a) I t is known that V-Ti-0 systems are able to activate se- lectively alkylaromatic substrates, giving rise to partial oxidation products. I t has been suggested that the slow step in ammoxidation is the same as for oxidation (Brill and Finely, 1964; Hadley, 1961; Ogata and Sakanishi, 1968; Simon and Germain, 1975), and therefore it can be in- teresting to verify the suitability of this system for the ammoxidation reaction. (b) Much work has been devoted to obtaining the understanding of the interaction between vanadia and Ti 02 (Bond and Bruckman, 1981; Bond et al., 1986; Gqsior et al., 1984; Haber, 1984; Roozeboom et al., 1980; Slinkard and de Groot, 1979; Wachs et al., 1985), which plays a role greater than that of just acting as a support for the active phase. This interaction gives rise to a more active and selective catalyst than pure vanadia in the mild oxidation of o-xylene to phthalic anhydride. (c) A detailed study of the ammoxidation reaction of al- kylaromatics, involving the effect of NH3 combustion and the effect of varying the vanadia concentration in the catalyst, has not yet been made. Some authors have stated that in o-xylene oxidation it is necessary to have the anatase structure of TiOz in order 0888-58851 871 2626-0639$01.50/0 to obtain a good catalyst (Gpsior et al., 1984; Haber, 1984; Wachs et al., 1985). Many attempts have been made to explain the mechanism of the modifying action of anatase on vanadia; particularly, some authors ascribe it to the selective exposure of the (010) face of vanadia on the surface (Inomata et al., 19831, due to the epitactic match between the same planes of the two oxides (Vejux and Courtine, 1978). This causes an increase in the number of V=O bonds exposed on the surface-active sites for hydrocarbon activation (Gpsior and Machey, 1983). This effect can also enhance weakening of the vanadyl bond (Roozeboom et al., 1980; Tarama et al., 1964) and favors its reducibility (Wachs et al., 1985). On the other hand, some authors (Cole et al., 1978; van Hengstum et al., 1983a) find that the crystalline form of Ti 02 is not important in determining the activity and selectivity of the catalyst, and the only important factor is the surface area of the catalyst itself. In same cases, the rutile form of titania gives better performances than the supported vanadia (Bond et al., 1979; Slinkard and de Groot, 1979). Moreover, we do think that the way to prepare the catalyst can be very important in determining the catalytic performance. V-Ti-0 catalysts usually characterized in the literature are prepared by the impregnation technique (Bond et al., 1979; Busca et al., 1986; Roozeboom et al., 1980; van Hengstum et al., 1983b) or by the mixing of vanadium and titanium oxides, followed by heating of the mixture at high temperatures (Andersson, 1982) or by the grafting technique (Bond and Bruckman, 1981; Busca et al., 1985). The aim of this work was to carry out an in- vestigation of the catalytic properties of V-Ti-0, prepared by the coprecipitation technique, in the ammoxidation of toluene to benzonitrile and, specifically, to study the fol- lowing problems: (1) What is the optimum amount of vanadia on titania? Many authors have found that a monolayer of vanadia on titania is the necessary quantity to obtain good performances for the oxidation of o-xylene (Bond and Konig, 1982; van Hengstum et al., 1983a; Wachs et al., 1985); an excess of vanadia had practically no effect on the performance. Somewhat different results were obtained by other authors (Andersson, 1982; Andersson and Andersson, 1985) in the ammoxidation of picoline. Indeed, in the ammoxidation reaction, a third reactant, 0 1987 American Chemical Society 640 Ind. Eng. Chem. Res., Vol. 26, No. 4, 1987 ammonia, is involved, and therefore it is interesting to study the role of surface and bulk vanadia in these con- ditions. (2) What is the effect of the TiO, crystalline structure on the activity and selectivity? (3) What is the role of the different vanadia species formed on the cata- Experimental Section Preparation of the Catalysts. The catalysts were prepared by contemporaneous precipitation of vanadium and titanium oxides from a solution containing both V(1V) and Ti(1V) ions. Specifically, the V(1V) solution was prepared by reducing V205 with an oxalic acid solution, until a deep blue solution was obtained. TiC1, was partially hydrolyzed in water (pH <1 by addition of HC1). The two solutions were then mixed in the right amounts necessary to obtain the desired amount of V205 in the final catalyst. The successive coprecipitation was carried out by a hy- drolysis at T >60 "C; depending on the temperature of hydrolysis, the anatase or rutile structure can be obtained. Characterization of the Catalysts. The catalysts were characterized by means of X-ray diffraction analyses, chemical analyses, and BET surface area measurements. I t is well known (Inomata et al., 1983; Yoshida et al., 1972) that treatment of the catalysts with a basic solution (30% NH40H/H20) leads to the dissolution of vanadium oxide which is not chemically bound to the titania. This method has been successfully used recently (Busca et al., 1986) to distinguish between the different species that are formed by the wet impregnation and grafting techniques of vanadia on preformed TiO,, and the data obtained were confirmed by spectroscopic analyses. Detailed studies are in course to more thoroughly characterize the nature of the vanadia species formed in V-Ti-0 catalysts prepared by the coprecipitation technique. Following this procedure, the calcined catalyst was treated with an ammonia solution (pH =10) to dissolve the vanadium oxide not strongly interacting with the support; the remaining solid was then dissolved in hot concentrated sulfuric acid. The two so- lutions were analyzed separately, with the manganometric method, to determine the amounts of vanadium