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Ind. Eng. Chem. Fundam. 1902, 21, 438-447

Experimental Criterion for the Absence of Artifacts in the Measurement of Rates of Heterogeneous Catalytic Reactions
Rostam J. Madon' and Mlchel Boudart'
Department of Chemical Engineering, Stanford University, Stanford, California 94305

An experimental criterion has been developed to assess whether measured catalytic activity is independent of the influence of transport phenomena. A simple theoretical analysis and experimental verification of the criterion have been carried out. This test may be used when heterogeneous catalysis is carried out in batch, continuous stirred tank, and tubular plug-flow reactors, and is best suited to be used with supported metal catalysts. In this case, the test should be performed with two or more samples with different metal loading but of similar metal dispersion. Absence of physical artifacts is established by the constancy of turnover numbers. I f the reaction is exothermic, the test should be repeated at another temperature.

Introduction It has been stated (Boudart, 1972; Carberry, 1966; Satterfield, 1970) that catalytic data should be free from all transport influences to obtain kinetic rate expressions and to yield the correct activity or selectivity of the catalyst. Though the dangers are known, it should be emphasized that scaling down to laboratory studies is fraught with problems to eliminate concentration and temperature gradients both within catalyst particles (intraparticle gradients) and between the external surface of particles and surrounding fluid (interphase gradients). In the past, a number of interesting and useful criteria have been developed to check for the influence of heat and mass transfer on observed catalytic rates. Most of these criteria have been explained in a detailed review by Mears (1971a). Several criteria have been assembled in Table I. The Weisz-Prater criterion (1954) for intraparticle diffusion, for which only directly observable quantities are required, has been criticized for lack of generality by Petersen (1965a). The Petersen criterion (Petersen, 1965a), however, does not contain only observables and is hence more difficult to use. The more generalized criterion of Bischoff (1967), where the integration of the rate expression is involved, or that of Hudgins (1968)and Stewart and Villadsen (1969), where the differentiation of the rate expression is necessary, all suffer from the fact that the rate expression must be known, be it the power law type or the Langmuir-Hinshelwood type law, and if it is the latter then numerical values for all equilibrium constants must be obtained before the criteria can be used. Hudgins (1972) derived a criterion for interphase diffusion, but it suffers from the same problem as stated above. The criteria to check for interphase and intraparticle temperature gradients are due to Mears (1971b) and Anderson (1963), respectively. To use the several criteria, some of the following experimental properties are necessary: effective diffusivity in the pores of the catalyst, the heat and mass transfer coefficients at the fluid-solid interface, and the thermal conductivity of the catalyst. A t the low particle Reynolds numbers used in laboratory packed bed reactors, the accuracy of the value of h obtained from known correlations is subject to question (Madon, 1975). Though numerous studies have been carried out for bulk diffusion and difCorporate Research-Science Laboratories, Exxon Research and Engineering Co., Linden, NJ 07036.
0196-4313/82/1021-0438$01.25/0

fusivities of fluids, it is difficult to obtain the effective diffusivity for different catalysts. Satterfield and Saraf (1965) have shown that diffusional characteristics may change throughout a pellet due to compression of the catalyst powder in a pelletizing machine. Intraparticle criteria include surface concentrations and surface temperatures. These are usually not known and bulk values can be substituted only if there are no interphase gradients. Though the heat transfer criteria can be used to check for temperature gradients in the presence of diffusion, the latter effect could cause the rate and activation energy to be low and the criteria to be obeyed. In the absence of diffusion with the true higher values of the rate and activation energy, the criteria could be disobeyed for the same reaction. Finally, the particle size is another important parameter. Often powders with a wide size range are used in laboratory reaction studies, and Aris (1957) showed that the mean effectiveness factor is given by
B = CBia[
i

Aris has warned against using average values for particle size to calculate 7, and in this light the above criteria could not be used except by using the largest and hence the most conservative value for the radius. Besides using the above correlations, experimental tests are often carried out to check for diffusion. In a flow system, if the space velocity is kept constant and then if the conversion remains constant as the flow rate is changed, the influence of external mass transfer is said to be negligible. A similar test is used in slurry reactors where the constancy of the reaction rate is checked as the agitation of the slurry is increased. Chambers and Boudart (1966) have indicated that at the low particle Reynolds numbers encountered in the laboratory the heat and mass transfer coefficients are quite insensitive to changes in flow rates, and hence the above diagnostic test may fail to indicate that the reaction rates are free from interphase concentration gradients. Moreover, this test cannot give any information regarding intraparticle diffusion. If activity of a catalyst is affected by altering pellet size, then this activity is said to be influenced by pore diffusion. However, if there is no change in activity with pellet size one cannot say for sure that there are negligible intraparticle concentration gradients. The influence of internal diffusion in the small pores of a bimodal pore distribution may still be important, and the test may just indicate that there is no diffusional influence in the larger set of pores.
