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Chemical Engineering Journal xxx (2012) xxx–xxx

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Chemical Engineering Journal
journal homepage: www.elsevier.com/locate/cej

Steam methane reforming reaction process intensification by using a
millistructured reactor: Experimental setup and model validation for global
kinetic reaction rate estimation
M. Mbodji a,⇑, J.M. Commenge a, L. Falk a, D. Di Marco b, F. Rossignol b, L. Prost c, S. Valentin c,
R. Joly c, P. Del-Gallo c
a

Laboratoire Réactions et Génie des Procédés, CNRS-Université de Lorraine, ENSIC, 1 rue Grandville, BP 20451, 54001 NANCY Cedex, France
Laboratoire des Science des Procédés Céramiques et Traitements de Surface, 12 rue Atlantis, 87068 Limoges Cedex, France
c
Air Liquide, Centre de Recherche Claude & Delorme, 1 chemin de la porte des Loges, BP 126, 78354 Jouy-En-Josas Cedex, France
b

h i g h l i g h t s
" Millistructured reactor is suitable for kinetic study of fast reactions.
" SMR process can be intensified with respect to energy efficiency and process size.
" SMR kinetics depending on catalyst microstructure is developed and validated.
" Highly-active Rh catalyst is suitable for industrial SMR process intensification.
" Hydraulic diameter of 400 lm is needed to suppress transport phenomena limitations.

a r t i c l e

i n f o

Article history:
Available online xxxx
Keywords:
Microstructured reactor
Methane reforming
Syngas
Hydrogen
Process intensification
Microreactor modeling
Kinetic data acquisition

a b s t r a c t
In the frame of steam methane reforming process intensification, a highly active and stable catalyst based
on rhodium with catalyst formulation and structure adapted to millistructured reactors has been formulated. This catalyst has been tested in industrial conditions (800, 850 or 900 °C and 20 bars) on a single
channel which is representative of one channel of a more complex millistructured SMR reactor. Then, a
detailed mathematical model for acquisition of the global reaction kinetics with this new catalyst has
been developed and validated from experimental catalytic tests. The developed kinetics is dependent
of the catalyst microstructure. This study presents the set-up, the model, the experimental catalytic runs
and the global kinetics estimation protocol. It demonstrates, on one hand, that millistructured reactor is
suitable for kinetic data acquisition and, on the other hand, the possibility of SMR process intensification,
for improved energy efficiency and process size reduction.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction
Steam methane reforming (SMR) of natural gas is the main
commercial process for synthesis gas production (H2, CO). In this
process, methane reacts with steam to produce a mixture of hydrogen, carbon dioxide and carbon monoxide. This reaction is highly
endothermic and is performed in the presence of a catalyst such
as nickel or rhodium at high temperature (800–1000 °C), high pressure (20–40 bars) and steam-to-carbon ratio varying between 1.8
and 4. In the classical process, a set of tubes filled with catalyst
is operated inside a furnace equipped with burners. These burners
provide the heat needed for the reaction. The exit temperature of
⇑ Corresponding author.
E-mail address: mamadou.mbodji@ensic.inpl-nancy.fr (M. Mbodji).

the process gas ranges from 700 to 950 °C. These conditions are
limited by the tube metallurgy. The reactor tube has a length of
10–12 m and an internal diameter in the order of 10 cm. This process is well known and controlled. However, the overall efficiency
of the process is decreased by heat losses. The intensification of the
SMR process by using microstructured reactors should enable on
the one hand to resolve this heat losses problem and on the other
hand to reduce substantially the size of process units, their energetic consumption and their environmental impact [1,2]. The high
surface-to-volume ratio of microstructured reactors provides a
highly efficient heat transfer and reduces the potential for temperature gradients in catalyst layers deposited on microchannel walls
when performing highly endothermic reactions. Compared to
conventional fixed-bed catalytic reactors, microstructured reactors
advantages are considerable particularly in terms of yield,

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.07.117

Please cite this article in press as: M. Mbodji et al., Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.117

Zeppieri et al. Nickel is the most common industrial catalyst used for SMR owing to its robustness. Their experiments were performed in the temperature range 600–840 °C.cej. Mbodji et al. they appear to be a very good tool for the acquisition of kinetic data and also for the determination of catalyst behavior and activity [3. Leventa et al. Over the temperature range 1000–1500 K.07. They found that the steam reforming reaction time scales for rhodium and nickel depend more on the reaction temperature than mixture composition. therefore. The pressure range was 2. Zeppieri et al. Review of SMR reactors Reactor miniaturization is known to improve heat and mass transfer. Microreactors are increasingly used as tools for catalytic activity measurement. and heavy metals. [8] bear Rsm Sco Tg Ts Tc uc XCH4 yg.3 K.5–2 and steam-to-methane ratio 2–3. J. The radial temperature gradient in the packed-bed reactor and in microchannel reactor by using 2D models for each type of reactor was also investigated. Steam acts as an inhibitor on the catalyst activity and the reaction rate.4].g Dh F0 FCH4.2012. The maximum temperature difference in the packed bed reactor was about 15 K whereas that in the microchannel reactor was only 0. Their results show that SMR reaction rate is first order with regard to methane and 0th order with regard to steam.5–9 bars. this strategy is not always sufficient for process intensification. http://dx. Noble metals such as ruthenium. Chem. However. rhodium. Mbodji et al.1016/j.j stoichiometric coefficient of species j in reaction i (–) k thermal conductivity of the gas (W/m/K) DrH850°C heat of reaction at 850 °C (J/mol) Dimensionless numbers Gzth thermal Graetz number (–) Gzm material Graetz number (–) Nu Nusselt number (–) Pr Prandtl number (–) Re Reynolds number (–) Sc Schmidt number (–) out these affirmations. [7] confirm that the rhodium–perovskite catalyst is the most active: high methane conversion close to the theoretical thermodynamic value is experimentally obtained with a low quantity of catalyst.01–1 g). The high selectivity of H2 is attributed to improved heat management in the microchannel. an increased steam-to-methane ratio in the feed moves the reforming reaction in the opposite direction. They found that the increase of H2-to-CH4 ratio in the feed enhances the catalyst activity. Eng. These results show that Please cite this article in press as: M. [7] investigate the kinetics of methane steam reforming reaction over a rhodium–perovskite catalyst of formula BaRhxZr(1x)O3 at atmospheric pressure and in the temperature range 723–1023 K. carbon deposition is lower than on a commercial nickel-based catalyst.0 Finert hloc kd. the steam reforming on rhodium is faster than on nickel by a factor of 3 to 20. (2012).doi. [10] studied steam reforming of ethanol over 2%Rh/20%CeO2/Al2O3 catalyst in a microchannel reactor. and palladium are also suitable for SMR.117 . such as sulfur.2 M. They compared microchannel reactor performance with that of a packed-bed reactor using 2%Rh/20%CeO2/Al2O3 catalyst at identical operating conditions and found the same activity but the selectivity to desired product was higher in the microchannel reactor. this change in production technology must be coupled to the development of highly active and stable new catalysts in order to ensure the same conversion rate at lower residence times and catalyst formulations adapted to microreactors. The H2 yield obtained in the microchannel reactor was 65 L/g/h as compared to 60 L/g/h in the packed-bed reactor. chloride. Stefanidis and Vlachos [6] studied the intensification of steam reforming of natural gas and tested whether steam reforming on nickel is feasible by intensifying the process via miniaturization. Furthermore. / Chemical Engineering Journal xxx (2012) xxx–xxx Notations Am R r1 active surface of active metal per mass of rhodium (m2sma /grhodium) total concentration in the gas phase (mol/m3) hydraulic diameter of the reactor (m) total molar flow rate of reactants (mol/s) molar methane flow rate at the reactor inlet (mol/s) molar flow rate of inert species (mol/s) heat-transfer coefficient between the gas and the walls (W/m2 K) mass-transfer coefficient between the gas and the catalytic wall (m/s) total pressure (Pa) contact perimeter between the catalytic bar and the gas (m) contact perimeter between the thermocouple and the gas (m) external reactor perimeter (m) contact perimeter between the catalytic bar and the reactor (m) contact perimeter between the gas and the reactor walls (m) universal gas constant (J/mol K) rate of the SMR reaction (mol/m2SampleSurface s) r2 rate of the WGS reaction (mol/m2SampleSurface s) Rsc thermal resistance between the catalytic bar and the reactor (m2 K/W) CT. Peela et al.j yc. Microreactors are also characterized by the use of very small reactants and catalyst quantities (usually in the range 0.1. Methane conversion is proportional to the partial pressure of methane and the contact time. Catalyst intensification is also needed to avoid hot spots [5]. Below this range. however. However. [9] studied SMR in a microreactor filled with an industrial catalyst containing 15% nickel.. Results from Iglesia et al. resulting in a more uniform temperature throughout the catalyst. steam reforming on rhodium is one order of magnitude faster than on nickel. 1.j z thermal resistance between the thermocouple and the reactor (m2 K/W) CO selectivity (–) gas temperature (K) reactor skin temperature (K) catalyst temperature (K) gas velocity (m/s) methane conversion (–) gas phase molar fraction of species j (–) molar fraction of species j in the catalyst (–) axial position along the channel (m) Greek notations a ratio between the height and the width of the reactor (– ) l dynamic gas viscosity (Pa s) ti. with hydrogen-to-methane ratio of 0.j P Pcg Pmg Ps Psc Psg selectivity to the desired product and safety. They also observed that the smaller diameter of the microreactor enabled decreasing the catalyst quantity and acquisition of reaction kinetics at high temperatures up to 840 °C without reaching equilibrium. its catalytic activity and its relative tolerance to poisons. Comparing the performances of a rhodium– perovskite catalyst to a commercial nickel-based catalyst.org/10. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation.

