ene Chemical Engineering Science, 1968, Vol.23, pp.537-550. Pergamon Press. Printed in Great Britain. Controlling mechanisms in benzene oxidation K, VAIDYANATHAN and L, K, DORAISWAMY Nations Chemical Laboratory, Poona &, India (inst received 27 June 1967; in revised form 10 November 1967) Abstract—The vapour-phuse oxidation of benzene has been the subject of several previous studies, ‘but the controlling mechanisms in this reaction have not been fully elucidated. In the present work, based on a scheme in which benzene is simultaneously and consecutively (through maleic anhydride) ‘oxidised to the final products of combustion (carbox dioxide and water), suitable first-order equations have been set up for the three reactions on a molybdenum-vanadium catalyst. The experimental results indicate that there isa definite shift in the controlling mechanism at about 350°C as evidenced by the change in the activation energy from about 20 kcal/g mole in the lower temperatare range to about 2 Kcall/g mole in the higher temperature range. A detailed analysis of the reaction in the highet temperature region has, however, shown that neither pore diffusion nor external mass transfer is controlling. It hs therefore been postulated that this change is probably due to a change in chemical ‘mechanism and not toa shift from the chemical toa diffusion regime. ares INTRODUCTION SEVERAL studies on the catalytic vapour-phase oxidation of benzene have been reported, but only a few of them relate to the kinetics of the ‘oxidation process. It has been suggested that the reaction proceeds through a number of inter- mediate steps including the formation (succes- sively) of phenol[2,3], hydroquinone(2, 4] and quinone[2, 4,5]. Traces vf formaldehyde and diphenyl have also been reported among the products{6]. However, for the kinetic analysis of the reaction, the following scheme has normally been employed{1, 8, 9]: () benzene +0,—!> maleic, carbon , water | anhydride dioxide (17) 3) @ | carbon , water carbon , water dioxide” (W) dioxide” (W) i) Hammar[7] has studied the oxidation of ben- zene over a number of catalysts consisting of 205 and MoO, on metallic aluminium. He has interpreted the data according to the above scheme. The rate of the first step (r,) is said to be very fast, being limited only by the mass transfer rate. The fact that the activation energy for this step was of the order of 25 kcal/g mole, which is inconsistent with mass transfer control, tas been explained by assuming that the active area of the catalyst available for the reaction is itself temperature dependent. ‘The rate of the total combustion of benzene (74) was found to be almost independent of mass transfer, the rate determining step being either re-adsorption of maleic anhydride or surface reaction. It is difficult to visualise the re-adsorp- tion of maleic anhydride as a possible controlling step since maleic anhydride is not involved in the direct total combustion of benzene to carbon dioxide and water. ‘The three kinetic steps were found by Hammar to be uninhibited first-order reactions with equal apparent activation energies. Ioffe and Lynbarskii(8] also found the oxidation velo- city of benzene to be first-order, but the activa- tion energies of the three steps were found to be unequal. At oxygen concentrations >10 per cent, the benzene oxidation was found to be independent of oxygen concentration in the ‘gas phase[8, 10]. Almost all the results reported in the literature have been presented in terms of first-order Kinetic constants for the three significant 3537steps considered. Among the few attempts to describe a plausible model is that of Hayashi and collaborators[12], who have proposed a steady-state model in which the rate of adsorp- tion of oxygen on the catalyst surface equals the rate of reaction with benzene (not adsorbed) on the surface. A similar model has been proposed by Mars and van Krevelen{13]. On the other hand, Bretton ¢7 al.