in the samples. A Carlo Erba Sorpty 1700 was used for the BET surface area measurements (one-point method). The X-ray diffraction analyses were carried out with a Philips diffractometer, using Ni-filtered Cu Kcuradiation. Catalytic Tests. Catalytic tests were carried out by using a fixed-bed flow reactor at atmospheric pressure. The reactor was a stainless steel tube (4-mm diameter, 600-mm long) placed in a copper bar and externally heated by electric resistances. The effluents, kept at 270 "C to prevent condensation, were analyzed by using two gas chromatographs on-line to the reactor. The first gas chromatograph analyzed the unconverted toluene and the benzonitrile formed; traces of other byproducts (benzene and benzaldehyde) were also detected. The column was a silicon oil DC 550, supported on Chromosorb W 80-100; the oven temperature was programmed from 80 to 220 "C (heating rate 16 deg/min). The uncondensable gases (O,, N2, CO, and C02) were an- alyzed by the second gas chromatograph, using a Carbo- sieve S column; the oven temperature was programmed from 20 to 240 "C (heating rate 8 deg/min). The catalyst was used either in the powder form (for V205/Ti02 (rutile) samples) or in a form supported on ceramic pellets (for V205/Ti02 (anatase) samples). In the former case, the particle size ranged from 0.125 to 0.250 mm, and 1 cm3 of catalyst (0.64 g) was used. In the second case, the active phase was a thin layer (60-pm thick) de- lyst? posited over the cylindrical pellets (670 by weight of active phase); 40 pellets (diameter, 4.0 mm; height, 4.1 mm) were used for each series of catalytic tests, corresponding to 0.38 g of active phase. The pellets were overlaid to constitute the catalytic bed, and a thermocouple was inserted along the channel formed by the overlaid pellets, possessing a central axial hole. In order to verify whether the use of the catalyst in the form of a thin layer supported on the pellets could lead to some differences in the catalytic behavior as compared with the conventional use in the form of powder, prelim- inary tests were made on a 2570 V205/Ti02 (anatase) sample, using it in both forms. The dependence of the selectivities on the reactant conversion are the same in the two cases. The only difference lies in the range of tem- perature of activity, which is slightly different; this dif- ference however is related to the different amounts of active phases in the two cases and to the different relative residence times. The pressure drop along the catalytic bed was in all cases lower than 0.15 kg/cm2. The absence of significant phe- nomena of bypass of the reactants was verified using H20 and N2 as gas tracers. The absence of homogeneous com- bustion of the reactants or of the products at high tem- peratures was verified. Pore diffusion was verified not to be rate limiting by varying the size of the particles (catalyst in the form of the powder). The absence of significant interparticle transport effects was verified by varying the amount of catalyst, at a constant W/ F ratio. Before catalytic tests, the catalysts were calcined in air at 400 "C and then left in the reactant mixture at the same temperature for about 10 h. After this period, the catalyst exhibits a stable catalytic behavior. Results Characterization of V205/ Ti 02 Catalysts. X-ray diffraction analyses of samples calcined at 400 "C show for the V2OS/Ti0, (rutile) samples, in addition to the lines relative to the rutile phase ( d =3.24, 2.49, 2.18, 1.69, 1.62, 1.47, 1.36 A), the most intense diffraction lines of V205 (d =4.38, 3.40,2.88 A) but only in the 25% V2OS/TiO2 (rutile) catalyst. A more detailed analysis of the maxima attributable to the rutile phase shows a shift of the reflections toward lower d values, with a parallel contraction of the cell volume and of the lattice parameter a. This indicates the formation of a substitutional solid solution of V4+in the rutile lattice (Andersson and Andersson, 1985; Bond et al., 1979); since the ionic radius of V4+is slightly smaller than that of Ti4+, a contraction of the unit cell occurs, to an extent which depends on the amount of vanadium incor- porated. In the case of the V205/Ti02 (anatase) catalysts, only the lines attributable to Ti02 can be distinguished, even at higher V20, contents (d =3.51, 2.38,1.89, 1.70, 1.66, 1.48 A). No modification of the cell volume or parameters was observed. Reported in Table I are the chemical analyses of three V205/Ti02 (rutile) samples, containing 5%, 15%, and 25% by weight V205, and in Table I1 are the analyses for three Vz05/Ti 02 (anatase) samples, containing 5%, 1070, and 25% by weight V,Ob All samples were calcined at 400 "C for 3 h before analysis. In particular the absolute amounts of soluble and insoluble vanadia are reported; also reported in the same tables are the values of surface area of the catalysts and the amount of V205 necessary to have a complete monolayer coverage of the support. These values are, of course, functions of the surface area of the supports Ind. Eng. Chem. Res., Vol. 26, No. 4, 1987 641 8 Y) 40- n % a - m- Table I. Chemical Analyses of VzO5/TiO2 (Rutile) Catalysts / i /:,./, --./ -e nominal V25 surface content, area, theoretical % w t m2/g soluble insoluble monolayere 50 49 traces 5.0 7.2 5b 49 traces 5.0 7.2 15' 68 8.4 6.6 10.0 15b 68 3.9 11.1 10.0 25" 92 13.3 11.7 13.5 25b 92 4.0 21.0 13.5 % wt Vz05 (vanadia) a After calcination. After catalytic tests. Bond and Bruck- man, 1981. Table 11. Chemical Analyses of V205/Ti02 (Anatase) Catalysts nominal v25 surface content, area, theore tical % w t m2/g soluble insoluble monolayerc 50 57 0.6 4.4 8.4 5b 57 0.9 4.1 8.4 10" 52 0.2 9.8 7.6 1 Ob 52 2.0 8.0 7.6 25" 50 3.0 22.0 7.3 25b 50 10.0 15.0 7.3 % wt V205 (vanadia) "After calcination. *After catalytic tests. 