Eng. The main goal of this work is to determine SMR and WGS kinetics reactions rates from experimental catalytic tests. Furthermore.07.3. Under these conditions.117 . Carbon formation. therefore only SMR reaction kinetic rate is studied is this work. Gibbs free energies of reactions (DrG) as a function of temperature. It is usually resolved by using a catalyst and a reactor material on which carbon formation is unlikely. 0 -20 -40 -60 -80 -100 600 SMR RM Methane cracking WGS Boudouard CO reduction 650 700 750 800 850 Temperature [°C] Fig. The present study is focused on syngas production by steam methane reforming in a millistructured reactor. on which catalytic tests have been performed. Thermodynamic analysis presented above shows that the water gas shift reaction is negligible in the operating conditions. Mbodji et al. (2012). In order to ensure a good mixture of the reagents.1016/j. Experiments are conducted at 800 °C. 1. Material and methods 2. Mbodji et al. Chem. 1. which are the most-commonly considered reactions when modeling steam methane reforming process.2012. outlet gas temperature and calculated values given by the reactor model. Reaction Name DrH850°C (kJ/mol) 1 2 3 4 5 6 Steam reforming reaction Reverse methanation Water gas shift Methane cracking Boudouard CO reduction 226 193 33 90 169 135 The reactor model developed in this work takes into account the SMR and WGS reactions. SMR. Experimental test rig The experimental set-up.doi. Catalysts based on Rh/Al2O3 enabling to reach high conversion at low residence times have been developed and tested.4. / Chemical Engineering Journal xxx (2012) xxx–xxx 1. reactor and catalyst intensification are increasingly controlled. in our operating conditions (above 800 °C and 20 bars). Indeed. As steam reforming is the major reaction. Results confirm the performance enhancement in microchannel reactors. is shown in Fig. all experiments are carried out above 800 °C.org/10. harmful to the operation of production units. the estimation of the kinetics reaction rate then consists in finding the pre-exponential rate constant and the activation energy for the SMR reaction. 20 bars and a steam-to-methane ratio of 3. 1.3 M.. Water gas shift reaction  and the exothermic water gas shift (WGS) CO þ H2 O () H2 þ CO2 ð3Þ The main drawback of SMR is the risk of carbon formation. The following sections present the experimental set-up and the model developed for data treatment. Description of the reacting system The following chemical reactions should be expected when performing steam methane reforming:  the endothermic steam reforming reaction (SMR) CH4 þ H2 O () 3H2 þ CO ð1Þ  the reverse methanation reaction (RM) CH4 þ 2H2 O () 4H2 þ CO2 40 20 Reaction Gibbs Free Energy [kJ/mol] microchannel reactors significantly reduce the temperature gradient over the reactor cross-section due to their high heat-transfer coefficient. 2. In Table 1 are reported the heats of these six reaction. 850 °C or 900 °C. Experimental results show that rhodium catalyst supported on MgO– Al2O3 is highly active and stable over a wide range of steam-to-carbon ratios and resistant to coke formation. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. [11] assessed methane steam reforming over Rh/ MgO–Al2O3 catalysts in microchannel chemical reactors.cej. J.1.2. 2. can be limited by using an excess of oxidizing agent as H2O. Thermodynamic analysis The Gibbs free energies (DG) of the most significant reactions occurring during steam methane reforming are given as a function of temperature in Fig. All of these studies show that currently methane steam reforming intensification is feasible. Carbon formation from methane cracking is catalyzed by chromium and iron and can be considered as a selectivity problem. According to these thermodynamic data. Care must be taken to avoid carbon formation due to:  methane cracking CH4 () C þ 2H2 ð4Þ  the Boudouard reaction 2CO () C þ CO2 ð5Þ  and CO reduction CO þ H2 () C þ H2 O ð6Þ Table 1 Reaction heats of steam reforming and carbon formation reactions. Wang et al. Methane steam reforming reaction rate on this catalyst in microchannel reactor was compared to that of a conventional micro-tubular reactor. The CO2 quantity recorded during catalytic tests was not significant. the global system can be considered as endothermic. RM and methane cracking are the most favorable reactions. and Gibbs free energy of the WGS reaction is positive for temperatures greater than 800 °C. a gas mixer and pre-heater is set before the reactor Please cite this article in press as: M. http://dx. ð2Þ 1. The experimental results coupled with a mathematical plug-flow reactor model taking into account heat and mass transfer between the reactant gas and the catalyst enables identification of the kinetic parameters (activation energies and pre-exponential rate constants) of SMR reaction by minimizing the sum of squared difference between measured methane conversion.