{14] believe that benzene is adsorbed and reaction occurs when oxygen from the gas phase strikes the adsorbed benzene molecules. ‘The object of the present work is to examine fully the Kinetics of this complex reaction on a selected catalyst, and to elucidate the effect (if any) of mass transfer and pore diffusion. EXPERIMENTAL Apparatus A diagramatic sketch of the reactor system is shown in Fig. 1. The vaporiser (A) consisted Fig. 1, Experimental set-up. 538 K. VAIDYANATHAN apd L. K, DORAISWAMY of a narrow graduated tube with @ bulb; a porcelain bead at the neck of the bulb prevented benzene from being carried away. Metered secondary air was mixed with metered primary air saturated with benzene from the vaporiser in the mixing bulb (F). The preheater (B) was electrically heated to prevent condensation of the organic vapour. The mixed preheated streain was passed down the reactor (C) contain- ing the catalyst and heated by s fluidized bed of bauxite which in turn was heated by electrical resistance wire through a voliage stabilizer and autotransformer, The temperature in the pre- heater and reactor was measured by chromel~ alumel sliding thermocouples. The products were condensed in receivers (1D) and the tail gas dried and passed through carbon dioxide absorbers. Procedure ‘Thiophene-free benzene and air from a com- pressed air cylinder were used. A~VAPORISER B~PREHEATER C-REACTOR D-RECEIVERS FOR SOLID PREDICTS E-GAS ABSORBERS F- MIXING BULBa a ‘Controlling mechanisms in benzene oxidation ‘Air was passed (after drying) through the catalyst bed for 30-60 min prior to the intro- duction of benzene. Readings were taken only after a steady state of operation had been attained. Experiments were carried out over wide ranges of benzene to air ratio, residence time and temperatuse. The life of the catalyst was repeatedly tested and care was taken to ensure that deactivation of the catalyst was absent in all the runs. The different lots of catalyst used for varying the WIF values were taken from the same batch of the catalyst prepared, although results could be reproduced to within 1-2 per cent by using samples from different batches Product analysis Maleic anhydride was estimated by titration against standard alkali[17}. Benzoquinone was analysed by a method analogous to that sug- gested by loffe et al.[18]. This consisted in treating the solution containing benzoquinone with I> in the acid medium. The liberated 1, was then titrated against $,0,-- by an indirect method. Carbon dioxide was estimated by the conventional method of absorption in caustic bulbs. Catalyst A comprehensive review has been presented by Egloff[18] of the various catalysts used in the vapour-phase oxidation of benzene. Vanadium pentoxide in conjunction with molybdenum trioxide appears to be the most widely used catalyst In the present work a number of composi- ns (Table 1) using vanadium pentoxide and ‘Table 1. Details of catalysts employed Totaloxides Ratioof Surface Pore Catalyst content” —-V,0,t0 area (BET) volume No. (MoO, (ang) (aati) 1 4 - - 2 4 4 038 3 4 236 ol 4 25 o - 5 33 5 a molybdenum trioxide on silica gel were evaluated in order to establish the influence of the oxides composition on the kinetic parameters of the reaction. A good catalyst is obviously one which gives high values of kiki +k, and kik, which can be regarded as selectivity criteria for maleic anhydride formation. A typical method of catalyst preparation ( U4 per cent total oxides content with VO: MoO, = 1:1) is given below. 9-255 parts of ammonia meta-vandate (NH,VO,:mol.wt.117) and 8-343 parts of ammonium molybdate ((NH,)jMo;O.. 4H,0:mol.wt. 1235-95) were dissolved in 250 parts of hot 10 per cent oxalic acid solution (10 g of oxalic acid in 100 ml distilled water), To this solution 100 parts of sitica gel (carrier) were added. The mass was evaporated to almost dryness with stirring over a water bath. It was then heated in a furnace at 120-150°C. for one hour, the clusters formed broken up, activated in a mufle for 8hr at 400°C., and then sieved to the required size. In this paper only catalysts 2 and 3 have been considered as they were found to be superior to