'Bond and Bruck- man, 1981. and were calculated based on the considerations made by Bond and Bruckman (1981) and by Roozeboom et al. (1980). These authors took into consideration the surface area occupied by one V02,5 species and calculated the number of these species necessary to cover a unit surface area of the support. These kinds of considerations have often been used for characterizing V2O5/TiO2 catalysts (Busca et al., 1986; Inomata et al., 1983; Roozeboom et d., 1980). The analyses of the catalysts after reaction are also reported in the same tables. The reacted samples do not show appreciable modifications in the values of surface area or in the X-ray diffraction patterns as compared to the fresh ones. Effect of Ammonia on Toluene Conversion. The dependence of benzonitrile and C0 2 productivities (the main products of toluene ammoxidation), on the NH3 partial pressure, on a catalyst containing 25% by weight Vz05 on anatase is reported in Figure 1. With amounts of ammonia up to the stoichiometric amount required for the reaction (which is not in the ratio 1:l because of the combustion of ammonia to nitrogen), the yield in benzo- nitrile is directly dependent on the ammonia partial pressure. On the contrary, the formation of COz decreases considerably with increasing amounts of ammonia in the feed. The overall conversion of toluene also decreases in the whole range of ammonia partial pressures tested, until it reaches an approximately constant value at high NH3 concentrations. At very low NH3 partial pressure, small amounts of benzaldehyde are also detected. Catalytic Activity of TiOz. Pure Ti02, prepared in the same way as the Vz05/Ti02 samples, was loaded in the reactor, both as anatase and as rutile. The yields in carbon oxides and nitrogen obtained for TiOz (rutile) as functions of the reaction temperature are reported in Figure 2. The sample showed formation of both carbon oxides and ni- trogen. Moreover, a lack in the carbon balance indicated the formation of heavy products, undetectable by gas chromatography; no trace of benzonitrile was observed. On the contrary, Ti 02 (anatase) did not show any ac- tivity in toluene or ammonia overoxidation, from 270 to \ \ 0.05 0.1 ( 0 0 ammonia part,pressure, atm. 5 Figure 1. Benzonitrile (A) and C02 productivities (0) as functions of the ammonia partial pressure at the reactor inlet; catalyst, 25% V205/Ti0, (anatase). Experimental conditions: reaction tempera- ture, 310 O C ; residence time, 1.79 s; Rtoluene). 0.0117 atm; P( 02) , 0.135 atm. -i i -- " m - 340 360 temperature, C 0 Figure 2. CO (A), COP (e), and N2 (m) yields as functions of the reaction temperature: catalyst, TiO, (rutile) (0.56 9). Experimental conditions: P(toluene), 0.0117 atm; P(NHJ , 0.075 atm; P( 02) , 0.0135 atm; residence time, 0.73 s. 0 2 4 6 8 1 0 ammonia part pressure , atm XIO* Figure 3. CO (0) and COz (0) yields from benzonitrile combustion as functions of the ammonia partial pressure at the inlet of the reactor: catalyst, Ti02 (0.56 g) as rutile (full symbols) and as anatase (open symbols). Experimental conditions: reaction temperature, 370 O C ; P(benzonitrile), 0.0125 atm; P( 02) , 0.135 atm; residence time, 0.73 s. 400 "C; only heavy products were formed. Other tests were made by feeding benzonitrile into the reactor, in the presence of oxygen and increasing amounts of ammonia (Figure 3). The benzonitrile burned on the Ti 02 surface, especially when low amounts of ammonia were present. Vz05/Ti02 (Anatase) Catalysts: Effect of Varying the Amount of Vanadium. A comparison between the catalytic behaviors of two catalysts containing different 642 Ind. Eng. Chem. Res., Vol. 26, No. 4, 1987 s . 0 0 s :i :4 temperature C Figure 4. Toluene conversion (0) and benzonitrile (A), CO (01, and COz (0) yields as functions of the reaction temperature, for the 10% Vz06/Ti02 (anatase) (full symbols) and the 25% VzO5/TiO2 (ana- tase) (open symbols) catalysta. Experimental conditions: P(toluene), 0.0117 atm; P(O,), 0.135 atm; P(NH3), 0.075 atm; residence time, 1.79 S. 3 5 60- 0 >. 40 - temperature C Fi gure 5. Nz (0) and NzO (0) yields as functions of the reaction temperature; catalysts and experimental conditions as in Figure 4. amounts of nominal Vz05 (10% and 25% by weight) on anatase is reported in Figures 4 and 5. The yields in benzonitrile and COz as functions of the reaction temperature are reported in Figure 4, while the yields in Nz and NzO are reported in Figure 5. The be- haviors of the two catalysts are very similar at low tem- peratures as regards the formation of benzonitrile. On the contrary, they exhibit different behaviors regarding the combustion of ammonia. I t can be seen that the formation of nitrogen is lower on the catalyst containing 10% Vz05 and that also the formation of NzO is shifted toward higher temperatures. Another difference lies in the range of temperatures where the product formed is stable. For the 10% Vz05/ TiOz (anatase) sample the product is stable over a wide range of temperatures (up to 380 "C), while for the 25% VZO5/TiO2 catalyst a sharper maximum in the yield is observed. The behavior of the 5% VzO5/TiO2 catalyst is shown in Figure 6. The very low number of active sites in the sample does not allow high levels of conversion to be reached. A comparison at conversions lower than 60% shows that the combustion of ammonia to Nz on this sample is lower, in correspondence to the same levels of toluene conversion. On the other hand, the selectivity is kept lower by the formation of heavy products, whose presence is not detectable by gas chromatography. In order to distinguish the role of the two species iden- tified by chemical analyses, an extraction of the vanadia which did not interact with the support was made on the spent catalyst (25% VzO5/TiO2, in the form of powder); and its catalytic activity was again verified. The catalytic behaviors of the unwashed (full lines) and washed catalysts (dotted lines) are reported in Figure 7. The latter sample temperature , C Figure 6. Toluene conversion (O), benzonitrile (A), CO ( O) , COz (W) N, (o), and NzO (A) yields, and lack of carbon balance (0) as functions of the reaction temperature; catalyst, 5% Vz06/Ti02 (anatase). Experimental conditions as in Figure 4. 