that contains the catalytic coated sample and CC3 denotes the oven around the non-catalytic part of the reactor. CC2 denotes the oven around the catalytic reactor itself. J. A mobile thermocouple is installed on the top wall of the inner channel in order to monitor the gas temperature along the reactor. three heat-transfer parameters need to be determined:  hloc: mean heat-transfer coefficient between the flowing gas and the internal walls.6 mm height and 47. Picture of the experimental setup exhibiting the reactor in the open furnace.07. (2012).117 .0017 to 0. 3a. The reactor model presented in this paper concerns the CC2 part without considering the non-catalytic reactor activity. 2. the set-up is equipped with a condenser and a weighing system for measurement of the mass of condensed water. Experimental temperature measurements have been performed for determining these three heat-transfer parameters.org/10.  Rsm: contact thermal resistance between the thermocouple and the reactor. In-line infrared analyzer is also used to analyze gases composition. the full reactor model is not presented in details. This is performed by coupling two reactor models in series. The total gas flow rate ranges from 0. Mbodji et al. 3a) and a cross-sectional view (Fig.0079 mol/s in order to operate with residence times between 40 and 200 ms in the CC2 part Fig.5 mm width. the part of conversion coming from the reactor metal alloy has been evaluated experimentally before and after the catalytic tests. Longitudinal view of the reactor.1. In order to estimate the fraction of conversion due to the reactor walls. reactor activity is quantified by fitting experimental emptyreactor conversion after catalytic tests. Chem. Eng. Four thermocouples are also set on the reactor outer skin to measure the temperature profile along the reactor. by using the full reactor model. In the CC2 part of the reactor. 3b) of the reactor with all geometric perimeters of interest that will be considered in the model for heat and mass transfer.. only the non-catalytic reactor activity of the walls is considered.doi.6 mm height and 20 cm length) coated with a rhodiumbased catalyst is introduced. 2. the model considers the two active areas: the reactor walls and the catalyst. whereas in the CC3 part. To provide the required heat to the endothermic reaction.  Rsc: contact thermal resistance between the catalytic bar and the reactor.75 cm length) within which a small bar of alumina (with dimensions of 5 mm width. This oven CC3 is used to prevent temperature gradient in CC2 and provide controlled temperature conditions to the reaction. Mbodji et al. 1. Fig. The reactor consists of a rectangular channel (with dimensions of 5. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. Experimental catalytic tests conditions The following experimental conditions have been used to perform the catalytic tests. 850 or 900 °C. 3 illustrates a longitudinal view (Fig. entrance. At the reactor outlet. In this study. 2.2012.cej. Results showed that the non-catalytic reactor activity has drastically evolved during the catalytic tests. Further. http://dx. it will be demonstrated that in the presence of catalyst sample. a full reactor model considering the non-catalytic reactor activity and the catalyst activity has been developed. Thus. For gas temperature measurements. For the reactor heat-transfer characterization. the reactor is electrically heated.1.1016/j.4 M. To facilitate the readability of the present paper. Two ovens are used to ensure the controlled heating of the system. The reactor is fed with methane and steam with a steam-to-carbon ratio of 3 at 800. Please cite this article in press as: M. two thermocouples are set at the inlet and outlet of the reactor. / Chemical Engineering Journal xxx (2012) xxx–xxx Fig. the non-catalytic reactor activity is negligible. and will be discussed further.

Characteristics of tested catalysts Sample 1 Sample 2 Wash-coat thickness (lm) Am (m2sma /grhodium) BET (m2/gcatalyst) Mass of catalyst (Mc) (mg) PR (rhodium quantity) (%) Dispersion (%) Rhodium particles size (nm) 2 80 10 235 10 4 20 18 6 10 22. 2. 4.% for the second sample. Catalyst holder. 2. The pressure for all experiments is set at 20 bars.3. Carbon and hydrogen balances are carried out to check mass balances and to detect potential coke formation. FCO and FCO2 respectively denote the methane.cej. they have to be used with caution since they are often based on empirical correlations. (2012).0. Variable XCH4 represents the methane conversion and SCO the CO selectivity determined from the change in gas composition. middle and head. The specific heat flux is one of the model parameters.1. denotes the methane flow rate at the reactor inlet. For a given residence time and temperature level (800. 4. The dry gas composition is then determined by on-line infrared analyzer. Reactor model for kinetics study In this section.5 M. [12].07. where the catalyst sample is located.1. the gas is quickly cooled and passed through a gas–liquid separator where the unreacted water is separated and weighed by means of a weighing machine. http://dx. The residence time is computed at the reactor inlet as the ratio between the reactor volume and the volume flow rate at the inlet gas temperature and pressure.0  F CH4 F CH4.4. Cross sectional view of the reactor. As demonstrated by Mladenov et al. Fig. then it is impregnated with an excess of aqueous rhodium nitrates solution. The assumptions detailed below have been considered. X CH4 ¼ SCO F CH4. The characteristics of the catalyst samples are summarized in Table 2. Eng. Mbodji et al. 2. Samples have been observed at three different locations of the substrate: bottom.117 . Chem. carbon monoxide and carbon dioxide flow rates along the reactor. Reactions occur on the surface of the wash-coat deposited on the sample holder.  There is no limitation by internal transfer in the wash-coat. At the reactor exit. the external mass-transfer Table 2 Characteristics of tested catalysts.2. the one-dimensional plug-flow reactor model developed for the reactor simulation is presented.  There is no heat transfer by radiation. the powder is treated by attrition. In this study. the non-catalytic reactor activity is not considered in the model version described in this paper. / Chemical Engineering Journal xxx (2012) xxx–xxx Psm Mobile thermocouple: Tm Gas: Tg Pmg Psg Catalyst sample: Tc Pcg Reactor wall: Ts Psc Ps Psm Mobile thermocouple: Tm Pmg Gas: Tg Psg Reactor wall: Ts Ps Fig. FCH4. The way this heat is transferred to the reactants is modeled by a usual convection transfer law. The behavior of gases is modeled by the ideal gas law. The heat is also provided uniformly through all the walls of the reactor.     To describe the concentration and temperature profiles along the reactor. Mbodji et al. 850 or 900 °C). Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. Residues obtained are finally calcined in air to form the catalyst phase. 25% CH4. Characterization The morphology and the thickness of catalysts layers have been evaluated using a Zeiss Ultra-55 scanning electron microscope before and after ageing in a steam methane reforming atmosphere at 850 °C.2012. Temperature-programmed reduction and chemisorption measurements have been carried out on a Micromeritics AutoChem II 2920 and an Asap 2020 on the catalyst powder before dip-coating to control the catalyst activity. Plug flow of the reactant gas. Characteristics of catalyst samples An example of the tested catalyst holders is presented in Fig. This model takes into account the SMR and WGS reactions and will be used for kinetic parameters identification from experimental tests. Mass-transfer coefficients are introduced in the model to account for the species transport limitation between the bulk gas mixture and the catalytic active surface.1. a one-dimensional plug-flow model including heat and mass transfer between the reactant gas and the catalyst has been developed. 3b. J. Synthesis of catalysts Catalysts are made of rhodium metallic active nanoparticles dispersed onto a commercial magnesium aluminate powder. No catalyst deactivation has been observed. The catalyst is supposed to be uniformly coated on the catalytic bar. the introduction of mass-transfer coefficients in the plug-flow reactor model improves its accuracy. For the experimental study.. The mass of rhodium nitrates is calculated to 20 wt. First. There is no reaction in homogeneous phase. The impregnation is conducted under heating at 150 °C and steering until water is completely evaporated. All the heat and mass balances described below are written under steady-state conditions.org/10. As indicated above. and 20 bars). However.doi. measurements have been performed during 72 h under reaction conditions (75% H2O.1016/j.4 1 53 2 Please cite this article in press as: M.0 F CO ¼ F CO þ F CO2 ð7Þ ð8Þ FCH4. 2.% rhodium in the final product for the first sample and 1 wt. catalysts are deposited as layers with a thickness less than 12 lm on alumina substrates by dip coating.2.