the other compositions tried (with respect to selectivity and relative cost) and comparable to the reported catalysts. A detailed evaluation of all the five compositions has been presented by Vaidyanathan [27]. The surface areas of catalysts 2 and 3 were determined by the BET method and the pore volumes by the usual displacement technique. The values obtained are recorded in Table 1 KINETIC ANALYSIS In the organisation of the experimental programme for determining the rate constants 6 the three principal reactions involved, the following ranges of the main variables were covered: Concentration of 0-61 x 10-# to 1-86 benzene x 10 atm (4-5-14 mm Hg) Time factor (W/F) Up io 400g/hrgmole ‘Temperature 310°-400°C. The contact time of the reaction has been defined in different ways, viz. as the free space available 539K, VAIDYANATHAN and L. K, DORAISWAMY in the catalyst bed divided by the volume rate of the total feed, the result being expressed in seconds. Here it is defined as the ratio W/F where W is the weight of the catalyst in g and Fis the hourly molal feed rate of benzene. It has been established conclusively by dif- ferent investigators[8, 10] that the partial pressure of oxygen has no influence on the Teaction; hence no attempt was made to vary this pressure in the present study. The experiments in this series were restricted to a catalyst of 5+ 12 B.S.S. mesh size. The effect of particle size is discussed in a subsequent section. Determination of the rate constants The reaction scheme considered may be stoichiometrically represented as follows: CyHe +10, Ab CH,0,+2C0,+2H.0 Gi C,H,0,+30, 5 4c0,+H,0 Gili CH, + #0, 6C0,43H,0. v) Dmuchovsky er al.[10] have assumed a different stoichiometry since their data were better represented (for their catalyst) by that stoi- chiometry. On the other hand, the stoichiometry shown above has been chosen as only traces of carbon monoxide were formed, and as shown later this stoichiometry represents our results remarkably well The rate equation for these reactions (based on pseudo-first-order kinetics) are: Equations (1), (2) and (3), on integration, give: Pa= pao KPa _rg-ciese— gt a eRe = Dip eg She ae eet hel mteysion yy 4. — AEP gat xle +p eae ee The value of (k,+hy), which represents the velocity constant for the total disappearance of benzene, can be obtained from the raw data by plotting Eq. (4) as log paula vs. t (i.e. WIF) Experimental data and the corresponding plots at different conditions have been presented for all the catalysts by Vaidyanathan [27]. Represen- tative data are shown in Table 2 for catalyst 2 at 350°C. and the corresponding first-order plot appears in Fig. 2. The individual values of ky, ke and k, can then be determined by one or ‘more of the following methods: (a) Equation (5) can be recast into a more convenient form[10} by multiplying both sides of the equation by pp» [exp— {kit ks)t —exp (~hyt)]. From the experimental molar ratios (py/pn) at two residence times, together with the experimentally determined constant (k,+ ky), the value of k; can be found. k, and ky can then be evaluated from simple algebraic procedures. (©) dpyfde can be evaluated for different values of t by finding the slopes of the curve of Pu vs. 1, and then k; and k, can be calculated DP © FomBa @) iB . (©) Equation (2) can be ve-written for the ar hPa kee (2) initial condition, ie. at I/F = 0, as j dpa) 7 2k, + 6ki)pa+ Aka 8 (Gt), = km ” where From the value of (dpy/dt) obtained from the plot mentioned in method (b), the value of A; can be directly determined. Thas been found that &,, ky and k, calculated 540Controlling mechanisms in benzene oxidation Table 2. Experimental ata for catalyst-2.at 380°C WIE paX10" — pyX 10" peX 10 py X10" 0 18 0-00 6.00 10 136 ost Benzene toait) 49 8 187 oe molar rato Bre 220 101 Cg = B83 10+ 31M 27 hs smole/l 286 12s 310 130 8 17 - 000 00 6 0. 0-820 0351 ee he wr ams sts molar ratio iso Ome 138 0-638 im = $:88% 10-+ 8 086s 151 os gmole?) 219 ast 479, O796 174 ose 0-000 0-000 6 OTB O82 os Sensenetoa 90 ee be toes molar ratio Jt 149 OES 0.885 0-469 ion 17. 