Chemical Engineering Science 62 (2007) 4992 4997 www.elsevier.

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Role of gas-phase chemistry in the rich combustion of H2 and CO over a Rh/Al2 O3 catalyst in annular reactor
Matteo Maestri, Alessandra Beretta , Tiziano Faravelli, Gianpiero Groppi, Enrico Tronconi
Dipartimento di Chimica, Materiali e Ingegneria Chimica Giulio Natta, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy Received 16 June 2006; received in revised form 27 December 2006; accepted 28 January 2007 Available online 12 February 2007

Abstract Experiments of H2 and CO fuel rich combustion, performed in an isothermal annular reactor over a Rh-catalyst, are herein analyzed by means of a 2D isothermal model. The model incorporates previously derived molecular surface kinetics of H2 and CO combustions as well as established detailed kinetic schemes for H2 and CO gas-phase combustions, developed by Ranzi and co-workers, which allowed to evaluate the relative role of heterogeneous and homogeneous reactions. In line with the experimental evidence, homogeneous ignition of the H2 /O2 mixture was predicted to occur above 650 C (though it was retarded by the presence of the surface reaction), while this did not occur for the CO/O2 mixture (only heterogeneously consumed). For both reaction systems, intermediate temperature windows were identied wherein the observed conversions exceeded the diffusion limit and could not be explained by the combined heterogeneous/homogeneous model. Radical seeding simulations showed that a low-temperature promotion of the gas-phase conversion of H2 can be explained by a proper temperaturedependent enrichment of radical species; however, the effect seems hardly consistent with the desorption of adsorbed intermediates, thus the indications are not conclusive on the existence of an interaction between surface and gas-phase chemistries. 2007 Elsevier Ltd. All rights reserved.
Keywords: Heterogeneous/homogeneous kinetics; H2 rich combustion; CO rich combustion; Annular reactor; Catalytic partial oxidation; Rh/Al2 O3 catalyst; 2D Reactor modeling

1. Introduction The catalytic partial oxidation (CPO) of methane and C2+ hydrocarbons has been extensively studied in the recent literature as an alternative route for the production of CO and H2 mixtures. The high void fractions which characterize the short contact time reactors, in combination with the high temperatures reached under autothermal operation suggest the possibility of the onset of homogeneous reactions, that can affect the selectivity of syngas and the reactor thermal behavior. In the case of methane, the literature suggests, after the results of experimental and theoretical investigations, that the production of synthesis gas in noble metal autothermal reactors is mainly due to the heterogeneous chemistry, that leads to the complete consumption of O2 , the limiting reactant, within a narrow

Corresponding author. Tel.: +39 0223993284; fax: +39 0223993318.

E-mail address: alessandra.beretta@polimi.it (A. Beretta). 0009-2509/$ - see front matter doi:10.1016/j.ces.2007.01.060 2007 Elsevier Ltd. All rights reserved.

reactor length (Deutschmann and Schmidt, 1998; Goralski et al., 2000; Quiceno et al., 2006). However, in a previous work (Maestri et al., 2005) we showed, through the application of a 1D dynamic model to the simulation of xed bed autothermal reactors with different support geometries (honeycombs vs. foams vs. small spheres), that at high ow-rates conditions favorable to gas-phase reactions can establish, wherein high temperatures, unconverted oxygen and synthesis gas co-exist. In this work, experiments of rich combustion of H2 and CO were performed in an isothermal annular reactor, under mass transfer limited consumption of O2 , thus reproducing conditions which may occur in short contact time CPO reactors. In order to evaluate the potential role of radical reactions, a quantitative interpretation of the experimental results was addressed. This demanded for the development of a 2D model of the annular reactor, which incorporates both the heterogeneous and the homogeneous kinetics and has the characteristics of robustness and reliability necessary to deal with the complexity of a process with strong radial and axial gradients.

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2. Experimental In a previous work (Tavazzi et al., 2006), catalytic tests of H2 and CO combustion were performed in an annular reactor as a part of a kinetic investigation on the production of CO/H2 mixtures via partial oxidation of CH4 over a 0.5% Rh/Al2 O3 catalyst. The reactor was composed by an internal mullite tube, over which the catalytic layer was deposited (1.5 cm long, 4050 m thick), coaxially inserted into an outer quartz tube; the gas mixtures owed in laminar regime through the annular duct (with geometry: aspect ratio = 0.5277, outer radius = 9 mm). The reactor was positioned inside a tubular furnace. Experiments of H2 and CO combustion were performed under rich conditions (H2 /O2 /N2 =4/1/95 and CO/O2 /N2 =4/1/95%v/v) and high ow-rates, according to the intent to reproduce the same conditions that prevail in the CH4 partial oxidation at very short contact times. The moisture content in the feed gases was limited to very few ppm. The effective dissipation of the reaction heat by radiation helped realizing catalytic tests under quasi isothermal conditions (thermal gradients lower than 10 C/cm). 3. Mathematical model A dynamic isothermal isobaric 2D model of the catalytic annular reactor was developed. Model equations are reported in Table 1 along with the boundary conditions. Fully developed laminar ow in concentric annular ducts was assumed (Shah and London, 1978). Physico-chemical properties, including molecular diffusivities, were estimated according to the CHEMKIN correlations (Kee et al., 1987); intraporous
Table 1 Model equations
Mass balance equations for the ith component: u() j i Di j i = + 2 jt L jz RO (1 R )2 where: R 1 j2 i j i + 2 1 + (R 1) j j +