@ 1982 American Chemical Society

15 <-r(cb) 1 Cbk. The Koros-Nowak Criterion [rate of reaction]/[ concentration of active material] = constant 1. Cb dr(C)/dC C=Cb For Intraparticle Heat Transfer 1 1 zero-order reaction first-order reaction second-order reaction Anderson (1963) Daw = [ . [rate of reaction (mol t 3 . E T For Interphase Heat Transfer Mears (1971b) [ .75--- RgTs . analyzed.Ind. No.77 Dan < -r(Cs) c s I dr(C)/dC I c=cs - 1 Bischoff (1967) In-70) For Combined Interphase and Intraparticle Heat and Mass Transport" Mears (1971a) R lr n . To circumvent the problems stated above.15 -- ri(Cis.. I t will be shown that when this test is obeyed there is neither poisoning nor poor contacting of the catalyst due to bypassing and channelling.A H 1 Rr X= < 0. 3 3 ~ 7 I Table 11. (b) the surface area of the active material per unit weight of the catalyst. The reaction rate. changing pellet sizes could cause distortion in the flow field wkich could affect contacting. Also.3 Petersen (1965a) Thiele modulus < where ri(5) = ri(C1.' g-l of catalyst)]/[surface moles of active material per unit weight of catalyst] = turnover number = r/f. a < 1+ 0 . Chem.T) ( dT )T=T. Eng..15- RgTb .0. isoconcentration conditions. and velocity gradients. C s 23 Hudgins (1 968) 0.l of active material) = constant 2.. = constant Furthermore. backmixing. The Koros-Nowak criterion can then be explained by noting that in the kinetic regime (a) the ratio of measured reaction rates must equal the ratio of the weight fractions of the active material in the different catalyst samples. <1 Stewart and Villadsen (1969) 0.0. the test will be explained.75 fi T) TI 1 AT. e.33nw) CbDe Note. The concentration of catalytically active material may be defined as (a) the weight fraction of the active material in the catalyst.75 Dan 4 -r(Cs) E yb For Combined Intraparticle Heat and Mass Transfer hTb Mears (1 971a) 1 De or for power law kinetics DaII < cs 1 dr(C)/dC I c=cs 1 -- (-AH) dr(C. or (b) the turnover number (defined as moles reacted per second per surface . and finally demonstrated to show that the cri- terion can be successfully applied when kinetic measurements are to be obtained. is directly proportional to the concentration of the active material (see Theoretical Section). [rate of reaction (mol s . (mol s'l g . This overall criterion provides that the NET distortion of the observed rate will be within 5% of the rate under isothermal.I g-l of catalyst)]/[weight of active material per unit weight of catalyst] = r/f. C2. Fundam. The Koros-Nowak Criterion The criterion is based on making rate measurements on catalyst samples in which the concentration of the catalytically active material has been changed. 4. Hudgins (1972) =- R2r R. in the kinetic regime. In the following sections. Vol. [rate of reaction (mol s . It will be shown that this criterion can be used as a test for interphase and intraparticle mass and heat transfer either when they occur separately or when the physical events are coupled during the course of a reaction. 0.* g-l of catalyst)]/[surface area of active material per unit weight of catalyst] = r/fa (mol s-l cm-2 of active material) = constant 3.A H [ R2r < 0. or (c) the surface moles of active material per unit weight of the catalyst. 1982 439 Table I. There is no guarantee of freedom from individual transport processes.7bPb I(1f 0.6 G0. as long as the dispersion of the active material does not change from one sample to the next. will cause the criterion to be disobeyed In all future discussion this test will be referred to as the Koros-Nowak (KN) criterion. deviations of plug flow behavior in tubular reactors due to transverse and longitudinal temperature and concentration gradients (interparticle gradients). 21. we wish to develop an experimental criterion which was first suggested by Koros and Nowak (1967) to check if reaction rates were free from mass transfer effects. Various Criteria Used t o Check for Transport Effects in Heterogeneous Catalysis For Intraparticle Mass Transfer For Interphase Mass Transfer Weisz and Prater (1954) DaII = -G 1 C De s Weisz (1957) Dan < 6 90.

There are two cases when the K N test. Koros and Nowak (1967) have explained how one can change the concentration of active material without changing the dimensions and pore diffusion properties of the pellets. will also be valid for f or fa. 1965. Three relations on which much of the following discussion will be based are r = kvdC. The selective chemisorption of hydrogen or carbon monoxide has been used by Sinfelt (1969) on 11 different supported metal catalysts to obtain reaction rates per unit area of active material. and either reactant consumption or product formation is observed with respect to residence time. In all following discussions f. Wanke and Dougharty. In plug flow reactors. rates cannot be measured directly unless the reactor is operated in a differential manner. . Hence.) . cannot be used. Let us take w1grams of a catalyst in which f m = f. It should be noted that no measurement of the number of surface sites is involved. it must be stressed that the test does not require a knowledge o f the number o f sites involved in the reaction. Intraparticle Mass and Heat Transfer. then the KN criterion is obeyed. then the KN criterion is obeyed if the observed conversion is invariant in both cases (see Theoretical Section). = fm1. Chern. Rates are directly obtained (Boudart. by experimentalists in the laboratory. with surface concentrations of active material f. by a certain factor a . Let us define a quantity analogous to space velocity and denote it by p . and the dispersion of the metal (defined as the ratio of the number of moles of surface metal to total metal) close for all the catalyst samples. the active space velocity p = tiO/wf. and f. then the KN criterion is obeyed. The concept of the CSTR has been used. The inert powder must have the same diffusional characteristics as the catalyst powder with which it is mixed. When surface concentration of the active material in different catalyst samples can be measured. l / p using a catalyst sample with f. 1972. of course. 4.. If the conversions at the same residence time in the two experiments are identical. then for the K N criterion to be obeyed the observed rate should change for the diluted catalyst over the initial undiluted catalyst by the same factor cy. 1968. The KN test may be used in a batch reactor system as follows. No. for catalysts with bimodal pore distributions. the conversion of a reactant is obtained at a known space velocity which may be defined as the molar flow rate of the reactant divided by the weight of the catalyst. Another way is to obtain values of conversion at different flow rates and to plot conversion vs. Their method consists of mixing catalyst particles with particles of an inert powder and then making pellets from this mixture. a slope of 1 denotes that artifacts are not influencing rate measurements. Fundarn. the logarithm of the surface concentration of active material. Another approach is to plot the logarithm of the reaction rate in mol s-l g-’ catalyst vs. in the form of the recycle reactor pioneered by Temkin (1962) and the continuous stirred tank catalytic reactor used by Tajbl et al.) (2) k 0: f m (3) . thus obeying the CSTR condition and allowing the rates to be obtained directly. For both metallic and nonmetallic catalysts this test can be used conveniently as follows. with caution. 