0251.08 0538 vor 2 0685 D556 2670597125 ous Benzene o air s mourns {1259 519% 10-4 amotel by the different methods listed above agree closely (io within 5-7 per cent). These values are listed in Table 3 for the two catalysts at five different temperatures, together with the values of the activation energy. For the sake of compari- son the values obtained by Hammar{1.7] at 375°C on V,O, and MoO, over metallic alumin- jum as catalyst may be noted: k= 96x 107%, k= 4:3 X 10° and k, = 3-5 x 107? (g moles) (hr)! X{B cat)! (atmy?, (Note: Although Hammar considered the partial pressure of oxygen in defining the units of k, the reaction rate was found to be insensitive to it.) Test of the calculated values of ky, ke, ks (i) Using the values reported in Table 2, the total benzene disappearance (Eq. (4)) and the 0.6683, 0.000 0-000 0-000 0588 oat 0-282 o-182 0540 0555 O40? 0-228 0530 O72 0-508 0326 0510 0882 0-577 0373 0-495 0930 0631 40s 0-482 ror 0-616 0-439 expected conversion (o maleic anhydride (Eq. (5)) have been calculated and compared with the experimental results, as shown in Figs. 3 and 4 respectively. The agreement is good, the average deviations being 5 and 8 per cent respectively. (ii) The time required for reaching the maximum molar ratio py/py at a given tempera- ture can be determined by differentiating Eq, (5) with respect to time, setting the result to zero, and solving for #//F. Thus 1 ki aU rhe) "hy = WIP \ wax =, 8) aus Using the values of the rate constants, (WF) mex can be calculated and compared with the experimental value. (WLF)max from Eq. (8) has a value of 320, as compared with 313 obtained $41 CES. Vol 236-02d | catauyst - 2 | Ten, aso{e } BENZENE : AIR o 1:50 . er 708 %e Fig, 2, Firstorder plot for benzene disappearance (cataly$t-2). “Table 3. Rate constants and activation energies for the three Signiicamt reactions involved in Benzene ‘oxidation Catalyst 2 Catalyst 3 Temperature — — o) X10 XI XI XI XU X10 S10 04308 “0126 330 067s 430 OS 0-686 0209 330 har 24880356 1358 ars 1292-2583 O08 (ass 0477 400 13612716 dat 1513 0519 F for temperature range Se 194 196 203 BT Be Bs keallgmole For temperature range 350-400°C 29 1 19 18 Ww 22 kcal/gmoleexperimentally at 350°C. Similar agreement was obtained at other temperatures. The results obtained in the present investiga- ‘ion are consistent with those reported earlier{1] although wider ranges of the variables have been covered. However, two activation energy values for each of the rate constants were observed in the present work (Table 3), and the significance of this is discussed in the next section, ANALYSIS OF CONTROLLING REGIMES The variation in the slope of the Arrhenius plot is indicative of a possible shift in the controlling mechanism. At relatively low ‘Contsolling mechanisms in benzene oxidation © ~ EXPERIMENTAL == caucuLaTED FROM EQUATION (4) “ie Fig, 3. Comparison of Eq, (4) with experimental data for total benzene conversion. temperatures a high value of the slope may be obtained, but as the temperature is increased the slope becomes equal to the arithmetic mean of the activation energies for reaction and diffusion and would be approximately half the value for chemical control, provided there is a transition to the pore diffusion regime{21}. This would be particularly true in the present case since Knudsen diffusion dominates in silica gel, and for this type of diffusion the activation energy is less than 1 kcal/g mole. With a further rise in temperature the activation energy may fall 10 less than 2 kcal/g mole, indicating external mass transfer control. 