100 0-0- temperature , C Fi gure 7. Toluene conversions and products yields as functions of the reaction temperature: catalyst, 25% VzO5/TiO2 (anatase) as powder (1.0 cm3, 0.639 g) (full lines) and washed 25% V2O5/TiO2 (anatase) (dotted lines). Experimental conditions: P(toluene), 0.0117 atm; P(O,), 0.135 atm; P(NH,), 0.075 atm; residence time, 0.73 s; symbols as in Figure 6. temperature , C Fi gure 8. Toluene conversion and products yields as functions of the reaction temperature: catalysts, 15% VzOS/TiOz (rutile) (full symbols) and 25% VzO5/TiO2 (rutile) (open symbols). Experimental conditions as in Figure 7; symbols as in Figure 4. exhibits the same behavior as the former one, thus showing that the vanadia not strongly interacting with the support does not have a specific role in the mechanism of the ammoxidation reaction, either in the activation and oxi- Ind. Eng. Chem. Res., Vol. 26, No. 4, 1987 643 loot P; O 3 0 0 320 340 360 380 temperature, C Figure 9. Nz (0) and N20 (0) yields as functions of the reaction temperature; catalysts and experimental conditions as in Figure 8. Figure 10. Toluene conversion and products yields as functions of the reaction temperature: catalyst, 5% VzO5/TiO2 (rutile). Exper- imental conditions as in Figure 8; symbols as in Figure 6. dation of toluene or in the oxidation of ammonia. Vz0,/TiO2 (Rutile) Catalysts: Effect of Varying the Amount of Vanadium. The yields in benzonitrile and carbon oxides from toluene and of Nz and NzO from ammonia are reported in Figures 8 and 9 as functions of the reaction temperature for two Vz05/Ti02 (rutile) cat- alysts containing 15% and 25% VzO,, respectively. Figure 10 shows the behavior of a 5% VZ0,/TiO2 catalyst. The 25% VzOs/TiOz sample is the most active in toluene conversion and shows high selectivities in benzonitrile formation (about 80% at total conversion). The 15% V205/Ti02 sample is less active but shows comparable selectivities in the benzonitrile. For the 5% VzO5/TiO2 sample, the overall toluene conversion is similar to that of the 15% VZO5/TiOz catalyst. I t can also be noted that the 5% VZ0,/TiOz catalyst shows a high for- mation, at low temperatures, of undetected heavy products, the formation of which decreases with increasing tem- perature, due to their combustion to carbon oxides. Another consideration that may be made concerns the shape of the curve representing the benzonitrile yield. In the 5% VzO5/TiO2 sample, the yield starts decreasing at 340 "C, with an increase in the formation of COz (due also to the combustion of heavy products) and CO. The 15% VZO5/TiOz sample exhibits a much wider maximum for the desired product. Only at very high temperatures does the yield start to decrease, in correspondence with the lack of ammonia in the reaction medium, due to its combustion to Nz and N20. The 25% V20,/TiOZ sample which shows the highest amount of ammonia combustion, shows a sharper maximum in benzonitrile. The 25% V205/Ti02 sample also was washed with a basic solution, to dissolve the vanadia not interacting with t A- I Figure 11. Benzonitrile (A), COz (O), and N2 (0) yields as functions of the reaction temperature: catalyst, 10% V2O6/TiO2 (anatase), undoped (full symbols) and doped with Cs (V/Cs =18/1) (open symbols). Experimental conditions as in Figure 4. the support; the catalyst showed the same degree of am- monia combustion, toluene conversion, and benzonitrile yield. Finally, some tests were made (for comparison) on a 10% Vz05/Ti02 (anatase) catalyst calcined at 560 "C in the reaction atmosphere, in order to transform the anatase into the rutile structure. The catalyst showed a consid- erable decrease in activity (the conversion was about 15% at 350 "C), while the selectivity of the catalyst remained approximately constant. Analyses of the catalyst showed that a considerable decrease in surface area (from 50 m2/g to less than 1 m2/g) occurred in correspondence with the crystalline transformation. Effect of Doping with Cesium. In order to verify whether or not doping our catalysts could lead to some enhancement in the catalytic behavior, for example, causing a variation in ammonia combustion, the 10% V2O5/TiOZ (anatase) catalyst was doped by adding CsCl during its preparation. The catalytic behavior of a 10% V20,/TiO2 (anatase) catalyst containing cesium in the amount necessary to obtain a V/Cs atomic weight ratio equal to 18:l is reported in Figure 11along with that of the undoped catalyst. I t is shown that the activity of the alkali-doped catalyst is lower and the attainment of the maximum benzonitrile yield is shifted to higher temperatures. On the contrary, no modification is observed in the ammonia combustion; the benzonitrile yield starts to decrease at the same tem- perature for the two catalysts, that is, in correspondence to the same degree of ammonia combustion. Discussion Comparison between V205/ Ti 02 (Anatase) and V205/Ti02 (Rutile) Catalysts. I t has been established in the scientific literature that a bidimensional vanadia structure is formed in VzO5/TiO2 catalysts on the surface of the TiOz (the so-called "monolayer") (Bond et al., 1986; Inomata et al., 1983; Saleh et al., 1986; Roozeboom et al., 1980). However, there is little agreement in the literature about the nature of this structure. The only certain con- sideration is that a strong interaction occurs with the centers on the Ti02 surface, leading to some kind of va- nadia species characterized by unique properties, such as higher reactivity with respect to vanadia as the bulk oxide (Niwa and Murakami, 1982; Roozeboom et al., 1980; Wachs et al., 1985). Over this monolayer coverage, both upper layers and aggregates of