1973). If we dilute a given catalyst. Benson et al. internal diffusion in the micropores may be important in both the diluted and undiluted catalyst samples. At the stationary state. # f m . when the catalyst has a bimodal pore distribution... The titration of adsorbed oxygen by hydrogen first used to measure platinum surface areas by Benson and Boudart (1965) has been recently extended to obtain the surface areas of rhodium (Wanke and Dougharty. and note the conversion at a certain residence time t . as is sometimes the case for catalysts used in liquid phase slurry reactors.. 1973) are now available to measure surface areas of the active metal in supported catalysts. then if the concentration of active material in the micropores of catalyst 1 is different from that in catalyst 2 by the same factor cy. Techniques (Whyte.. Theoretical Section A. If this plot coincides with the plot when we repeat the experiment using a catalyst sample with f . 1966) in the case of continuous stirred tank reactors (CSTR) operating at the stationary state. Before concluding this section describing the K N criterion. Let us now see how the KN criterion may be used in the different kinds of reactors used to carry out chemical reactions. 21. the K N test may be carried out. The recycle reactor consists of a loop which includes a reactor containing a small amount of catalyst and a recirculation pump. When investigating heterogeneous catalytic reactions in a batch reactor. Explanations regarding the deviation of this slope from unity are given in the Theoretical Section. the system is assumed to be in a stationary state. where f. carried out by diluting a given catalyst as described above.. take w 2grams of a catalyst in which f m = f m . will be used to denote the concentration of active material. = f. (1) If two experiments are performed and f . 1973. We must modify the way to use the KN criterion from the method described above to a method compatible with the observables in the tubular flow system. In the case of supported metal catalysts. and hence the KN criterion is easily used. 1972) and palladium (Benson et al. Secondly.. by the method described above. and if the KN criterion is obeyed it may just indicate that there is no diffusional influence in the larger set of pores. 1 and 2. (1966). if the particle size of catalysts used in the reaction is close to the size of the powder from which the “diluted” pellets are made.where f. Denbigh. respectively. = afmg. then the KN test as described above cannot be used. Rather./fm.440 Ind.. the composition in the loop and exit line is practically identical. when the flow rate of chemical components in and out of the loop is small compared to the recirculation rate. First. 1982 mole of the active material) or the reaction rate referred to unit surface area of the active material must be invariant as the concentration of active material is changed. Eng. Benson and Boudart. concentrations of active material may he changed by changing the metal loading on the inert support but keeping the preparation and pretreatment procedure identical. SO that ~2 = wl(fm. if we have two catalysts. Table I1 summarizes the K N criterion. then the K N criterion cannot be used to check for the effect of intraparticle mass transfer in catalysts with bimodal pore distributions. In a second experiment. The initial particles in the mixture must be much smaller than the final pellets used in the reaction. The CSTR condition states that mixing is complete so that all the properties of the reaction mixture are the same in all parts of the reactor and in the exit stream. is changed but p is kept constant in each experiment. Vol.) and note the conversion at the same residence time t as the first experiment. (The discussions.

It must be noted that if p is a large negative number s may become less than 0. p is zero and hence s is unity.. When diffusional influence exists but is small. It is interesting to note that at point c' where q is unity and there is perfect compensation (the rise in the reaction rate due to the increase in the temperature within the pellet compensates the decrease in the measured rate due to the influence of mass transfer). is changed. 21. v Using eq 2. In $J for isothermal and nonisothermal exothermic and endothermic reactions (Weisz and Hicks. If s is unity at two different temperatures. say in a slurry reactor. The largest (d In q)/(d In 4) will be at the inflexion point a' where s will also have its largest value. Vol. Equation 3 is characteristic for heterogeneous catalytic reactions taking place in the kinetic regime.. As the Arrhenius number Y = E/R. indicating correctly that the exothermic nonisothermal reaction is being influenced by intraparticle diffusion. the value of s will tend to 1/2.Ind.5 and also zero or a negative number. the limits for curves A and B are in between those described above: -1 I I p 0 and ' I 2Is I1. When intraparticle diffusion and low values of q. In the KN criterion.-1. Here the values of p are greater than zero between points P and Q. p 0 and s < 1. A t Q and R. No. 1962). (d In q)/(d In 4) m and hence s m. Chem. s will be referred to as the Koros-Nowak number or slope. if the amount of active material is doubled then the rate should be doubled. Typical plots of In 7 vs. whereas the latter limit indicates severe . and in the kinetic regime the reaction rate is directly proportional to the concentration of active material.) s is the slope obtained on plotting In r against In f . 4.and 6 r = kd%!(c. we must clarify the above explanation by stating that the KN criterion is not the same as the well-known test in which if the weight of a catalyst is doubled. For the exothermic reaction a similar situation exists for part b to c (Figure 2). s 1/2 P = (-WDeCs/XTs (10) increase. Eng. is an extensive property and is directly proportional to the amount (Le. q = Figure 3. The effectiveness factor at b is higher than unity. of any curve. Between a and b. graphs as shown in Figure 3 may arise (Weisz and Hicks.s-1 and when p The former limit corresponds to 7 1. A plot of In 7 vs. no intraparticle diffusion. and C in Figure 1. Fundam. surface area. weight.g. Figure 2. and the rate is hence higher than the true isothermal rate..Ts (9) and the heat generation parameter p-0. At point b. The slope. 1962).. p is greater than zero and hence s is greater than 1. defined in moles per unit time. or surface moles) of active material.. similar to the zero diffusional influence point a. In $J for a nonisothermal exothermic reaction (Weisz and Hicks. Equation 2 indicates that the observed rate is dependent on the effectiveness factor which in turn is a function of the dimensionless Thiele modulus defined in eq 4. a > 0 for C. 1962). An easy way to resolve this ambiguity is to perform the experimental criterion at another temperature which would move the point in question either to the left or right of point b. A plot of In 7 vs. 1962). B. Let us consider the curves A.e. the reaction rate should be doubled if there is no influence of interphase mass transfer. at any point is dlnq dlnv p=-=(-1 I Ia) p dln4 dln$ where CY = 0 for A and B. i. then one can be assured that one is not concerned with the rather rare occurrence of being at point b. 1982 441 I 1 1 n@ u 1n@ Figure 1. - - . the concentration of active material in the catalyst. rather than just the weight of the catalyst. Between Q and R. The rate of a catalytic reaction. 4. Before proceeding. e. In $J for a nonisothermal exothermic reaction (Weisz and Hicks.