543K, VAIDYANATHAN and L. K, DORAISWAMY onl onl 7 CaO caraurss 2 Teme = 50% O~ EXPERIMENTAL =~ catcuiares FROM EQuATiON (5) 300 a ie Fig, 4. Comparison of Ea. (5) with experimental data for maleic anhvkcide formation, Arrhenius plots of the three first-order constants for catalysts 2 and 3 are shown in Figs. 5 and 6. The activation energy in the higher temperature range (350°-400°C) is of the order of Zkcal/g mole, while in the lower temperature range (310°-350°C) it is about 20 keal/g mole (Table 3). It is clear therefore that there is a shift in the controlling mechanism at about 350°C. A similar fall in the activation energy has been reported by Pinchbeck{15] for the oxida: tion of naphthalene and by Dixon{i} in his review of the work of Holsen(20] on the oxida- tion of maleic anhydride, but no mechanism has been proposed. From Figs. 5 and 6 it is apparent that pore diffusion does not play any significant part, since the middle region corresponding to an activation energy approaching 10 kcal/g mole is almost entirely absent. This was further exam- ined by determining the rate constants for different particle sizes (-$+12, —12+22, -22+36, —36+60 B.S.S. mesh) of catalyst 3 at 350°C and plotting them as a function of particle size (Fig. 7). These studies were restricted to the overall rate constant k(= k, + ks) since all the rate constants, k,, ke, ks and k, exhibit identical behaviour with change in temperature. The observed rate constant would 544Controlling mechanisms in benzene oxidation CATALYST ~ 2 + E5180 keal. /om. mole | = 12:55 keal / gm. mole kx i | GwANBE IN MECHANISM 1 evewent (MATURE UNCERTAIN) en | 1 controw hm 1 i 1c + 1 W tow Fig. 5. Identification of controlling regimes from Arrhenius plots for catalyst 2. actually be the product of the intrinsic rate constant and catalyst effectiveness factor, ek. When extrapolated to d, =0 this gives an asymptotic value which is the intrinsic rate constant, &. The effectiveness factor, ¢, for any Particle size is then obtained from (9) The values of ¢ for different particle sizes are summarized in Table 4. The Thiele modulus, é ae fain) {10) was calculated for catalyst 3 by estimating D. from the equation for Knudsen flow[21] using the catalyst properties listed in Table I. The estimated value of D, is 1-57 x10 cm*)sec. ‘Table 4, Experimental effectiveness factors fr differ ‘ent values ofthe Thiele modulus Particle size (BS.S.mesh) KX . 6 +12 1811-08 O61 422 20330977 OTL 436 2043 0-984 0-038, +60 208) 4.000 _0023,K.VAIDYANATHAN and L. K, DORAISWAMY {= ‘CATALYST k x0? a, Cg = 22.75 kcal. gm mole ' ah nae 1 ' E iS CHANGE Ww mECHANISo | cvemene ete: a c | CONTROL iN o hos z dis \e 1 a = x0 de Fig. 6. (demifieation of eomrofhing regimes from Armhenius plots for catalyst 3, Expressing & in Eq, (10) in units of I/sec, ¢ was calcutated for all the particle sizes used, and the resulting values are included in Table 4. These are plotted 95 4 function of ¢ in Fig. 8 which also shows the theoretical curve for a first-order reaction in a spherical catalyst. Clearly the effect of pore diffusion is absent in this case. Since the activation energy in the high temperature range has a value of about 2 kcalfg mole, mass transfer would appear to be the controlling resistance in this region. But it has been pointed out by Petersen [23] that external mass transfer can never by itself be the control- Jing resistance for any reaction and that it is always accompanied by pore diffusional resis- tance of a higher magnitude, However, this conclusion needs to be examined for the resion where pore diffusion is absent, as in the present case. Peterson (23) has derived the equation, pe v 1+6 a where o is a mass transfer factor and @ is a dimensionless number defined by (2) 546,, Controtiing mechanisms in benzene oxidation ek x 107 38 BT PARTICLE SIZE catauyst— 1 Teme - asorc a 36 Incnes. Fig. 7. Effect of particle size on observed rate constant Im Eq, (125 ke is based on unit external area and has units of length/time. @ may therefore be regarded as a reaction number based on unit external area, thus making it possible to compare chemical reaction with external mass transfer. 6 can also be expressed in terms of the Thiele . modulus{23}: D, =3¢%e, 3) 6 3O DE (13) By combining Eq, (11) and (13) and setting «= 1, 1 D, +3g22. 