crystalline V205 are formed (In- omata et al., 1983; Bond et al., 1986); the latter species not directly interacting with the TiOz surface can be selectively 644 Ind. Eng. Chem. Res., Vol. 26, No. 4, 1987 dissolved by means of a washing with a basic solution (Yoshida et al., 1972). A very important consideration arising from our data is that the soluble vanadia has no catalytic activity, as shown by the tests on the washed catalysts. Therefore, all the correlations between the activity and the amount of vanadium in the catalyst must be made taking into account only the insoluble part. This is in agreement with the suggestions of some authors about the role of excess vanadia in the oxidation of o-xylene (Bond et al., 1986; Vanhove and Blanchard, 1971; van Hengstum et al., 1983a). The two series of catalysts, characterized by the different natures of the supports, have similar surface areas, in the range 50-90 m2/g. However, there are remarkable dif- ferences in the relative distribution of the two vanadia species. In particular, the amount of interacting vanadia is higher for the VzO5/TiO2 (anatase) samples, except for the 5% Vz05/Ti02 one. This is in agreement with the indications given in the scientific literature about the su- perior ability of the anatase structure in the formation of the monolayer as compared with the rutile structure (Haber, 1984; Saleh et al., 1986). This difference has been related to the presence, in the former case, of a crystallo- graphic fit between some planes of Vz05 and the growth planes of anatase (Vejux and Courtine, 1978). It is interesting, however, to compare these data with those of the samples after reaction. In both series of samples, a modification of the chemical situation occurred, with a redistribution of the two vanadia species. In par- ticular, for the V2O5/TiO2 (anatase) catalysts, the amount of soluble vanadia generally increases for the three samples during the permanence in the reaction medium, while the amount of insoluble vanadia decreases. The opposite oc- curs for the VzO5/TiO2 (rutile) samples. An explanation of the phenomenon may be obtained by comparing the amounts of the vanadium species with those corresponding to the theoretical monolayer. The values reported indicate that before reaction in the VzO5/TiO2 (rutile) samples, the amount of interacting vanadia is lower than the theoretical amount necessary for the formation of a monolayer. Moreover, it must be considered that part of the insoluble vanadia is probably present in solid solution in the rutile lattice, as indicated by the X-ray diffraction analyses. Following the indications of Bond et al. (1979) and of Andersson and Andersson (1985), the amount of vanadium in solid solution should not exceed 3-4% by weight, ex- pressed as Vz05. The opposite is true for the VzO5/TiO2 (anatase) Sam- ples. The amount of insoluble vanadia is higher, before reaction (except for the 5% VzO5/TiO2 sample), than the theoretical amount for the monolayer; work by Bond et al. (1986) and by Inomata et al. (1983) indicates the pos- sibility of forming more than one monolayer of vanadium (thus, of multilayers or towers of vanadium oxide) in V2O5/TiO2 (anatase) catalysts. I t is interesting to note that after reactions the two series of catalysts appear very similar; thus, during reaction, the weakly interacting vanadia spreads over the free rutile surface. In the case of the VzO5/TiO2 (anatase) catalysts, on the contrary, the insoluble vanadium partly segregates, forming soluble bulk Vz05. Therefore, after reaction all the samples reach a chemical situation that is a function (for the same amount of nominal V205) of the surface area and not of the crystalline structure of the TiOP More in detail, after reaction, in the case of the lowest amount of VZO5 ( 5%) , in both V205/Ti02 (anatase) and VzO,/TiOz (rutile) samples, the vanadia is overall lower than the theoretical amount for monolayer coverage; therefore, it can be thought that part of the TiOz surface remains ex- posed to the gas phase. In the case of the 10% VZO5/TiOz (anatase) and 15% VzO5/TiO2 (rutile), the amount of va- nadia which strongly interacts with the TiOz (and therefore can not be dissolved) is in both cases very near to the theoretical monolayer. Finally, for the highest Vz05-con- taining catalysts, the amount of vanadia considerably ex- ceeds the theoretical amount for monolayer formation; in particular, the amount of strongly interacting vanadium is in both cases about double that necessary to form a monolayer. The similarity of V205/Ti02 (anatase) and V2O5/TiO2 (rutile) catalysts is accompanied by a very similar catalytic behavior of the samples. A comparison between the 25% V2O5/TiOZ (anatase) and the 25% V2O5/TiOZ (rutile) catalysts can be made by comparing tests reported in Figures 7 and 8. In fact, in both cases tests were made with the same weight of active phase and by using the catalysts in the form of particles with the same dimensions. I t is seen that they both are rather selective in benzo- nitrile and exhibit a decrease in yield when the combustion of ammonia becomes relevant. A difference lies instead in the activity of the two samples. The 25% VzO5/TiO2 (rutile) catalyst is more active than the 25% VzO5/TiO2 (anatase), but this difference can be attributed to the higher surface area of the latter sample. Effect of NH3 Partial Pressure. Figure 1 shows that ammonia has an inhibiting effect over the toluene con- version. This effect can be explained by competition be- tween ammonia and the hydrocarbon for the same active sites (Cavalli et al., 1986); a similar effect also occurs in the case of paraffin ammoxidation, with a shift of the activity toward higher temperatures with respect to the oxidation when ammonia is added to the feed (Cavani et al., 1986). Another effect of adding ammonia to the feed is the very strong decrease in the products of combustion. The