and interphase heat or mass transfer. rate = qkg(Cs) = k..98 0.58 0.l)/s (17) Knowing s from the KN criterion and the observed concentration dependence m.4 coth 4 . Interphase Mass Transfer. must be identical. From eq 8 n = 1 + (m. we have two bounds when the KN criterion is used 1.where n is the true reaction order. 21. In 4 are similar .) (18) As k.81 0. Chem. CSs. << qk rate = constant Cb and s = 0 2. changing the latter will not change the rate and the KN number s will be zero. and 16. >> qk rate = constant fm1/2Cb and s = y2 Though easily shown for a first-order reaction.a(Cb .53 0. n Between R and S. a k . For porous catalysts.] (19) It can be easily shown for a first-order reaction that rate = k’Cb where Remembering that for a severe internal diffusion problem 7 0: fm-lI2 and using eq 3 and 20. is independent of the concentration of active material.94 0. 1982 Table 111. detailed by Satterfield (1970).c. In 4 plots similar in shape to the ones described above are obtained. Carberry (1961). 4. Irreversible.a[Cb . a short corollary may be easily deduced from the above algebra. Numerical Values for the Case of an Isothermal. It should be noted that the value of s equal to unity also means that the turnover numbers. the same limits apply for more complex rate expressions...C. and Hutchings and Carberry (1966).. (15) The apparent rate constant k may be taken out of the function r ( C ) . Equations given by Weisz and Hicks (1962). e. then See Table I11 for numerical values.37 0..27 0. at effectiveness factors 10. Bischoff (1965).62 0.C28.73 0.90 0. 1970) 7 = #P = ”[ 4 coth 4 dlnq d4 i] (12) 7 oc k-lI2 (16) From eq 2. p > 0 and s > 1.75 0.1 Before ending the section on intraparticle diffusion.. Analysis. Fundam.83 0. if the concentration function g(CJ is described by Cisn.67 0. Vol. Aris (1965). it can be easily seen that under Severe intraparticle diffusion conditions for any rate expression s = -P ’ dlnq d In 4 -4 - 2 . It is essential to note that the above analysis for intraparticle diffusion holds not only for reactions obeying simple power rate laws but also the more complex Langmuir-Hinshelwood rate expressions including strong product inhibition. for all cases with intraparticle diffusional influence.95 0. Interphase heat or mass transfer influences can complicate the problem (i. isothermal first-order reaction in a spherical catalyst pellet the above conclusions may be obtained analytically from results of others (Satterfield. for isothermal operation.98 50 20 10 7 5 3 2 1 0. Large Intraparticle Concentration Gradients. Computations are not made so easily for other situations. obtained for different values off. and the local curvature and hence the shape of the catalyst particle is of minimal importance. Values .14 0. nonisothermal reactions. when the Nusselt numbers are low) by being coupled with the intraparticle case. I n short. the Koros-Nowak number is approximately equal to q.8.35 0.4’ csch2 4 4 coth 4 .e. Eng.55 0.g. ak. Hence r(Cs) = kro(Cs) r0(CJ may be a power rate law or a Langmuir-Hinshelwood type expression..059 0. Hutchings and Carberry (1966) and Carberry (1961) have shown that interphase heat transfer influence raises q for exothermic cases whereas interphase mass transfer tends to reduce 7 Once again the plots In 7 vs. p will deviate from zero and s will deviate from one. show that In 7 vs. where A is the normalized Thiele modulus where m is the observed reaction order.12 0. and others have to be solved and numerical differentiation carried out to give (d In d / ( d In 4) = P. with or without t h e complexity of strong product inhibition. intraparticle heat transfer.98 and r(CJ = ?(CIS. when there is a large interphase mass transfer influence the effectiveness factor is usually low.94 0. In eq 7. Beyond S the arguments are similar to the isothermal case. . and Petersen (196513) have demonstrated that the effectiveness factor is asymptotically h-l for a general case. When the reaction rate is strongly dependent on the interphase transport of reactants to the active material on a catalyst N = k. B.82 0. one can obtain the true order of reaction n. as only the active material at the mouth of the pores participates in the reaction. First-Order Reaction on a Spherical Catalyst Pellet rl q = l/A (13) where d -p 0.55 0. No. For an irreversible.48 0. Under extreme diffusion conditions only a thin layer of a catalyst particle is useful.51 0. It is interesting to note that for the firsborder reaction considered.442 Ind. to the ones described above.5 0.032 s = 1 i @/2) 0.3.