the enthalpy balance is written by equalizing the heat flux provided by the furnace. Heat losses on the experimental device and boundary conditions of the reactor models For a good estimation of kinetic parameters. Chem.1016/j. it is very important to know accurately. the most important steps are: (1) decomposition of methane on a metal surface to hydrocarbon fragments and carbon atoms.g is the total concentration in the gas phase. In the CC2 reactor part.j  yc.j C T. power law Pellet kinetics.j the mass-transfer coefficient between the gas and the catalytic wall.j r1 þ m2j r2 ¼ 0 ð10Þ where r1 and r2 are the reaction rates of SMR and WGS 1 and 2. There is a general agreement on the first order kinetics with respect to methane. z the axial position along the channel.3. several thermocouples provide the experimental reactor temperature profile. Mbodji et al. The net flux of component j from the bulk fluid to the wall is composed of a classical convectodiffusive term and a net flux due to the reaction stoichiometry. 9467a2  1. 2537a5 Þ where a denotes ratio between the height and the width of the reactor. the gas and the reactor walls. Combining the mass balance for each species to the overall mass balance enables to describe the evolution of the gas phase composition as:   dðyg. To describe the pressure drop under laminar flow conditions. and the gas and the mobile thermocouple. (15) by the experimental reactor temperature. [15] Rostrup-Nielsen [16] Tottrup [17] Xu and Froment [18] Aparaicio [19] Langmuir–Hinshelwood Temkin Identity Two-step kinetics. To reach that goal.j the molar fraction of species j in the catalyst. the reactor temperature is assumed to be equal to the temperature measured by the mobile thermocouple. Reaction rates The kinetics of steam methane reforming reaction has been studied extensively by several groups. kd.doi. The work presented in this paper is part of a preliminary design approach of a millistructured reactor heat-exchanger for the production of syngas. (2012). Experimental tests have been conducted in order to estimate the heat losses in the experimental device. H2O.6 M. Several kinetic studies on SMR reaction can be found in the literature.j denotes the gas phase molar fraction of species j. 7012a3 þ 0. U ¼ hloc ½Pcg ðT g  T c Þ þ Psg ðT g  T s Þ þ Pmg ðT g  T m Þ where hloc denotes the mean local heat-transfer coefficient by convection between the gas and the reactor internal elements. the gas and the mobile thermocouple and the gas and the reactor walls. respectively.j Þ þ   m1j  2yg.j dz ð9Þ where yg.g C pg dT g þU¼0 dz ð11Þ where U denotes the heat transferred by convection between the gas and the catalyst sample.g ðyg.117 . the source term related to the reforming reaction of methane and the Water Gas Shift reaction: Psc ðT c  T s Þ þ hloc Pcg ðT c  T g Þ þ r 1 DrH1 Psc þ r2 DrH2 Psc ¼ 0 Rsc ð12Þ where DrH1 and DrH2 denote the heat of SMR and WGS reactions. 9564a4 Psm Psc ðT s  T m Þ þ ðT s  T c Þ Rsm Rsc  ð15Þ where Ps denotes the external reactor perimeter and u the specific heat flux received by the reactor. by performing a heat balance based on the inlet and the outlet gas temperature and methane conversion. P the total pressure.j Psc F 0 þ F inert þ 2X 1 F CH4 . The kinetic parameters estimated for each boundary condition will be compared. Table 3 presents some of them [14–19]. and will be presented further. the reaction rate of the Table 3 Kinetic models of steam reforming of hydrocarbons.cej. The mass balance in the catalyst layer is written as the equality between the molar flux transferred from the gas and the flux consumed by chemical reactions: kd.2012.  0.4. H2. CO. The concentration evolution of the considered species j (j = CH4. respectively.0 c. Mbodji et al.org/10. In the model presented here.07. Wei and Iglesia [20] proposed a simple equation for kinetics of steam methane reforming. This flux is one of the model parameters. yc.j Þ P=ðRT g Þ ðy  yg.. Within the catalyst layer. Eng. CO2) in the gas phase results from the gas convection and the reaction at the catalytic wall. Pcg. They found that the activity at 600–700 °C only depends on the partial pressure of methane. (2) dissociative adsorption of water to H and OH species (3) OH or O species combine with C to form CO. These differences might be explained by experimental inaccuracies due to transport restrictions in the sense of diffusion and heat restrictions. J. 3553a þ 1. This can be done by replacing the Eq. Tg the gas temperature. 2. Finert the molar flow rate of inert species. For the CC3 part where there is no reactor thermocouple and catalyst sample. 2. implying that the rate determining step is the initial activation of a C–H bond in methane. the heat received by the catalytic surface. it is still possible to determine the experimental heat flux consumed by the endothermic SMR reaction for each test. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. for each experiment. / Chemical Engineering Journal xxx (2012) xxx–xxx coefficient was evaluated by numerical simulation using FLUENTÒ. Despite these large values. It is also possible to set the experimental reactor temperature as a boundary condition. Results show that heat losses are very large depending on the reactant gas residence time: heat losses range from 80% to 93% of the total experimental heat flux furnished by the electrical heat. CT. While the exact mechanism of the steam methane reforming reaction is still under debate today. power law Langmuir–Hinshelwood Microkinetic analysis Please cite this article in press as: M. and Psc the contact perimeter between the catalyst surface and the gas. F0 the total molar flow rate of reactants. but the activation energies vary between 20–160 kJ/mol. Shah and London [13] correlation is used: dP 2luc ¼ f Re 2 dz Dh ð13Þ f Re ¼ 24ð1  1. the flux exchanged with the gas phase. the specific heat flux u is considered as the thermal boundary conditions. A heat balance on the mobile thermocouple and on the reactor enables to describe their temperature profiles as: Psm ðT s  T m Þ  hloc Pmg ðT m  T g Þ ¼ 0 Rsm  uPS ¼ hloc Psg ðT s  T g Þ þ ð14Þ Reference Form of the kinetics law Bodrov [14] Kohmenko et al.j Þ ¼ kd. Recently. Psg and Pmg respectively correspond to the contact perimeters between the gas and the catalyst. A heat balance on the gas phase enables to describe the evolution of the gas temperature along the reactor with the following relation: uc Xc C T. http://dx.