1436 c= «ay ‘This equation relates the external mass transfer factor with the Thiele modulus for the case where the effectiveness factor is unity. It can be readily seen from Eq, (14) that the mass transfer factor is also unity, Thus neither external mass transfer nor pore diffusion offers any significant resistance to the oxidation of benzene. The absence of the external mass transfer effect was also confirmed from the charts of Hougen ef al.(261. It may be concluded that, while in the low temperature range chemical reaction is obviously the controlling mechanism, in the high tempera~ ture range also it seems to be the controlling 347K. VAIDYANATHAN and LK. DORAISWAMY Cs ria carauysr = 3 +H — rarorericat i © EXPERIMENTAL a U REGION (ui) { Fig. 8, Theoretical effectiveness factor (e) curve fora first-order reaction, showing also the experimental values of « mechanism since both pore diffusion and external mass transfer have been shown to be insignificant. However, there is a definite change in the chemical mechanism, which might be due to a favourable change in the catalyst structure and orientation. Hammar’s conchusion[7] that mass transfer offers the controlling resistance is not borne out by the experimental results of the present investigation. It is interesting ta note that in two other systems involving oxidation with gaseous oxygen (air), a similar shift in the controlling mechanism has been observed: in the reaction between oxy- gen and coal{24]; and in the oxidation of a bed of porous coke particles by oxygen(25}. It has already been pointed out that the oxidation of naphthalene{15] is also characterised by a shift in mechanism at high temperatures (although the controlling mechanism has not been delineated). It would therefore appear that wherever solid~ gas reactions are involved in which the gas phase is oxygen (air) and the solid phase is a catalyst or a reacting solid, a shift in the controlling mechanism may be anticipated. SUMMARY AND CONCLUSIONS Standard catalysts are available for the oxidation of benzene, but in the present study several compositions were prepared by varying the proportion of V.O, and MoO, on silica gel (cartier), in order to establish the influence of the oxides composition on the kinetic parameters of the reaction (inchiding the two selectivity terms, hulk and kyk,+k;). Earlier studies in this area were of a qualitative nature. ‘This part of the work(27] provided the basis for selecting the best catalysts for the system, and the studies reported here were undertaken with the catalysts thus selected. In the light of the present work, the following significant aspects of benzene oxidation may be 548,Controlling mechanisms in benzene oxidation were identified Gn accordance with the existing postulations), and it was found that simple first-order rate equations could be fitted to each of these reaction steps. (i) A shift in the controlling mechanism was observed around 350°C, the activation energy falling from 20kcal/g mole in the temperature range, 310°-3S0°C, to 2kcal/g mole in the temperature range, 350°-400°C. The possibility of pore diffusion and/or mass transfer being the controlling step in the high temperature range was fully examined, and it was found that neither of these was operative. It is therefore likely that the reaction is chemically controlled over the entire temperature range and the fall in the activation energy is due to a favourable change in the structure and orientation of the catalyst at higher temperature. (iii) Based on reported data and on the results of the present work, there appears 10 be a case for postulating a shift in mechanism at high temperatures for oxidation reactions in general in solid-gas systems. NOTATION 4 constant A constant of Arthenius equation d, particle diameter, cm D bulk diffusion, em*jsec Dz. effective diffusion coefficient, cm*)sec activation energy, kcal/g mole F feed rate, g moles/hr rate constant for maleic anhydride forma- tion, g moles/(hr)(g cat)(atm) ky rate constant for maleic anhydride decom- position, g toles/(hr\(g cat)(atm) ks Fate constant for total combustion of ben- zene, g moles/(hri(g cat)(atm) k, reaction velocity constant based on exteraal surface area, cm/sec p partial pressure, atm 7 rate of maleic anhydride formation, g moles/ (hrV(g cat) rate of maleic anhydride decomposition, g moles/(hr)(g cat) fy Fate of total combustion of benzene, g moles) g moles/(hr)(g cat) effective radius of catalyst pellet, em temperature, °K weight of catalyst, g total benzene reacted, g mole/g mole fed x 4% Greek letters € = effectiveness factor 0 = dimensionless group.