am- monia stabilizes the intermediate of toluene activation (which in these conditions would be otherwise burnt to carbon oxides) with the formation of benzonitrile (Cavalli et al., 1986); this product is very stable in the reaction environment, allowing high selectivities to be obtained. Effect of Varying the Amount of Vanadium. a. Pure TiOp Figures 2 and 3 show that pure TiOz possesses some activity in the toluene or ammonia conversion. In particular, both pure anatase and rutile activate toluene, giving rise to the formation of heavy products, undetect- able by gas chromatography. I t has been reported that on acid supports the formation of heavy products from aro- matic condensation can easily occur (Niwa et al., 1981). Moreover, the rutile shows activity in the combustion of toluene to carbon oxides and in the oxidation of ammonia to nitrogen. Similar activity is not shown by pure anatase. This difference between the two crystalline modifications of TiOz has also been found for other kinds of reactions (Cunningham et al., 1981; Onishi and Hamamura, 1970; Svintsova et al., 1977); it has been attributed to the greater reducibility and Lewis acidity of coordinatively unsatu- rated Ti4+ions at the rutile surface (Woning and van Santen, 1983). Finally, both supports show some activity in the combustion of benzonitrile, above all in the absence of ammonia. This seems to indicate that the acid centers on the surface of titania can activate the basic benzonitrile, causing its combustion. The presence of ammonia can decrease this phenomenon, probably through a competition with the product for the acid centers. Similarly, it has been Ind. Eng. Chem. Res., Vol. 26, No. 4, 1987 645 found that the TiOz surface is responsible for phthalic anhydride combustion in the oxidation of o-xylene (Ggsior et al., 1984; Wachs et al., 1985). b. Submonolayer Region. As indicated before, the 5% VZ0,/TiO2 (anatase) and 5% V2O5/TiO2 (rutile) sam- ples probably possess some fraction of exposed Ti 02 sur- face, because of the low amount of V205, with respect to their areas. I n agreement, both samples form heavy products. The low selectivity in benzonitrile (due to tol- uene combustion) and the relatively high ammonia com- bustion of the 5% Vz05/Ti02 (rutile) sample also are at- tributable to the exposed rutile surface. The same sample shows a decrease at high temperatures in the yield in benzonitrile. This can be due either to the exposed rutile, which has been shown to be active in the product over- oxidation, or to the combustion of the intermediate of toluene activation. The latter, in the absence of ammonia (mainly burnt to nitrogen), cannot be converted to the stable product; Figure 1 shows that at low ammonia partial pressure the main products obtained are carbon oxides. In the case of the 5% Vz05/Ti02 (anatase), the low number of active sites (a lower amount of catalyst was used) does not allow considerations to be made at high conversion. It is, however, seen that at low conversion the combustion of ammonia is particularly low; this is in agreement with the tests made on pure anatase, which was found to be inactive in this kind of reaction. c. Monolayer Region. The 10% V2O5/TiO2 (anatase) and 15% V2O5/TiO2 (rutile) catalysts have an amount of insoluble vanadia which corresponds to the theoretical monolayer coverage. Therefore, in the two cases the fraction of exposed titania surface must be very low, and no effect due to the support should be present. In agreement, no formation of heavy products is observed in the two samples, since the carbon balance is very good. Moreover, in the case of the 15% V205/Ti02 (rutile) catalyst, the oxidation of ammonia to nitrogen decreases considerably with respect to the 5% VzO5/TiO2 (rutile), along with an increase in the selectivity in benzonitrile (due to the absence of the parallel reaction of toluene com- bustion over the free rutile surface). In both samples, the low degree of ammonia overoxidation allows a wider range of temperatures where the benzonitrile can be obtained with high yields. Thus, the ammonia in the gas phase is always sufficient (except at very high temperatures) to stabilize the intermediate with the formation of benzo- nitrile. d. Supramonol ayer Region. The 25% V205/Ti02 (anatase) and 25% VZO5/TiOz (rutile) catalysts have high amounts of insoluble vanadia, about twice as much as that necessary for obtaining total monolayer coverage. It is therefore probable that some kind of structure is formed over the first coverage of the support, which also interacts chemically with the latter. The catalytic data show that both 25% Vz05/Ti02 (anatase) and 25% VzO5/TiO2 (rutile) are more active in the ammonia overoxidation to N2 and NzO than the 10% VzO5/TiO2 (anatase) and the 15% V205/Ti02 (rutile) samples, respectively. Because of the increased ammonia combustion, the range of high yield in benzonitrile becomes narrower for both of the catalysts. Moreover, while the 25% Vz05/Ti02 (rutile) is more active than the 15% V2O5/TiO2 (rutile) in toluene con- version, the 25% and 10% VzO5/TiO2 (anatase) show the same activity. It is possible to explain this different be- havior considering that the 25% V205/Ti02 (rutile) sample has a surface area higher than the 15% V2O5/TiOZ (rutile) one; the amount of vanadium constituting the first cov- Scheme I. General Network of the Reaction p NzO1N2 NH, \ Ph CHO \ heavy products - co. co, erage of the Ti 02 is also higher (Bond and Bruckman, 1981) and leads to enhanced activity. On the contrary, the 25% V205/Ti02 (anatase) sample has the same surface area as the 10% VZO5/TiOz (anatase) one, and therefore, the amount of vanadium constituting the complete support coverage is the same in the two samples. These data indicate, therefore, that the activity in tol- uene conversion is a function of the amount of vanadium oxide constituting the first TiOz