J.35 0.3252   26. 5. P sc Rsc þ h1 5ðT s  T g Þ ð16Þ loc hloc Pmg Rsm Tg Psm h P R 1 þ loc mg sm Psm Ts þ Tm ¼ ð17Þ Temperature [°C] 860 CC2 part 850 840 Reactor Mobile thermocouple 830 820 0 0. it is useful to provide a good description of the heat and mass-transfer phenomena that occur between the reactant gas and the catalyst. Such a lumped kinetics reaction rate will enable to properly design a milli-structured exchanger reactor for syngas production at the industrial scale. After integration of the set of equations. Kpreexp1 and Kpreexp2 [mol/m2ActiveMetal /s] denote the pre-exponential rate constants of SMR and WGS reactions. the same formalism as used by Tonkovich et al..4 0. From a purely numerical point of view.CO c.08 0. the WGS reaction can be neglected under the operating conditions of this study.6.g Pmg Rsm þ dz Psm The reactor model is a set of differential and algebraic equations. on the mobile thermocouple and on the catalytic bar than enable to relate their temperatures as follows: Heat balance on the gas: 2 dT g 1 P mg 4 ¼ F inert C T.1016/j.04 0. Once thermal steady state is reached.CO2 yc. However. Without going into details. Please cite this article in press as: M. Ea1 and Ea2 (J/mol) denote the activation energy of the SMR and WGS reactions. For these tests.5. Mbodji et al. / Chemical Engineering Journal xxx (2012) xxx–xxx main reaction (steam methane reforming: SMR) has to be measured precisely in the same operating conditions as the future reactor. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. Kl is a constant depending on the catalyst microstructure [m2ActiveMetal =m2surface of holder ] and might be expressed by first approximation as: Kl ¼ Am M c PR Psc L where Am denotes the active surface of active metal per unit of mass of rhodium (m2sma /grhodium). In the CC2 part containing the catalyst sample. This solver uses the Gear method which is adapted to the resolution of stiff systems. the reactor is fed with nitrogen.cej. (2012). Experimental temperature profiles along the reactor with active catalyst sample in the CC2 part.H2 O  P r 1 ¼ K pre exp 1 exp  Kl RT c K eq1    yc. These parameters have been determined from experimental temperatures measurements without chemical reaction.16 0.2 Reactor length [m] Temperature [°C] 2.07. (Psc  L) the surface of the holder on which the catalyst sample is coated. From the end of the CC2 part to the middle of CC3.117 . Estimation of the kinetics reaction rate then consists in finding the pre-exponential rate constant and the activation energy of the SMR reaction. the reactor temperature is constant. the reactor model described above is complete and ready to be computed.H2 O  Kl r 2 ¼ K pre exp 2 exp  RT c K eq2 where the reaction rates r1 and r2 are expressed in [mol/ m2SampleSurface /s].12 0.H2 Ea2 yc.25 0. 1 hloc 3 P cg 850 800 CC3 part 750 700 Mobile thermocouple 650 0. to make it more reliable and to correctly reproduce the experimental results. In order to express this overall reaction rate. A heat flux is set at the external reactor walls. Eng. The resolution of the system requires the knowledge of specific parameters as the following three heat-transfer parameters defined above: hloc.1 0.18 0. heat and mass transfer in the reactor are investigated. Rsm and Rsc. K eq1 ¼ 101. Heat balances on the gas.06 0.7 M. Reactor model resolution þ hloc P sg þ Pcg Temperature of the mobile thermocouple   4400 K eq2 ¼ exp  4:036 Equilibrium constant of WGS reaction ½— Tc As said previously. respectively. In the following section. The reaction kinetics can be determined from the comparison between the experimental tests and the calculated results computed from the heat and mass balances presented above. respectively. 5. which makes them particularly suitable for kinetics studies.org/10. This can be explained by the fact that heat consumption by SMR reaction is not significant because most of the methane quantity has already been consumed by reaction in the CC2 part. Their remarkable heat-transfer capacity is due to the fact that the heat-transfer coefficient is proportional to the reciprocal of the channel hydraulic diameter. [21] to describe SMR reaction over a rhodium on Mg-spinel catalyst. Therefore.3 0. is adapted in the model by adding a constant depending on the catalyst microstructure. it must be emphasized that a global kinetics model is more appropriate than the microkinetics of the SMR reaction with detailed reaction mechanism and determination of the limiting step.H2 yc.CO yc.02 0. An example of experimental temperature profiles along the reactor during catalytic tests in the presence of active catalyst sample is shown in Fig. Heat transfer in the reactor Microchannels are known as apparatuses that provide high heat-transfer coefficients. respectively. the reactor temperature decreases along the reactor length as a result of the heat consumption by the endothermic steam reforming reaction.CH4 yc.doi.45 Reactor length [m] Fig.2 0. PR the rhodium quantity in the catalyst.2012. Mbodji et al. mass and overall enthalpy balances are computed and satisfied with less than 0.001% and 1%.14 0. Chem. Reactor temperature decreases at the end of the CC3 part due to heat losses by natural convection between the experimental setup and the surrounding air.830  exp  þ 30:114 Equilibrium constant of SMR ½Pa2  Tc 2. the experimental temperatures of the gas. Mc the mass of catalyst. The solver function ode15s available on MATLABÒ is used to solve this system. the mobile thermocouple and the reactor are recorded. the SMR and WGS reactions rates can be written as: !   y y3 Ea1 2 c. http://dx.