the rate will increase from rl to r2 so that N1 = N 2 and s = 1. Tal we must have T.)g(Ca.. Vol.T.. In the rare case when the coupling gives s = 1. 4). Mears (1973) has recently shown the relative importance of transport effects.. is the same.. can be used to establish the nonexistence of interphase temperature gradients. is increased from f. it is assumed that there is no diffusional influence and C. It is interesting to rationalize the value of s for interphase heat transfer without diffusion when rate expressions are of the type r = kg(C.. r2 > rl and hence T. fm.... N1 # N2. > f. . Tar. the heat released by the reaction is equal to that transferred to the bulk fluid.A’ exp(-E/R. (-mr ha(T.W r i = ha(T. This is inconsistent with eq 22 and 23 because when their left-hand sides are different as r2 > rl.. and external temperature gradients are important. It is useful to keep these generalities in mind when using the KN criterion. Tb and T.experiments done at a new bulk temperature would shift the value of s from 1 if transport influences are important. Deviations from plug flow are due to the influence of transverse and longitudinal temperature and concentration gradients (interparticle gradients). . Deviations from Plug Flow Behavior in Tubular Reactors (Interparticle Gradients). C. > T. In r .. (22) . If there is external heat transfer influence then iff..)g(C. As explained above. > f. are used respectively. Plug flow in tubular reactors may be defined as a state of flow when the flow rate and all fluid properties over any cross section normal to the fluid flow are identical and the residence time of all volume elements..Ind. N 2 < N1and s < 1. velocity gradients. Interphase Heat Transfer. These individual influences of external heat and mass transfer can be coupled as indicated diagramatically in Figure 4 in order that a value between s = 0 and s > 1 would be obtained. and f. we have T.. and Twis the temperature of the wall. In the following discussion. when there is no transport influence and f.. 21.... This occurs when by increasing the rate we may enter the heat transfer influence regime. Tb or (case 2): T. keeping all other conditions the same In . 1982 of s between 0 and ‘I2 would then indicate a coupled influence of the interphase and intraparticle mass transfer. Let us use the KN criterion. Though the arguments are for exothermic reactions. > f.. Mears (1973) has shown that interphase heat transfer effects become significant before the corresponding mass transfer effects unless /3 is very small in which case. Tal Tb. endothermic reactions may be treated similarly. to indicate diagramatically the Koros-Nowak criterion for interphase heat transfer (exothermic reaction) and its coupling with interphase mass transfer. N1 = N 2 .. > f... Plots of In f. ..). when T?. Ts. Case 1 is easily explained. and backmixing in the tubular reactor. Using the Arrhenius form for the rate constant and separating f. D. (c) T. the right-hand sides cannot remain identical.. Case 2. At steady state... to f. (b) T. Hence N 2 > N1 and s > 1 (see Figure - - - - . TS2 Taland r i >> r.. there is interphase heat transfer influence. 4. of course.. Chem.Tb) = (21) Let us change the concentration of active material on the catalyst from f. T.f (rurfoce mol g -1 catalyst) ( . we get fm. is equal to c b ...T. Though longitudinal concentration gradients are always present in plug flow reactors..) fm. A ’ exp (-E/RgTa. > T b indicates interphase heat transfer influence. Figure 5 indicates usual values of N and s for the KN criterion. Denbigh (1966) has indicated that transverse temperature gradients most often affect and invalidate the plug flow assumption. N1 = N2..) Divide by exp(-E/RTb) This equality holds if either (case 1): T. If Tal and T. it should be noted > that due to the exponential nature of the temperature dependence the rate r i increases over r2 more than rl’ increases over rl. the KN criterion. For endothermic reactions as f. represent the axial temperatures when catalysts with the concentration of active material f. Eng. f m . (a) When Tss > Tal > Tb. to f.... > Tal. as when the surface temperatures tend to the bulk temperature there is a minimal gradient and hence negligible heat transfer influence. and iff. Nl # N2. when there is only isothermal interphase mass transfer influence s = 0. where f. problems due to heat transfer will not arise. Therefore. Fundam.Tb) (23) I Coupled Interphore Transfer I As f. > Tal > T w <T w for a nonisothermal exothermic reaction. from the preexponential term.. Figure 4. Hence.- - As explained before.Tb) ( . > Tal Tb.m r 2 = ha(T. these gradients may influence the transport of reagents by causing them to reach the reactor outlet more rapidly than they would by bulk flow alone. vs..to check for interphase heat transport influence. and the order was interphase heat transport > intraparticle mass transport > interphase mass transport > intraparticle heat transport. Tal> Tb. No. and Tap < T. > f. entering the reactor..

= afm2W2 (30) If there is any significant deviation from plug flow behavior due to the influence of transverse and longitudinal temperature or concentration gradients.. A similar analysis may be obtained for the problem of longitudinal temperature gradients. and shows limits for the values of s when interphase and intraparticle effects exist separately or are coupled together. : I .. if in two experiments using different values of f. and the weights of the catalysts taken be w1 and w2. Vol. E. Poor contacting of the catalyst may be due to the fluid channelling and bypassing the catalyst. will change as f ... 1978). It will be shown that when this occurs the measured turnover numbers. respectively... Poisoning and Poor Contacting of the Catalyst. 0.. Denbigh.' are then equal only when where r here is expressed in mol sd g-' of catalyst. The chart indicates the trend of the turnover numbers N1 and N 2 when f..' = rl .. ... . then the KN criterion is said to hold and deviations from plug flow behavior will be negligible. Chem. Interphase and intraparticle transport effects. -WW2) fmz N. This is not possible except in the case 61 = Cyf... Eng. Of course a negative result for the test will also be obtained if besides nonideal flow behavior interphase or intraparticle concentration or temperature gradients are present. Experimental Results and Discussion The liquid phase hydrogenation of cyclohexene was studied over supported Pt/Si02 catalysts. Hence. is not obeyed.. The relation used for tubular reactors (Boudart. the calculated turnover numbers will be In the case when the reaction is carried out under no poisoning conditions and good catalyst contacting Figure 5.. materials.. ...W1 (29) and 6.I . 61 W1 for a nonisothermal endothermic reaction.. 21.. the KN criterion should be conducted at a second reaction temperature... Fundam. or due to backmixing and velocity gradients. w1/2 and w2/3) and the measurement of the rates repeated. > f.6 1 / ~ 1 ) fm1 N. Multiplying the above equation on both sides by f .0: 0 a coupling of various transport phenomena causes the test to be apparently obeyed. then transport effects are influencing the reaction. ..... at the second temperature.. 1968. If the test. .. conversions in the plug flow reactor. The details of the apparatus.. then there is no catalyst poisoning or poor catalyst contacting.. is changed but p is kept constant.' and N. 1982 interpiare - rmc lntroparticla 0 Transport E'fect. 1966) where the plug flow assumption is valid may be written as and using (26) and (27) N.... where radial temperature gradients are significant...444 Ind. the above equation will be invalid... No. and f.. using catalyst samples with different values off. wl not be the same and the KN criterion wl il il therefore be disobeyed. This case and the case of catalyst poisoning would result in a certain number 6 moles of active material not being used for the reaction. procedure.. As the dependence of the rate on temperature is exponential. Hence.. . and results are given elsewhere (Madon et al. 4...NDividing (28) by f.' = Nfm.. The "true" rate rl is then related to rl' by r.!:.. In the rare event that To check for this case the weights of the catalysts should be changed by an unequal amount (say. In two separate experiments let the measured rates in mol d 8 .l of catalyst be r< and r2/ and the concentration of active material in surface mol g-l of catalyst be f .' = Similarly N(fml. If again turnover numbers are found to be equal... The reaction was tested via the above criterion for any transport effects. but keeping p constant the same conversion is obtained.