coverage and, therefore, of the surface area of the sample. A common peculiarity of the 25% V2O5/TiO2 (anatase) and 25% V205/Ti02 (rutile) samples is that they both exhibit a strong increase in N2 and NzO formation with respect to the samples containing lower amounts of va- nadium. For instance, in correspondence to an increase from 20% to 60% toluene conversion at 290 "C (for the 15% V205/Ti02 (rutile) and the 25% Vz05/Ti02 (rutile) samples, respectively), there is an increase in Nz yield from about 5% to 45%. The 10% Vz05/Ti02 (anatase) and the 25% V2O5/TiO2 (anatase) catalysts possess the same ac- tivity in toluene conversion, while the latter sample is more active in the ammonia overoxidation. This means that higher vanadium oxide contents than the amounts nec- essary for the formation of the monolayer lead to the formation of specific sites for ammonia overoxidation, in both V2O5/TiO2 (anatase) and VzO5/TiO2 (rutile) catalysts. On the contrary, the amounts of vanadium oxide corre- sponding to the formation of only one layer coverage (monolayer). lead to the formation of sites responsible for toluene and ammonia selective activation. The hypothesis of the existence of two different kinds of active sites is also supported by a kinetic analysis, which showed that while toluene conversion is influenced by the ammonia partial pressure (Figure l), the ammonia overoxidation is not affected by the toluene partial pressure (Cavalli et al., 1987). Effect of Cesium. Alkali metals are known to influence the catalytic activity of V205 (Mross, 1983). Their pro- moting action was found to increase from lithium to cesium (Krupay and Ross, 1977). Also in the case of alkylaromatic ammoxidation, alkali-doped vanadium-based catalysts have been suggested to be more selective than the undoped ones (Ogata and Sakanishi, 1966). In particular, alkali metals are known to lower the surface acidity (Wainwright and Foster, 1979) and, therefore, in our case, should modify the interaction of ammonia with the catalyst. The experimental evidence is that the overoxidation of ammonia is not influenced by the addition of small amounts of cesium, while the centers that selectively ac- tivate toluene and ammonia are partially inhibited. This is a further confirmation of the existence of two different kinds of active sites in these catalysts, one for toluene and ammonia selective activation (and formation of benzo- nitrile) and one for ammonia overoxidation to N2 and N20. General Network of Reaction. The results can be finally correlated with the general network reported in Scheme I. The toluene is first activated, forming probably 646 Ind. Eng. Chem. Res., Vol. 26. No. 4, 1987 some kind of radical species (Ogata and Sakanishi, 1968; Simon and Germain, 1975; Weiss et al., 1973); this reaction is the slow step, and the intermediate is quickly converted to a first product, such as benzaldehyde or benzylamine (Cavalli et al., 1986; Andersson, 1986). The data at low ammonia concentration indicate that low yields of benzaldehyde are formed in these conditions. However, tests at very low residence times showed the formation of benzylamine, suggesting it could be the first product formed (Cavalli et al., 1986). Whichever it is, this product is then quickly converted to benzonitrile. The latter is very stable and doesnt undergo successive reac- tions of combustion; this explains the generally high se- lectivities that are obtained. Only in the case when an exposed Ti 02 surface is present on the catalyst and when there is a lack of ammonia in the gas phase can the ben- zonitrile be overoxidized to carbon oxides (Figure 3). Together with the reaction of benzonitrile formation, there is a parallel one of combustion over the reactant itself or over the intermediate. This reaction generally occurs to a low extent and becomes important only in the fol- lowing cases: (1) the presence of an exposed rutile surface in V205/Ti02 (rutile) catalysts; (2) the absence of ammonia in the gas phase. The latter phenomenon occurs when the catalyst is particularly active in the overoxidation of am- monia, thus in the presence of a rutile-free surface or with catalysts containing high amounts of vanadium oxide (higher than the one necessary for the formation of a monolayer). In these conditions, the intermediate of toluene activation (or alternatively the benzaldehyde formed) that is rather unstable in these conditions cannot react with the ammonia to form the benzonitrile and is mainly burnt to carbon oxides. Another source of decreasing selectivity is the parallel formation of heavy products, on the free TiOa surface; at high temperature, the products are burnt to carbon oxides. In conclusion, the best catalyst for this kind of reaction is the one with the amount of vanadium oxide necessary for obtaining only a monolayer coverage of Ti02, regardless of the crystalline structure of the latter. Conclusions The following considerations can be made based on the results reported. (1) The contemporaneous precipitation of vanadium and titanium oxides leads to catalysts characterized by either the anatase or rutile structures for TiO,; V205/Ti 02 (anatase) and V205/Ti02 (rutile) samples have, after calcination, similar values of surface areas, in the range 50-90 m2/g. (2) Two species of vanadia are present in the catalysts after calcination: a vanadium species that is soluble in a basic medium (weakly interacting with the support) and an insoluble vanadia, strongly interacting with Ti02. The former species is prevalent in V205/Ti02 (rutile) catalysts, while the contrary is true in VzO5/TiO2 (anatase) catalysts. In the case of V205/Ti02 (rutile) samples, a solid solution of vanadium in the rutile lattice also is formed. (3) The permanence in the reaction medium changes the relative distribution of the two species in the samples; thus, after reaction, the V20,/Ti02 (anatase) and V205/Ti02 (rutile) samples are more similar and have similar relative amounts of the two species. (4) With increasing nominal amounts of vanadia in the preparation, the quantity of the insoluble species increases, up to the formation of more than one theoretical layer coverage of the Ti 02 surface. (5) Pure TiO,, both as anatase and rutile, exhibits ac- tivity in heavy products formation and benzonitrile ov- eroxidation; rutile is also active in toluene combustion and ammonia overoxidation to Nz and N20. (6) Excess vanadium oxide, present as soluble bulk V205, is not active in toluene ammoxidation and ammonia ov- eroxidation. (7) For lower amounts of vanadium oxide, which do not lead to a complete monolayer coverage of the Ti02, the catalysts are less active in benzonitrile formation; in the case of the 5% V205/Ti02 (rutile) catalyst, the exposed rutile surface leads to a high activity in N2 formation. (8) For amounts of vanadium oxide corresponding to a monolayer coverage of TiOz, the catalysts are active and selective in benzonitrile formation, while the activity in ammonia overoxidation is relatively low; the desired product can be obtained with high yields over a wide range of temperatures. (9) For both Vz05/Ti02 (anatase) and V205/Ti02 (rutile) catalysts with amounts of vanadia higher than that nec- essary for the formation of the monolayer, a strong increase in N2 formation from NH, occurs. This leads to a decrease in the yield in benzonitrile at high temperatures, because of the instability of the intermediate of toluene activation in the absence of ammonia. (10) The catalytic behaviors of the Vz05/Ti02 (anatase) and V205/Ti02 (rutile) catalysts are very similar, sug- gesting that the crystalline structure of Ti02 is not im- portant in determining the catalytic performance. (11) The best performances in the reaction of toluene ammoxidation are therefore obtained, for both Vz05/Ti02 (anatase) and V2O5/TiOZ (rutile) catalysts, when approx- imately a monolayer coverage of the Ti02 surface is ob- tained. Acknowledgment The present work was sponsored by ENICHEM Sintesi, Italy. Registry No. PhCH,, 108-88-3; PhCN, 100-47-0; V,06, 1314-62-1; Ti02, 13463-67-7. Literature Cited Ai, M. Bull. Soc. Chem. Jpn. 1976, 49, 1328. Andersson, A. J. Catal. 1982, 76, 144. Andersson, A. J . Catal. 1986, 100, 414. Andersson, A.; Andersson, S. L. T. In Solid St at e Chemistry i n Catalysis; Grasselli, R. K., Brazdil, J . F., Eds.; ACS Symposium Series 279; American Chemical Society: Washington, DC, 1985; p 121. Bond, G. C.; Bruckman, K. Faraday Discuss. Chem. 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Received f or review December 26, 1985 Revised manuscript received September 15, 1986 Accepted November 3, 1986 Selective Aromatization of Light Paraffins on Platinum-Ion-Exchanged Gallium-Silicate Bifunctional Cat a1 ys t s Tomoyuki Inui,* Yoshinori Makino, Fumio Okazumi, Susumu Nagano, and Akira Miyamoto Depart ment of Hydrocarbon Chemi st ry, Faculty of Engineering, Kyot o Uni versi t y, Sakyo- ku, Kyot o 606, Japan Direct conversion of propane to aromatics was investigated on Ga-ion-exchanged H-ZSM-5 (Ga/ H-ZSM-5), Pt-ion-exchanged H-ZSM-5 (Pt/H-ZSM-5), gallium-silicate having the pentasil pore- opening structure (Ga-silicate), and Pt-ion-exchanged Ga-silicate (Pt/Ga-silicate). Among the catalysts, Pt/Ga-silicate exhibited the best performance; the conversion of propane and selectivity to aromatics attained 92.3% and 60.770, respectively, at 600 OC. Although Ga/H-ZSM-5 with low Ga content was active and selective for the propane aromatization, the increase in Ga content did not improve the performance. As for Ga-silicate, various amounts of Ga were incorporated in the framework of silicate crystal, and it was therefore more active and selective than the Ga/H-ZSM-5. Although Pt/H-ZSM-5 was much more active than Ga-silicate, the former catalyst was not selective for the aromatization. The Pt/Ga-silicate was also effective for the aromatization of such light paraffins as ethane, butane, and pentane. It was also found that Pt in Pt/Ga-silicate plays an important role to reduce the catalyst decay and to regenerate the decayed catalyst with air. Bi- functional roles of Pt and Ga were proposed to understand catalytic behaviors of the Pt/Gasilicate. Effective utilization of C24, light paraffins is one of the most important subjects of investigation in both chemistry and industry of hydrocarbons. Much attention has re- cently been given to a catalytic process for the direct conversion of the light paraffins to aromatic hydrocarbons such as benzene, toluene, and xylenes (e.g., Chu, 1978; Chester and Chu, 1982; Dave et al., 1982; J ahnson and Hilder, 1984; Inui and Okazumi, 1984a; Mole et al., 1985; Engelen et al., 1985; Inomata et al., 1985; Inui et al., 1986a,b). These aromatics can be utilized as a booster for the high-octane-number gasoline and are important as fundamental raw materials in petrochemical industry. It has been found that Ga- or Zn-ion-exchanged H-ZSM-5 (Ga/H-ZSM-5 or Zn/H-ZSM-5) is useful for this reaction (e.g., Chu, 1978; Chester and Chu, 1982; Dave et al., 1982; Mole et al., 1985). We have also shown that Pt-ion-ex- changed H-ZSM-5 (Pt/H-ZSM-5) is effective for the re- action (Inui and Okazumi, 1984a; Inui et al., 198613). However, further improvements of catalysts seem neces- sary to establish the process for the direct conversion of the light paraffins to aromatics. ZSM-5 is an aluminosilicate crystal having the pentasil pore-opening structure. The aluminum ingredient in ZSM-5 is responsible for the formation of strong acid sites which play active sites for various reactions. The pore structure of ZSM-5 leads to various types of shape selec- tivity reactant shape selectivity, product shape selectivity, and transition-state shape selectivity (e.g., Weisz, 1981; 08S8-5885/87/2626-0647~0~.50~0 0 1987 American Chemical Society