“ o = mass transfer factor - Thiele modulus. A/3 (kfDo) Subscripts B= Benzene C= Carbon dioxide M = Maleic anhydride = Oxygen REFERENCES U] DIXONS. K, nnd LONGFIELD J. E,, Catalysis (Edited by P. H. Emmett) Vol. 7, Chap. 3. Reinhobd 1960 [2] NEWITT D.M. and BURGOYNE. H., Proc. R.S0¢. 1936. A 153488 (3] ZALKIND Y. 8, and ZOLOTAREV S.J. appl. Chem. USSR 1933 6 681; Chem. Abstr, 1934 284039. (4) PIGULEVSKLUV. Vand YARZHEMSKAYA E. Yit,J. gen. Chem, USSR 1938 8 1620: Chen, Abstr. 1936 30 1978 [5] TAKIKAWAS, J. Sac. Chem, Id Japan 1945 8837: Chem (6] WEISS. M. and DOWNS CR, nd. Emerg, Chem, 1920 12228: 948 42 6324 Soe. Chem. (nd. 1926 451 188, 7] HAMMAR. G. B., Svensk ken. Tdshr. 1952 68 165: Chem. Abstr 1952 46 8945 5, {8] 1OFFE 1. Land LYUBARSKIT A. G., Kinet, Kata 19623261: Chem, Abstr, 1963 58 553 {9) STEGER, American Cyanamid Company. ungublished results (cf. [1]. [10] DMUCHOVSKY B., FREEKS M. C,, PIERRON E. D., MUNCH R. Hand ZIENTY F. B., J. Catalysis 1963 4291 U1) BENSON 8.W., The Foundations of Chemical Kinetics, p. 35. 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Chemical Reaction Analysis. Prentice-Hall 985, [24] WICKE E., Z. Elekara chem. 1956.60 774 [28 HEDDEN K., Chem. Engng Sei. 1964 44 317. [26] YOSHIDA F.. RAMASWAMI D. und HOUGEN O, A..A..Ci-E. convention, Washington D.C. 1960, (27) VAIDYANATHAN K.. Ph.D. Thesis, University of Bombay 1967, Résumé— L‘oxydation du benzéne en phase de vapeur w donné lieu & de nombreuses études antée’ cures, mais ley mécanismes content cette réaction a’ont pas été totalement élucidés. Dans Pétude présente, basée sur un programme dans lequel le benzene est simultunément et consécutiverent (par Vintermédiaire anhydrire maléique) oxide jusquau produit final de combustion (broxyde de carbone et eau), on a établi des Equations converahles de peemies ordre pour les trois Féastions Sur tun catalyseur molybdéne-vanaiium, Les résultats expérimentaux indiqueat la présence, dans le mécan: igme de conteale. d'une dérivation définie Cenviran 450°C... comme cela a été mis en evidence par le changement. dans 'énergie d'activation, environ 20 kealimole dans la game de basses tempt tures, & environ 2 kcal/mole dan la parame supérieure. Une anatyse abtuillée de ta réaction dans ki région de haute température a, wutefois, montré que le contrOle ne se fat ni par la diffusion des pores. si par fe transfert extérieur de ta masse’ On a Gone postulé que le chungement est probablement dit & tune modification dans le mécanisme chimique et non pas & une mulation d'une régime chimique 3 ‘un régime de difssion, ‘Zusammenfassung — Die Damplphasenoxidation von Benzol ist Gagenstand frtkerer Untersuchungen Bewesen, dabei wurden die kontrollirenden Mechanismen dieser Reaktion noch nicht voisti auigekbirt. In der vorliegenden Arbeit, die aut und Folgereaktionen (ber Muleinsijureanhydrid) zu den endgiltigen Verbcennungspradukten (Kohlendioxid und Wasser) osidiest wird, wurden passende Reaktionsgleichungen 1. Ordaung fur dig 3 Reaktionen an einem Molybdin — Vanadium-Katalysatar wufuestellt. Dig experimentelien Ergeb- nisse zeigen, dass es bei dem kontrollierenden Mechanismus bei etwa 350°C cine bestimmte Verschie- bung gibt. kas durch den Wechsel der Aksivierungsenertie von etwa 20;kcalfg mot bei niederen Temperaturen auf etwa 2kcalig mol bei hiheren Temperaturen bewiesen ist. Fine genaue Unier- ‘suchung der Reaktion in hohen Tempersturbereichen hut jedoch wezeigt, dass weder die Porendifiu- sjon noch externer Stoffuustausch eine Rolle spielen. Es wurde deshalb fesigestellt, dass diese Anderung auf einen Wechsel des chemischen Mechanismus vurickzufihrea ist und nicht auf eine Verschiebung vom chemischen System auf ein Diffusionssystem. 350