38% Pt/SiOz samples had the identical dispersion of 100% and N was found to be 2. Conditions: r corrected for 101. though the possibility of external mass transfer influence was eliminated. exP(-ED.5% and 0.50% Pt/SiOp D=lOO% 02. Eng. that using values of activation energy alone to explain diffusional influence could lead to errors.. At high agitation intensities. at the plateau value. Satterin field et al. and using eq 4. 7 = 1/4. by shaking it.51 s-l at 307 K. 5 3 % Pt/BO2 E 62% = W 56% I 0 1 . Mears and Boudart (1966) studied the liquid phase dehydrogenation of isopropyl alcohol on nickel catalysts reduced with sodium borohydride and on Raney nickel in a slurry reactor.3 kPa Hz.3 kPa H2. Calculations to substantiate these observations are given elsewhere (Madon. r cc (kDe)'/2..33 s-l at 275 K and 8. The activation energy of the reaction.T) k = A exp(-E/R. a value of 18.. 1982 445 in fm (rvrface mol Pt g-1 catalyst) In i.38% Pt/SiO2 BlOO% 0. From Figure 6.6) = 18. the activation energy of the reaction in the 100 to 200 mesh Pt/SiO. Fundam. as does Figure 6. The identity of the turnover numbers at two different temperatures is another way of looking at the test and indicates. we ascertain that with the catalyst size fraction (a) there is negligible transport influence as s is equal to 1. 4.50% 0 2. As the slurry agitation rate was increased the reaction rate increased and then leveled off to a plateau. Using an activation energy of 12. 1968). Surface areas of the nickel catalysts were determined by the fatty acid adsorption method of Smith and Fuzek (1946) and by the nitrogen BET technique.40 s-' and 2.One may express k and De by simple Arrhenius relationships (Satterfield. solvent-cyclohexane = 20 cm3. Figure 6. 1970.5 cm3. The Koros-Nowak criterion applied in the study of the liquid phase hydrogenation of cyclohexene on Pt/SiOz catalysts. Mears and Boudart argued that.5 cm3. respectively.T) The reaction was carried out with three different size fractions of Pt/SiO.at 275 K cyclohexene added = 2 cm3. however.)./R.4 kJ mol-l whereas using the larger size (100 to 200 mesh) particles when s = 1/2. catalysts: (a) greater than 200 mesh.67 s-' and 8. i. The slurry was agitated either by stirring it with a propeller or. and (c) 60 to 100 mesh. the value of s being 1/2.53% Pt/Si02 Figure 7. when s = 1.9 kJ mol-' was obtained.5 kJ mol-'. 1970. they prepared nickel catalysts of different surface areas and noted that chromium acted as a structural promoter and increased the specific surface area of the active nickel component. and N was found to be 2. the rate constant per unit surface area remained essentially constant over a sevenfold variation in the specific area of the catalyst. The Koros-Nowak criterion applied in the study of the liquid phase hydrogenation of cyclohexene on Pt/Si02 catalysts. severe internal diffusion. Chem. catalyst particle size > 200 mesh. The rate expression for the liquid phase hydrogenation of cyclohexene may be written in the form r = kvg(C.9 kJ mol-'.53% Pt/SiO. Conditions: r corrected for 101. the rates could still be affected by pore diffusion.51 s-' at 275 K and 9. To check the latter point.6 kJ mol-' for the diffusion of H2 cyclohexane (Satterfield. solvent-cyclohexane = 20 cm3. The 2. (ruriace mol pt g-l catalyst) -I 1 I IO -1 I I -1 0 I -9 0 1 . 21. It should be noted that only catalysts with dispersions that are identical or very close must be compared when the KN criterion is used. Mears and Boudart concluded that this observation provided strong evidence + + . to study the effect of mass transfer under different hydrodynamic conditions.e. Vol. No. it must be stressed.02 s-' at 307 K. Satterfield et al. using the small size particles. 1968) De = A.67 s-' and 2." and indicate clearly whether mass transport effects play a dominant role. samples had dispersions of 62% and 56%.30% V Pt/SiO2 Pt/SiO2 BlOO% W 62% E 56% = 0 0. The 1. 1970) that there is no influence of external mass transfer on the reaction rates at the plateau value. whereas with the two larger size fractions (Figure 7) the observed reaction rates are found to be severely affected by intraparticle concentration gradients. Though this is close to the observed value of 18. Observed reaction rates on the three separate catalyst size fractions have been plotted in Figures 6 and 7.cyclohexene added = 0.3% and 0. that the reaction rates are not influenced by any physical events.at 307 K cyclohexene added = 0. 1975)..30% Pt/SiO2 v 0 . particles is '/&4.4 12. It is also interesting to note the values of the turnover numbers when catalysts with size fraction (a) were used. For Hence the observed activation energy for the severely internal diffusion influenced reaction is given by '/z(EDe E).16 s-l and 9.was found to be 24. which are diagrammatic representations of the KN criterion written as r a f. It is usually inferred (Satterfield.Ind. (b) 100 to 200 mesh.