diffusional resistances were accounted for by-isothermal effectiveness factor using the generalized Thiele modulus method (Maestri et al., 2005). The effective intraporous diffusivities were calculated according to the Wakao and Smith (1962) correlation, neglecting the contribution of micropores, assuming an average pore diameter equal to 100 nm (monomodal pore distribution) and a macropore void fraction of 0.6 after the results of Hg porosimetry measurements (Tavazzi et al., 2006). The model consists of NC partial differential equations with three independent variables (time, radial and axial coordinates), where NC is the number of species in the system. The equation system was solved numerically by the method of lines (Finlayson, 1980); namely, the model equations were discretized along the axial and radial coordinates by backward differences. For the time integration of the resulting ODE system the C++ Class BzzDaeDoubleStiff of the BzzMath 5.0 library (Buzzi-Ferraris, 2006) was used. Convergence of the solution in time was checked by the internal criteria of the integrator, whereas for the axial convergence an adaptive mesh criterion was used. Details about the numerical methods are given elsewhere (Maestri et al., 2007). The following steady-state molecular rate expressions for CO and H2 combustion over Rh were incorporated: RH2 = kH2 pH2 and RCO = kCO pCO with 1 1 T 773

kH2 = 2 103 exp 5000

Di j2 i + Rihom MW i L2 jz2

RO r ; RO R I

z =

z ; L

R =

RI RO

Boundary conditions:

=0:

j i j

=0

= 0,

z ,

=1:

Di j i RO (1 R ) j Di j i L u jz

=1

= Rihet wcat MW i ,

z ,

z = 0 :

z =0+

=(

i,0+

i,0 ),

z = 1 :

j i jz

z =1

= 0,

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and kCO = 9 10 exp 7000 1 1 T 773

60

.
50 CO conversion [%] 40 30 20 10 0 0 100 200 300 400 500 600 700 800 Taver. catalyst [C]

Rates R are expressed in (mol/kg/s), p in (atm) and T in (K). is a limiting factor (dened as pO2 /106 +pO2 ) that translates the zeroth kinetic order of oxygen, except when approaching complete O2 conversion. These simple rate expressions are part of a kinetic scheme of CH4 partial oxidation over Rh catalyst, developed on the basis of a wide experimental campaign in annular reactor at high space velocity (Tavazzi et al., 2006; Maestri et al., 2005). To evaluate the role of the homogeneous chemistry, the detailed kinetic schemes for H2 and CO gas phase combustion developed by Ranzi and co-workers were incorporated in the model. The whole set of reactions and their kinetic parameters are reported elsewhere (Ranzi et al., 1994; Frassoldati et al., 2006). 4. Results and discussion 4.1. Experimental trends

60 50

H2 conversion [%]

Three levels of ow-rate were investigated (0.274, 0.548 and 1.096 Nl/min), but only at the highest one the conversion of oxygen (the limiting reactant) and fuels could be limited within a kinetically relevant range. For that case (corresponding to the space velocity of 7.6 106 Nl/kgcat/h referred to the catalyst load), Fig. 1 shows the measured trends of CO and H2 conversion at increasing catalyst temperature. The rich combustions of CO and H2 were fast and very fast processes, respectively. CO oxidation started at about 250 C and conversion rapidly grew with temperature. H2 rich combustion started at about 100 C; the reaction was so fast that, in the temperature range 100150 C a step-wise increase of the reactant consumption occurred. At higher temperatures, the slope of the conversion proles decreased and the consumption of reactants increased more gradually; at about 690 C a sharp increase of the reactants conversion up to the complete consumption of O2 and 50% consumption of H2 was observed. 4.2. Heterogeneous model The modeling analysis consisted of an initial investigation on the limiting case of a purely heterogeneous reaction process (gas-phase reactions neglected, Rihom = 0 in Table 1). Simulation parameters are listed in Table 2. As shown in Fig. 1, the agreement between predicted and measured fuel conversion was good at low temperatures for both reaction systems; however, at temperatures higher than 300 C for the H2 /O2 system and 450 C for the CO/O2 system the simulations systematically underestimated the experimental data. The analysis of the calculated concentration proles showed that in the range of low to medium temperatures the annular reactor worked under a mixed chemicaldiffusional regime (the calculated radial gradients were smooth and the wall concentration of oxygen was not zero). Above approximately 450 C for the case of CO