and Nu the Nusselt number defined as: Nu ¼ hloc Dh k For a mean temperature of 400 °C. Tw and Tg the wall temperature and the mass-averaged gas temperature. When the flow is fully developed. required for the reactor model accuracy.16 0. This result is not surprising since there is no direct temperature measurement on the catalytic bar. Eng.117 . Dh the hydraulic diameter.org/10. Thermal resistances.013 0.06 0.14 0. The relatively large error on the resistance Rsc indicates that this parameter is not properly estimated. 3b).. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. Mass transfer in the reactor Mass-transfer coefficients must also be preliminary determined to study the kinetics of the reaction. the Nusselt number tends towards a constant value of 4. For each simulation.02 0.1016/j. However. http://dx. in order to have a good description of the heat transfer in the reactor model. and the thermal resistance between the catalytic bar and the reactor and their standard deviation are presented in Table 4.7. respectively.0038 0. simulations with the commercial CFD package FLUENTÒ have been performed without chemical reaction by setting a constant wall-temperature boundary condition and feeding a N2 flow at inlet temperature.1 0.07. are also estimated by experimental temperature measurements. They enabled description of the Nusselt variation as a function of the thermal Graetz number along the reactor with this following relation: Nu ¼ 4:58 expð0:003Gzth Þ with Gzth ¼ RePr Dh z The variation of the Nusselt number as a function of the thermal Graetz number along the reactor is shown in Fig. Tm = Tc = Ts.2012. 0 0. 7. 6. Convection gas heat-transfer coefficient in microreactors depends on the hydraulic diameter and on the gas composition and usually ranges from 400 to 2000 W/m2. The experimental results give an average value of 442 W/m2 K with a standard deviation of 65 W/m2 K. For all tests. This result is in agreement with those obtained by Kays and London [23].15 0. Fig. The three heat-transfer parameters have been identified by minimizing the sum of squared differences between measured and modeled temperatures.doi. Temperature profiles in the reactor without reaction for calibration of heattransfer.58exp(0.cej. This difference can be explained by the fact that hloc from the experimental tests is an average value from several experiments and by the assumption that considers that hloc is constant Heat-transfer parameter hloc (W/m2 K) Rsm (m2 K/W) Rsc (m2 K/W) Average value Standard deviation 442 65 0. 6 shows an example of temperature profiles along the reactor after heattransfer parameters identification. Please cite this article in press as: M. It is difficult to perform reliable mass-transfer coefficient measurement in microdevices and mass transfer has been evaluated here by CFD simulations using 440 Gas Model Outlet gas Experimental Mobile thermocouple Model 430 12 Mobile thermocouple Experimental 410 Reactor Experimental Nusselt Number [-] Temperature [°C] 420 Catalytic bar Model 400 390 380 10 8 6 370 360 350 CFD results with Fluent Nu = 4. since the standard deviation on Rsc is larger than its average value. 7.0005 0.8 M. Chem.2 0.25 1 / Graetz Number [-] Fig. hloc calculated from Kays and Crawford [22] correlation is 235 W/m2 K.04 0.05 0. the average values of the mean heat-transfer coefficient between the flowing gas and the reactor internal elements (catalytic bar. The slight difference can be explained by reactor cross section that is slightly different from a perfect rectangle due to the presence of the mobile thermocouple (see Fig. 2. Several simulations have been performed by varying the gas inlet velocity. hloc Pcg Rsc Ts þ Tg Psc Tc ¼ hloc Pcg Rsc 1þ Psc ð18Þ It is important to point out here the fact that when both thermal resistances Rsm and Rsc are set equal to 0.1 0. A mean difference of 2 °C between modeled and experimental temperature has been obtained. Nusselt variation as a function of the thermal Graetz number along the reactor.12 0. the local Nusselt number is computed with the following relation: Nu ¼ QDh ðT w  T g Þk where Q denotes the heat flux at the wall. It is well known that hloc is constant only for fully-developed flows.08 0. Mbodji et al. the temperature of the catalytic bar and that of the mobile thermocouple are equal to the reactor temperature i.016 along the reactor.2 Reactor length [m] Fig. mobile thermocouple and reactor walls).58. J. (2012).003Gz th) 14 4 0 0. the thermal resistance between the thermocouple and the reactor. Mbodji et al. / Chemical Engineering Journal xxx (2012) xxx–xxx Temperature on the catalytic surface Table 4 Experimental heat-transfer parameters.18 0. Kays and Crawford [22] proposed the following correlation to estimate Nusselt number for fully-developed laminar flow in rectangular ducts with constant heat flux condition: 2 3 4 5 Nu ¼ 8:235ð1  1:883a þ 3:767a  5:814a þ 5:361a  2a Þ where a is ratio between the height and the width of the reactor.e.

The function Fminsearch available in MATLABÒ optimization toolbox. that residence time is computed along the reactor by considering the CC2 and CC3 part. Boundary conditions for mass-transfer study. Kays and London [23] reported an average Nusselt number of 3. Please cite this article in press as: M. the Sherwood number is constant and tends towards its limiting value 3. 9 depicts the Sherwood number variation as a function of the material Graetz number.05 0. the heat and mass transfer are assumed analogous. / Chemical Engineering Journal xxx (2012) xxx–xxx Temperature profile has been established between Sherwood number and the material Graetz number.0023*Gzm) X 0 @ X model  X experiment CH4 CH4 X experiment CH4 10 8 6 !2 þ T model  T experiment g g T experiment g !2 1 A Kinetic parameters determination then consists in solving a nonlinear optimization problem without constraints. For Graetz numbers above 10. Sherwood number variation as a function of the material Graetz number. experimental tests with an inert holder have been carried out before and after the catalytic tests. FLUENTÒ. 9.5 150 200 250 300 350 400 450 500 550 600 650 Residence time [ms] 1 / Graetz material Number [-] Fig.2 0.9 in the case of a rectangular channel having the same aspect ratio a (heigh/width) and boundary conditions.doi. When the material Graetz number is less than 10. the material Graetz number is introduced: Gzm ¼ ReScDh z Fig. CO2 and CH4 and the outlet gas temperature are measured and recorded.2012. Thus.cej. CO. for all simulations.35 0. adiabatic boundary conditions are used (see Fig. Impact of the non-catalytic reactor activity on the overall methane conversion In order to properly determine the reaction kinetics..99. J. 8). The following function F is minimized: 70 60 50 40 30 20 10 4 0 100 0 0. based on the SIMPLEX method.9 M. 8. Male et al. Uniform wall temperature 3.97*exp(0. Sherwood number is computed by using the following relation: Sh  Nu ¼ QDh ðT c  T g Þk Sherwood number at the reactor entrance varies strongly as a function of the gas inlet velocity. the following correlation CFD results with Fluent Sh = 3.3 0. Adiabatic wall temperature Oulet Inlet Sh ¼ 3:97 expð0:0023Gzm Þ This correlation is used in the reactor model to represent the external mass transfer between the gas and the catalytic surface. Mbodji et al. Several simulations have been performed by varying the N2 velocity inlet. From these simulations results. 4. To consider the entrance effects on the mass-transfer. we must ensure that the activity of the metallic walls of the reactor. (2012).org/10. After several tests.25 0.15 0. is used to find kinetic parameters (activation energies and pre-exponential rate constants). Fig. outlet gas temperature and calculated values given by the reactor model. Fig.4 0. Non-catalytic reactor conversion without catalyst before and after the catalytic tests. 90 Methane conversion before catalytic tests Methane conversion after catalytic tests 80 12 Sherwood Number [-] F¼ Non-catalytic reactor activity at 850°C 14 For each catalytic test.45 0. Mbodji et al.07. It is important to precise here. the gas phase molar fraction of H2. [24] investigated mass transfer in a microreactor by using a similar method. the reactor intrinsic activity increases and is not negligible compared to some experiments with active catalyst sample. The kinetic parameters are estimated by minimizing the sum of the squared difference F between measured methane conversion.1 0. For simulation of the catalytic wall. Kinetic parameters identification Fig. estimated by the methane conversion. This parametric optimization is performed simultaneously on several experiments conducted at different residence times and temperature levels. 10 depicts the non-catalytic reactor conversion in presence of an inert catalyst sample before and after the tests. One can note that the non-catalytic reactor activity has drastically evolved during the catalytic tests. is negligible compared to the activity of the catalyst holder. Chem.1016/j.117 . However. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. Eng. numerical heat-transfer simulations with appropriate boundary conditions have been performed in order to find a correlation which describes the analogous mass transfer. the Sherwood number tends towards an asymptotic value of 3.99 which is in very good agreement with literature. a uniform wall temperature boundary condition is used. Therefore. 10. As there is no mass transfer on the other walls. Indeed. the entrance effects cannot be neglected. http://dx. To perform these simulations.