6 .. 1966). C. Satterfleld. s = surface property eq = equilibrium Literature Cited Amirnazmi. Chem.cyclohexene (Segal et al. N. Chem. Sci. S. Hudglns. O'Connell. N. 1965. Boudart..350. 22. Carberry. = volume of the catalyst particle. E. J. R. = concentration of active material. Ser. one can be sure that the observed kinetic data are free of artifacts such as mass or heat transport. Fundam. M. Hanson. J cm-2 s-l K-l A H = heat of reaction. J. Chem. 1961.. Stanford Unlverslly. J. Ma. 1973) on supported Pt catalysts. 7. NJ. E. V. Eng. 1978). Harkins. Chem. 72. Cambridge University Press: Cambridge. Eng. 1978). J. Scl. Eng. Boudart. Anderson. If the test is not obeyed. Scl. AIChE J. A. 30. A.446 Ind. Schlatter. AIChE J.. J. Catal. cm R. cm s-l k = rate constant .. K. = concentration of active material. Chem.of catalyst ~) r ( C ) = rate expression. P. Sci. 1973. 127. D. E. C. J. cm3 w = weight of the catalyst. J. 6. defined by eq 9 6 = unused moles of active material. S.. kJ mol-' f. Petersen. Ark. 23. The Koros-Nowak criterion has also been used successfully on vapor phase reactions: hydrogenation of ethylene (Schlatter and Boudart. K. 37. M.. 1965b. Koros. 4. 470. D. 22. 28. Chambers. and oxygen (Hanson and Boudart. Boudart. (London). Dougharty. 525. A. Chem. 227. defiied as the ratio of the actual rate for a catalyst particle to the rate evaluated at external surface conditions X = thermal conductivity of the catalyst. 1966. "Mass Transfer In Heterogeneous Catalysis": MIT Press: Cambridge. Boudart. J. E. 58(10). Catal. AIChE J. Prentlce-Hall: Englewood Cliffs. Ind. 19658. Eng. A. 6 . 2 4 . E. The KN criterion cannot be used for catalysts with a bimodal pore distribution if one uses the dilution method suggested by Koros and Nowak (1967). M. 351. Boudart.. J. defined by eq 1 I$= Thiele modulus. Bischoff.C2s. defined by eq 14 v = stoichiometric coefficient t = Ci/Ci. cyclopropane (Boudart et al. Can. J. Sherwood. Catal. performed with several catalysts in which the surface area of the active component was varied and used to conclude that reaction rates at the plateau value were free from both internal and external mass transfer. "Kinetics of Chemical Processes". 313. 1963. and its use in the laboratory demonstrated. R. D. Ind. and with increased agitation the reaction rate increased due to better suspension of the catalyst in the slurry with breakup of catalyst aggregates. or A'fw A. though good characterization of the catalyst used and some understanding of the reaction being studied may help one to understand which artifact influences the reaction rate. M. M. J.. Scl. 18. 1965. 0. J. Saraf. R. AIChE J. surface moles of active material g-' of catalyst f. J. M. was in effect the diagnostic criterion later proposed by Koros and Nowak (1967). 704. E.. Petersen. 2.. E. J. MA. 262. s-' N = molar flux. defined by eq 10 y = Arrhenius number. at two different temperatures. cm2 s-l E = activation energy. C . Bischoff. 1968. Eng. J. Satterfield. Catal. Though in general the test may be used for any catalyst if an appropriate inert diluent can be obtained. R. 1966. R. J. 20. 451. J cm-' s-l K-' h = normalized Thiele modulus.. 22. Boudart. "Chemical Reactor Theory". defined by eq 4 x = defined in Table I w = defined in Table I Subscripts a = property at the axis of a tubular reactor b = bulk property i = species 1. They argued that at low agitation intensities the reaction rate was reduced as a result of internal (and to a certain extent external) mass transfer due to catalyst agglomeration and clumping. Nomenclature a = external surface area of catalyst per unit volume of the k' = defined by eq 20 m = observed reaction order n = true reaction order AO = molar flow rate. Inst. E. 541. Eng. Catal. and during differential or integral rate measurements. 1971a. R . M. Khammouma. E. Madon. 20. Eng. Catal. B. Eng. Hutchlngs... J. Chem. 3. p = active space velocity. . E. Benson.427. Boudart. Dev. J. Prentice-Hall: Englewood Cliffs. and ammonia synthesis on supported Fe catalysts (Dumesic et al. 1971b. see eq 28 rate 7 = effectiveness factor. it may be difficult to say exactly which physical event is affecting the rate data.) concentration function in the rate = expression h = heat transfer coefficient. 1975. Cafal. C. Carberry. Aidag.... 1966.CBs. Benson. C. Mears. SatterfleM. Chem. and contacting. Chem. Catal. catalyst. NJ.. 93. 1972. 12. Chem. J. Nowak. K. R. = preexponential factor in the Arrhenius relationship for D.. Catal. 1970. Chem. M. Hwang. Eng. Denbigh. 4 . = gas constant s = Koros-Nowak criterion number or slope S. 40.283. B. decomposition of NO (Amirnazmi et al. G.D. Benson. M.. Ind. 1975). 10.. 24. 1967. 30. Boudart. 92. J. J. Symp.. T. Eng. 50. 1973. Mears.. 1972. 482. Boudart.. Fundam. R.147. 1957. K. H. 1966.. Topsm. Mears. 1982 against any influence of internal or external diffusion. Conclusion An experimental criterion to check for true reaction rates in heterogeneous catalysis has been developed. The test. J mol-' k . Eng. K V . Eng. Scl.. The test may be used with batch. F. 1975. 4 . 904. N. J. J. Fundam. 53. cm2 t = time. = mass transfer coefficient. Eng. 465. Aris. s T = temperature. M. R. 1978. continuous stirred. J. J. "Chemlcal Reaction Analysis". Dissertation. g x = conversion Greek Letters a = any integer or fraction a' = volume fraction p = heat generation function. c ==concentration. M. Boudart. AIChE J. M... 78. 1972). 1966. 1978. K. Process Des. 4. D. Ph.. A simple analysis of the criterion has been given. Dumesic. N. 1966. Chem. 587. Benson.mol cm-3 DaII = Damkohler number of the second kind DaIv = Damkohler number of the fourth kind De = effective diffusivity. 1973. Mears. cm2of active material g-' of catalyst f. defined by eq 15 R = radius. 1966. 30. AIChE J. J. mol s-l cm-3 p = defined by eq 5 r = reaction rate.503. If the KN test is obeyed.56. 141. 1 1 . = external surface of the catalyst particle. 1985. Hudgins. mol s-l 8-l (or ~ m . catalyst poisoning. J.. M. J. H. 1967. Cafal. g of active material g-' of catalyst g(CJ = g(Cls. E. 1968. No. Chem. 20. mol s-' N = turnover number. cm-l A' = preexponential factor of the rate constant A = A'fm.. R. 1965.: Boudart. 146. E. Carberry.. or plug flow reactors. 21.. Madon. E. it is most readily and easily used for supported metal catalysts where the support is inert and for heterogenized homogeneous organometallic catalysts. Y. = concentration of active material. H.55. 1972. B. Boudart. Ind. A'fa. S. Vol.