40 30 20 10 0 0 100 200 300 400 500 600 700 800 Taver. catalyst [C]

Fig. 1. Comparison between experimental and predicted conversion of fuels at different catalyst temperatures: (a) CO conversion: symbols = experimental data, solid line = prediction of the heterogeneous model; (b) H2 conversion: symbols = experimental data, solid line = prediction of the heterogeneous model, dotted line = prediction of the homogeneous/heterogeneous model. Flow-rate = 1.096 Nl/min, GHSV = 7.6 106 Nl/kgcat/h, Fuel/O2 /N2 = 4/1/94 v/v.

Table 2 Simulation parameters

Inner radius (mm) Outer radius (mm) Reactor length (mm) Catalyst weight (g) Operating pressure (atm) Flowrate (Nl/min) 2.35 4.50 15 0.0082 1 1.096

combustion and 300 C for the case of H2 combustion, instead, the reactor entered a mass transfer limited regime; steep radial gradients for the oxygen concentration with practically zero concentration at the catalytic wall were in fact predicted.

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The high temperature diffusional asymptotes predicted by the model were successfully checked against those expected from the analogy between gas/solid mass transfer in the annular reactor and heat transfer in a concentric annular duct with adiabatic outer wall and constant temperature inner wall (Shah and London, 1978). In fact, the calculations of the present 2D heterogeneous model were fully in line with those of a previously developed and validated 1D model of the annular reactor relying on the same analogy (Tavazzi et al., 2006). 1D mass transfer correlation were validated by comparison with asymptotic trends of O2 conversion in CH4 CPO experiments (Tavazzi et al., 2006). Concerning internal mass transfer, the low fuel concentrations in the diluted streams of our runs rule out significant errors due to neglecting multicomponent diffusion. Thus the discrepancy between model predictions and experimental data cannot be ascribed to a lack of adequacy either of the heterogeneous kinetic expressions, or of the transport part of the model. 4.3. Homogeneous model Simulations were then performed considering the other limiting case of a purely homogeneous reactor (surface reactions neglected, Rihet = 0 in Table 1). At the highest ow-rate of 1.096 Nl/min, in the temperature range 100700 C, no gasphase conversion of the CO/O2 rich mixture was predicted. Conversely, the H2 /O2 mixture is more reactive and ignition was predicted to occur at 648 C; it presented an onoff trend, with absence of any effect below the threshold temperature and abrupt attainment of complete O2 conversion above it. Analysis of the calculated ignition dynamics (which will be discussed in detail in a forthcoming full-paper, Maestri et al., 2007) reveals that this step-wise effect is associated with the back-end mechanism of formation of a radical pool followed by a backward propagation of the reaction front, driven by axial diffusion; eventually, a steady-state solution is reached, wherein the process is conned at the entrance of the reactor and the limiting reactant is completely consumed. 4.4. Heterogeneous/homogeneous model In the case of the CO/O2 reaction system, incorporation of the homogeneous scheme in the heterogeneous reactor model did not affect the simulations within the range of investigated temperatures. The response of the heterogeneous/homogeneous model and that of the purely heterogeneous model, thus, were totally coincident and the underestimation of the measured CO conversions kept unchanged. In the case of the H2 /O2 reaction system, Fig. 1(b) compares the predictions of the heterogeneous/homogeneous model with the experimental trend at high ow-rate. The inclusion of the homogeneous chemistry in the heterogeneous model had no effect for temperatures lower than 654 C, the threshold at which the step-wise onset of the gas-phase reactions was predicted (the calculated H2 and O2 conversion abruptly reached 50 and 100%, respectively); thus, model simulations still un-