conversion (left) and outlet gas temperature (right). The calculated values of the methane conversion and the gas temperature are in very good agreement with the experimental ones.6 0. http://dx. 850°C 800°C 900°C sample 1 90 sample 2 thermodynamic equilibrium 90 CH4 Conversion [%] The activity of the non-catalytic walls of the reactor is quantified by fitting experimental reactor activity after the catalytic tests. Eng.2 % 849 0. In the CC2 part. only the non-catalytic reactor activity is considered. As described above..07.5°C 840 840 845 Model [-] 850 Model [-] Fig.4 843 0. Comparison between model and experiment results for the non-catalytic reactor activity.10 M.117 .65 848 0.3 0. 90 80 80 80 70 70 70 60 60 60 50 50 50 40 40 40 30 30 30 20 50 100 150 Residence time [ms] 20 50 100 150 Residence time [ms] 20 50 100 150 Residence time [ms] Fig. Please cite this article in press as: M. the reactor model considers the two active areas: the reactor walls and the catalyst.35 842 0.5 0. The full reactor model consists in coupling two reactors in series.doi.45 846 845 844 0. to evaluate the influence of this noncatalytic activity. the full reactor model taking into account the non-catalytic reactor activity has been used. 11.cej.5 0. (2012).25 0. 12. Chem.2012.55 0.6 847 Experiment [-] Experiment [-] 0. Mbodji et al. Methane conversion as a function of the residence time and the temperature. / Chemical Engineering Journal xxx (2012) xxx–xxx 0. Comparison between model and experimental results for the noncatalytic reactor activity is shown in Fig.3 841 0.1016/j.org/10.75 850 Methane conversion + or .7 Outlet gas temperature + or . 11. J. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation.4 0.7 0. Mbodji et al. In the CC3 part.

cej. rhodium particle size and dispersion.4 0.4 0. Mbodji et al. Methane conversion increases with increasing residence time and/or temperature. http://dx.2 0. One can note a good agreement between model and experimental results despite the experimental measurements uncertainties. Kinetics parameters identification taking into account the noncatalytic reactor activity 5. by using the full reactor model with several active areas.2. Eng.5 Reactor length [m] Fig. In order to quantify the kinetic reaction rate of the SMR reaction on the catalyst. The kinetics of the SMR reaction specific to the reactor walls was already evaluated in the presence of an inert sample.2012. Both these samples can be distinguished by their wash-coat thickness.1 0 0 0 0.5 Active catalyst sample 0.8 Catalyst Reactor CC2 part Reactor CC3 part Catalyst Reactor CC2 part Reactor CC3 part 0.3 0.117 . the kinetic parameters (Kpreexp1 and Ea1) of the catalytic SMR reaction can be identified. Experimental results of the catalytic tests with catalyst sample Here are presented the first tested samples. These samples enable to validate the determination of the kinetic parameters. rhodium quantity. illustrated in Fig. 12 shows methane conversion as a function of the residence time and temperature for samples 1 and 2.5 Reactor length [m] 0 0.3 0. The kinetics constants of the methane steam reforming are: Please cite this article in press as: M. the part of conversion due to the catalyst sample and a comparison between experiment and model results in terms of methane conversion and outlet gas temperature. Chem.1 Inert catalyst sample 0. The good performances of sample 2 could be explained by the good dispersion of the rhodium particles. sample 2 is more active than sample 1 despite the fact that sample 2 has less rhodium quantity.4 0.2 0. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. the full reactor model considering the non-catalytic activity of the reactor walls and the catalyst activity of the holder has been used. J. Then. Results 5. Mbodji et al. They have been tested at 800. Indeed methane conversion with sample 2 is greater than that obtained by sample 1. 5. Comparison between SMR kinetic reaction rate on the catalyst sample and on the non-catalytic walls reactor (temperature conditions.1016/j. However. / Chemical Engineering Journal xxx (2012) xxx–xxx Table 5 Kinetic parameters for SMR reaction by considering the non-catalytic reactor activity and comparison between model and experimental results.07. Fig. 5). the small rhodium particle size provides to the catalyst a high specific surface. Table 5 shows the estimated kinetic parameters.2 0.org/10.6 0. These results are obtained by setting a constant heat flux at the reactor walls. 13.1 0. Furthermore.1.11 M.3 0..05 0. 850 and 900 °C and for residence times between 40 and 150 ms.1 0.doi.7 Reaction rates [mol/m2/s] Reaction rates [mol/m2/s] 0. (2012). Residence time (ms) Methane conversion (%) Outlet gas temperature (°C) Part of methane conversion due to the catalyst sample (%) Model Experiment Model Experiment 40 60 100 147 Sample 2 (800 °C) 33 40 51 60 35 41 51 60 816 807 806 815 793 795 799 801 90 94 97 99 40 60 100 147 Sample 1 (800 °C) 30 37 45 50 30 35 42 50 776 768 764 785 777 780 787 791 95 97 98 99 40 60 100 147 Sample 1 (850 °C) 43 51 65 70 43 50 64 69 845 840 852 852 849 852 856 858 86 91 96 98 0.