229. Catai. Am. Whyte.2 and C. freeze drying. 1978a. Phys. B.' Jos6 L. stickiness can be a major problem. and drum drying. Previous mechanistic speculations are nearly all qualitative and incomplete.: Dougharty. Sonora. resulting in unpleasant sensory characteristics and/or degradation. TaJbl. 1962.. J. C. Temkin. such as lumpiness and caking. were attributed to this incipient liquid state. i. B. Eng. A. porous particles with better rehydration and handling characteristics and/or more pleasing and consistent color. 28. Fundam. A t higher temperatures and/or humidities. of the order of 10l2Pa. 68. detergents.: Simons. Hermosillo. 0196-4313/82/1021-0447$01. 3 . J. often of high molecular weight. F. have also been used to combat stickiness in spray drying (Brennan et al. J. they reconstitute less readily. This can lead to lower product yields. S. Catal. Weisz. Receiued for reuiew September 28. because the cakes are less porous. easily handled and stored products in an economical fashion. E. In their model. water absorbs on particle surfaces. 265. B. Chem.-. Cincinnati. 45.Ind.1946. Rev. forming a saturated solution and thereby making the particles sticky and capable of forming 0 1982 American Chemical Society . & e m . Berkeiey. and pharmaceuticals. so that surfaces become sticky and clusters form via particle collisions and adherence.. Tg.. J. 'Mezquital de Oro. V. White and Cakebread (1966) recognized dried liquid foods as amorphous glasses. Viscosities corresponding to experimentally measured sticky-point temperatures fell consistently within the range 0. Downton. Klnet. A familiar example of stickiness is caking during storage. J .e. thereby lending support to the proposed mechanism and quantitative model. Several techniques. Ind. Amorphous Powders Galen E. 1972. P. For heat-sensitive products this can also lead to overheating. Eng. as well as repeated contact. 24. 1971. H. 21. 52. J. P. Rev. amorphous powders are interpreted in terms of a mechanism of viscous flow driven by surface energy during particle contact. Soc. (Frankfurt am Main) 1957. caking. or a fine mist of water. D. are available for producing dried powders from a wide range of raw materials including liquid foods. Stickiness defects. which occurs when particles which are insufficiently dry collide with one another or with the walls of the drying apparatus and become stuck. R. with moisture contents in the range of 2 to 7% w/w. Chem.. Introduction Dehydration of liquid materials is widely used to produce stable. Viscosity measurements of the bulk-solution specimens were made with both a falirg-baii method and a rheogoniometer.. There is as yet no quantitative model which describes the mechanism of stickiness in dried powders and explains the success of failure of past approaches to the problem. University of Callfornia. is agglomeration. Various additives.1977). 1. E. Prater. 8 . M.1973. plastics. Ab. E. Flores-Luna. Cafai. a process commonly used with dehydrated powders to obtain larger. shape.b) and in powders (Peleg and Mannheim. 1976. N. 367. Smith. Vllladsen. Sinfelt. Chem.. and agglomeration tendencies of hygroscopic. Gupta. W. 6210 Center Hill Road. 1962. Stewart. Peleg and Mannheim (1977) attributed caking of onion powder to moisture absorption and proposed a humidity-based caking mechanism. temperatures below Tg.s (Jones. Eng. T. J . Sci. D. 1954. Coffee Division. 1978a. AIChEJ. Relat. The Winton Hill Technical Center. 1981 Accepted May 7. Carbeny. I . S. M. with a lower viscosity. 1982 Mechanism of Stickiness in Hygroscopic. 117. Both bulk-solution and : powdered specimens of a 7l w/w mixture of sucrose and fructose were prepared. such as spray drying. Mexico. J.. Kafal. Gupta. P. Fundam. fertilizers. and appearance. J. Coping with stickiness in spray dryers and in powdered products and achievement of successful agglomeration have largely been matters of trial-and-error experimentation to find conditions which avoid or control the sticky characteristics of a given material. 143. 3. the glass assumes more of a liquid nature. The mechanism predicts that stickiness should occur for combinations of temperature and moisture content corresponding to viscosities of the amorphous material below some relatively constant value.25/0 operating problems. Procter and Gamble Company. Boudart. which for short-time contact should be within the range loe to 10' Pas. Wanke. Sub/. California 94720 Sticking.. Z . 1989. This operation is redly one of controlled stickiness. A. B. Judson King' Department of Chemical Engineering. 509. Cooling the dryer walls and flushing them with cool air have been employed to avoid stickiness in spray dryers (Lazar et al. 1 7 . and powder-handlingdifficulties. which can be turned into an attribute.. One phenomenon frequently encountered during production and storage of these dried powders is stickiness. E. 1982. metastable. 6. OH 45224..3 X lo7 to 4. C9fel. J. 1973. moist air. Hygroscopic dried foods such as instant coffee or drink mixes tend to form hard cakes when subjected to high temperatures and/or humidities. 1956. Madon. Apdo. J . Cafal. thereby explaining the inverse relationship between sticky-point temperature and moisture content for such powders. Chem. supercooled liquids below their glass-transition temperature. particles are deliberately subjected to steam. viscosity is exAt the tremely high. c 447 . 3 . 75. 175. 1966. Weisz.b). I 1 I . In spray drying. The powder is no longer free-flowing and. amorphous sugars-from being successfully dehydrated. H. Fuzek.: Hicks. Another example of stickiness. 1956). 1969. The viscosity is affected by both moisture content and temperature. Postal 138. (3. These problems are preventing some materials-notably fruit juices which contain large amounts of hygroscopic. 77.0 X lo7 Paos. 1969. Welsz. 447-451 Segal.