derestimated the experimental data in the temperature range 300650 C (in analogy with the purely heterogeneous model), but described well the measured conversion at high temperatures (Table 2). In line with the literature (Vlachos, 1996; Appel et al., 2002), it was found that the presence of the catalytic reaction slightly retarded the gas-phase ignition (648 C vs. 654 C). A sensitivity analysis showed that this effect is due to the inhibiting effect of water, produced at the catalyst wall, on gas-phase reactions; such an inhibition is related with the high third body efciency of H2 O in the H + O2 + M = HO2 + M reaction. The same factor inuences also the dynamics of ignition; the analysis of transient solutions showed in fact that the initial build-up of the radical pool occurred at the back-end of the reactor but far from the catalytic surface; the reaction front tends thus to propagate both radially towards the catalytic wall and backwards along the axial coordinate. At steady state, the homogeneous process practically replaces the catalytic process so that the reactants are mainly consumed at the inlet of the reactor within a relatively small gas-phase volume. For temperatures higher than 300 C, but lower than the homogeneous ignition temperature, the difference between predicted and experimental data could not be explained by the simple superposition of the independent solid-phase and gas-phase reactions. 4.5. Radical seeding In order to evaluate the possible role of an interaction between the surface and the gas-phase chemistries, the sensitivity of the model to the addition of trace amounts of radical species was analyzed. The case of the H2 /O2 reaction system was considered and surface reactions were neglected for simplicity (purely homogeneous model, Rihet = 0 in Eq. (3)). This methodology of investigation had been adopted by Davis and Schmidt, 1999) in the case of methane fuel rich combustion. Fig. 2 reports the calculated proles of oxygen conversion vs. temperature, which were obtained by simulating the enrichment of the feed stream with increasing amounts of the radical O in the range of mole fractions 106 104 . In contrast with the ndings of Davis and Schmidt for the CH4 /O2 system, it was found that the gas-phase conversion of H2 and O2 is highly sensitive to the co-feed of radicals. Two main effects manifest and affect the shape of the ignition curve: on one side it is observed that high values of conversion are reached at progressively lower temperatures (anticipation of the ignition), on the other side a low-temperature tail appears in the conversion vs. temperature curve, which smoothens the trend into a S-shaped prole. The co-feeding of radicals resulted in fact in a slight increase of the reactants conversion in the range 300 < T < 600 C. Such a low-temperature contribution to the gas-phase conversion is a peculiar effect, distinct from the true ignition of the gas-phase process occurring only at higher temperatures. The calculated axial concentration proles (herein not reported for brevity) show that the enrichment of O causes a fast reorganization among radical and molecular species, with consequent formation of a small amount of

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extend the investigation to include the interaction between surface and gas-phase, thus verifying whether the release of adsorbed radicals from the catalyst surface can explain a promotion of the gas-phase reactions at intermediate temperatures, a detailed kinetic scheme of the catalytic process must be implemented. The simple heterogeneous kinetics considered at this stage are in fact inadequate at the scope: a dedicated treatment will be the subject of a future work. Notation Di L MW i pi r RI RO Rihom Rihet t T u wcat z diffusivity of species I in the mixture, m2 /s reactor length, m molecular weight, kg/kmol partial pressure, atm radial coordinate, m inner radius of annular duct, m outer radius of annular duct, m production rate of i-species due to gas-phase chemistry, kmol/m3 /s effective production rate of i-species due to surface chemistry, kmol/kgcat /s time, s temperature, K axial velocity, m/s catalyst load, kgcat /m2 reactor axial coordinate, m

Fig. 2. Lines: oxygen conversion predicted by the homogeneous model vs catalyst temperature for the ow-rate equal to 1.096 Nl/min for different values of O radical seeded in the feed stream. Symbols: calculated gap between measured oxygen conversions and predictions of the heterogeneous/homogeneous model.

H2 O (thus a small net consumption of reactants) right at the entrance of the reactor; such amount increases with increasing reactor temperature. At low-temperatures (below 500 C) the phenomenon is localized and does not propagate throughout the reactor length; at high temperatures, this effect combines with the back-end build-up of the radical pool, which results in progressively increasing conversions along the axial coordinate. The effect is not specic of the radical O. The same qualitative result was obtained by seeding other radicals (e.g. H, OH), though different seeding efciencies were found, in line with the results of Davis and Schmidt, 1999). To better visualize the outcome of the sensitivity analysis, Fig. 2 also displays in symbols the calculated gap between the conversion of H2 as predicted by the heterogeneous homogeneous model and the experimental measurements, in the range 300650 C wherein measured conversions were higher than the diffusional limit. Qualitatively, the comparison suggests that the observed promotion of conversion could be explained by the release of radicals from the catalyst surface, provided that the amount of seeded radicals decreased with increasing temperature. However, this is inconsistent with the thermodynamics of desorption. Also, the amount of radicals that at 300400 C could explain an appreciable contribution of the gas-phase reactions to H2 conversion is greater than 5 104 , which appears a relatively high concentration as compared to typical surface coverages of intermediate species. 5. Conclusive remarks The present work provides a quantitative analysis of the CO/O2 and H2 /O2 reaction systems under the assumption of non-interacting heterogeneous and homogeneous chemistries. The analysis points out systematic deviations between model and experiments at intermediate temperatures. In order to

Greek letters kinetic limiting factor for O2 dependence, dimensionless density kg/m3 mass fraction, dimensionless References
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