Depending on residence time and temperature level.500  Kpreexp1 = 1.12 M. J.  Ea1 = 166. methane conversion due to the non-catalytic reactor activity can be considered as negligible. Chem. 7. we noted some difficulties to estimate kinetic parameters from experimental tests conducted at 900 °C on sample 1. the SMR reaction rate on the catalyst is equal to 0 and all the methane conversion is due to the non-catalytic reactor activity.e. Please cite this article in press as: M. / Chemical Engineering Journal xxx (2012) xxx–xxx  Kpreexp1 = 9. Table 6 Comparison of identified kinetic parameters with literature results..68  108 165. Mbodji et al. inlet and outlet gas temperature. and estimated the SMR kinetic reaction rate by fitting kinetic data. [21] Kinetic parameters Kpreexp1 (mol/m2sma /s) Ea1 (J/mol) 9.310 1. The reactor model has been improved in order to avoid these uncertainties by setting an experimental reactor temperature as the thermal boundary condition.07. SMR kinetic reaction rate on the catalyst and on the non-catalytic reactor walls is shown in Fig. these results show that when an active catalyst sample is placed inside the reactor. due to the difference in the kinetic formulation. (2012).740 Kpreexp1 (mol/m3catalyst /s) Ea1 (J/mol) 1. By contrast. Comparison with literature results Tonkovich et al. Kinetic parameters Methane conversion due to the catalyst sample increases with the residence times and the catalyst activity. by using the reactor model presented previously.org/10.+ 2 % 30 40 50 Model 60 70 760 Outlet gas temperature [°C] + or .  Ea1 = 165.47  107 mol/m2sma /s. it is also possible to consider the experimental heat provided to catalytic holder for the endothermic reaction from the thermal balance based on methane conversion.47  107 166. http://dx. A very good agreement between model and experimental results has been obtained. the activation energies are in the same order of magnitude. Kinetic parameters were also estimated by considering that all methane conversion is due to the catalyst i. However. The pre-exponential constants are not directly comparable. The kinetics constants of the methane steam reforming are: This work By considering the non-catalytic reactor activity Without considering the non-catalytic reactor activity Tonkovich et al. 13.117 . This can be explained by the fact that the catalyst sample is located at the reactor entrance and its activation energy is almost twice less than the non-catalytic reactor activation energy.68  108 mol/m2sma /s. Conversion (left) and outlet gas temperature (right). Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. [21] conducted steam methane reforming reaction by using a rhodium on Mg-spinel catalyst. experimental results and model-predicted values are in perfect agreement. This is explained by heat and external mass transfer limitations which appear when 75 860 70 65 840 60 Experiment Experiment 55 50 45 820 800 40 35 780 30 25 20 20 Methane conversion [%] + or .doi. 850 and 900 °C on sample 2. methane conversion due to the catalyst activity ranges from 86 to 99% of the overall methane conversion. However. Otherwise. As presented in the model equations. 14.310 J/mol.1016/j. Discussion The detailed mathematical model for acquisition of kinetic data developed in this work enabled to find CH4 reforming kinetic reaction rate. Eng.cej.10°C 760 780 800 820 840 860 Model Fig. all methane conversion is due to the catalyst sample which confirms that the non-catalytic reactor activity is then negligible. Their kinetic parameters and those obtained in this work are summarized in Table 6. The kinetics values obtained with the new boundary conditions are similar to those obtained with the first boundary condition.740 J/mol. Experimental heat received by the reactor during the catalytic tests was difficult to estimate due to the large heat losses. When an inert catalyst sample is located in the CC2 part of the reactor. 14. Comparison between model and experiment by considering that all methane conversion is due to the catalyst for tests at 800 and 850 °C on sample 1 and 800 °C on sample 2.2012. when an active catalyst sample is used. 6. As can be seen in Fig. Mbodji et al.275  108 169.

8.500 J/mol).15 0. Conclusions Steam methane reforming process intensification by using a millistructured reactor and a rhodium-based catalyst has been investigated in this work. [25] who investigated steam methane reforming intensification by using a squared monolith channel and a nickel-based catalyst.05 0. 15.35–2. Eng. The reactant gas temperature ranges from 650 °C to 900 °C. Mbodji et al. The fact that the part of methane conversion coming from the non-catalytic reactor is negligible in the presence of active catalyst sample is studied experimentally and will be the subject of another publication. For a reactor with a hydraulic diameter of 1 mm.07. results showed that. Further tests are required with reactor hydraulic diameter below 400 lm for reduction of the heat and mass-transfer limitations.1 0. suitable and adapted to millistructured reactor. Two catalyst samples with different wash-coat thicknesses. heat and/or external masstransfer limitations appear and become more and more pronounced when increasing temperature. the reaction and external mass-transfer characteristic times are in the same order of magnitude for temperatures near 780 °C. / Chemical Engineering Journal xxx (2012) xxx–xxx 2 2 10 10 Reaction External mass transfer Characteristic time [ms] Characteristic time [ms] Reaction External mass transfer 1 10 0 10 1 10 0 10 Hydraulic diameter 1 mm Hydraulic diameter 0. the same tests are conducted on a reactor coated with alumina in order to suppress reactor activity.4 mm. Characteristic times of reaction and external mass transfer decrease along the reactor due to the increasing temperature.2 Reactor length [m] 10 0 0. Characteristic times of SMR reaction and external mass transfer have been investigated and are shown in Fig.15 0. this study demonstrates on one hand that rhodium catalyst is highly active.2012. Characteristic times analysis.310/165. heat transfer has been characterized by measuring experimental reactor temperatures profiles. In the case of a rhodium-based catalyst which is more active than the nickel based catalyst. Mbodji et al. and on the other hand that. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation. The final module design still has to be chosen after economic assessment and by considering additional technical aspects related to the mechanical resistance of the device or the manufacturing of the microstructured system or the possibilities for catalyst coating inside the reactor. (2012). In order to increase the accuracy of the model. Some of these tests also fulfill the conditions of kinetic parameters identification and enable to validate the mathematical model for kinetic reaction rate estimation.1016/j.org/10. The full reactor model enabled to estimate kinetic reaction rate of SMR from the catalytic tests in spite of the reactor activity and complex heat management inside the reactor. for SMR process intensification. rhodium particle size and dispersion have been tested at 800. performing SMR reaction on a highly active catalyst at high temperature in a microchannel reactor having a large hydraulic diameter (>1 mm). Currently. Numerical simulations of heat and mass transfer with FLUENTÒ have been performed in order to find a correlation which describes precisely transfer coefficients between the bulk of the flow and the surface in the reactor model.4 mm -1 10 -1 0 0.doi. For temperatures greater than this value. The catalytic performance is different as a function of the catalyst dispersion in the wash-coat.2 Reactor length [m] Fig. which is Please cite this article in press as: M. it is needed to use a hydraulic diameter below 0.7 mm is a sufficiently low dimension for SMR process intensification. http://dx. J. it is needed to reduce the reactor hydraulic diameter below 400 lm for heat and mass-transfer limitations elimination. To sum it up. Experimental results showed that the single channel reactor is a very good tool for the determination of catalyst behavior and activity. The identified rhodium activation energies (166.117 . A similar result was found by Arzamendi et al.8 mm.. 850 and 900 °C and for residence times between 40 and 150 ms. Chem. to eliminate heat or mass-transfer limitations and for process intensification.740 J/mol) by considering or not the non-catalytic reactor activity are in good accordance with the literature value (169.1 0. Catalytic tests performed on these samples showed the importance of the catalyst characteristics on the performance.cej. By varying channel sides between 0.13 M. A steam-to-carbon ratio of 3 has been used. they showed that 0. instead of using one of the available correlations. A one-dimensional heterogeneous plug-flow reactor taking into account heat and mass transfer between the flowing gas and the catalytic surface of the wash-coat has been chosen for the reactor model. 15.05 0. A detailed mathematical model for kinetic reaction rate measurement from experimental catalytic tests has been developed in order to obtain the kinetics of the reactions which depends on the catalyst microstructure. rhodium quantity.

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