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Article
The Interplay of Kinetics and Thermodynamics in the
Catalytic Steam Methane Reforming over Ni/MgO-SiO2
Naoki Kageyama, Brigitte R. Devocht, Atsushi Takagaki, Kenneth
Toch, Joris W. Thybaut, Guy B Marin, and S. Ted Oyama
Ind. Eng. Chem. Res., Just Accepted Manuscript DOI: 10.1021/acs.iecr.6b03614 Publication Date (Web): 10 Jan 2017
Downloaded from http://pubs.acs.org on January 11, 2017

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Page 1 of 42 Industrial & Engineering Chemistry Research

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The Interplay of Kinetics and Thermodynamics in the Catalytic Steam Methane Reforming over
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Ni/MgO-SiO2
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11 Naoki Kageyamaa, Brigitte R. Devochtb, Atsushi Takagakia,c, Kenneth Tochb, Joris W. Thybautb*, Guy
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14 B. Marinb, S. Ted Oyamaa,c,d*
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17 Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku,
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20 Tokyo, 113-8656, Japan
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23 Laboratory for Chemical Technology, Ghent University, Tech Lane Ghent Science Park Campus A,
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26 Technologiepark 914, B-9052 Ghent, Belgium
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College of Chemical Engineering, Fuzhou University, Fuzhou 350116, China
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Environmental Catalysis and Nanomaterials Laboratory, Department of Chemical Engineering,
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35 Virginia Polytechnic Institute and State University, Blacksburg, VA 24061-0211, United States
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41 *Corresponding authors: STO oyama@vt.edu, JWT joris.thybaut@ugent.be
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4 ABSTRACT
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The steam methane reforming (SMR) reaction was studied on a Ni/MgO-SiO2 catalyst at 923 K (650
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9 C) and 0.40 MPa in a tubular packed-bed reactor. The partial pressures of CH4 and H2O were varied
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11 between 20 and 140 kPa and 80 and 320 kPa respectively. Measurements were carried out without mass
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13 and heat transport limitations, as verified by the Weisz-Prater and Mears criteria. Experimentally, the
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CH4 conversion increased with the inlet partial pressure of H2O and decreased with the inlet partial
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18 pressure of CH4. However, at low CH4 inlet partial pressures, i.e., at 40 and 60 kPa, the conversion
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20 passed through a maximum. Rate expressions were derived based on a simple two-step sequence. A
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22 statistical analysis led to a globally significant, weighted regression and resulted in a good agreement
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24 between the model and the experimental data, as indicated by a low F value of model adequacy of 2.84.
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27 The rate and equilibrium coefficient parameters were statistically significant as indicated by narrow
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29 confidence intervals. The model was able to correctly describe the experimentally observed maximum
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31 in the methane conversion and allowed to relate this behavior to CH4 and H2O surface coverages. The
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33 model was able to capture the increasing selectivity of CO2 with the H2O inlet partial pressure and
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increasing methane conversion. The effect of changing the total pressure and H2O/CH4 ratio on the CH4
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38 conversion as a function of the space velocity was simulated and corresponded to both the experimental
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40 and literature data. A major finding of the modelling is that as flow rate is increased there is a
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42 crossover in the order of conversion with pressure due to a transition from thermodynamic to kinetic
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44 control. Although the SMR equilibrium conversion decreases with pressure, away from equilibrium at
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47 high flow rates, conversion is higher at higher pressures due to enhanced adsorption rates.
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49 Keywords: steam methane reforming; Ni/MgO-SiO2 catalyst; integral kinetic analysis; kinetics and
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51 thermodynamics
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1. INTRODUCTION
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Hydrogen plays an important role in todays chemical industry, especially in the refining of petroleum
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12 and the synthesis of chemical products. Recently, hydrogen has received attention as a potential energy
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15 source for fuel cells because of its high energy conversion efficiency 1. The majority of hydrogen is
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18 produced by fossil fuel reforming 2 , especially via steam reforming of natural gas, whose main
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21 component is methane. Steam Methane Reforming (SMR) is a strongly endothermic reaction (Eq. 1)
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24 which is generally accompanied by the moderately exothermic water-gas shift reaction (Eq. 2).
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28 Ho298 = +206 kJ mol-1 Eq. 1
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31 Ho298 = -41 kJ mol-1 Eq. 2
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34 Both reactions contribute to the production of H2. In contrast, the much studied dry-reforming of
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methane (CH4 + CO2 2 CO + 2H2) cannot be used for commercial hydrogen production
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41 because the reverse water-gas shift reaction (CO2 + H2 CO + H2O) consumes hydrogen to
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produce water. 3 The SMR process is operated industrially at 0.3-2.5 MPa total pressure and at high
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47 temperature, i.e., typically between 900 and 1300 K. The energy requirement is considerable and is
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50 commonly supplied by the combustion of natural gas, c.q., methane, in a furnace in which the SMR
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53 reactor is placed. In general, this results in a high energy consumption and large CO2 emissions. The
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56 simultaneously occurring water-gas shift reaction 4 produces additional H2 and CO2. There have been
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many attempts to improve the process efficiency. In a study by Zheng et al., the energy required for the
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endothermic reforming was supplied using solar energy as a renewable energy source 5 . In an
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11 investigation by Hafizi et al., chemical looping was employed by cycling fine metal powders between
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14 oxidation and reduction steps for hydrogen production from methane 6. In addition to these attempts,
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17 efforts have been made to develop new catalysts.
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20 Kinetic modeling bridges the gap between phenomena occurring at the conceptual and practical scale.
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23 It provides essential information for reaction design and corresponding process scale-up 7 as well as for
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26 understanding catalyst deactivation 8. It can also be used to better understand the catalyst activity so as
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29 to allow its improvement. As such a better understanding is pursued in this work with a model
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32 accounting for the most kinetically relevant steps. Although some studies aim for increasingly more
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35 detailed descriptions of the reaction 9,10,11 this work takes an opposite approach to produce the simplest
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38 possible analysis. The significance of the work is two-fold. First, it presents a minimal kinetic model
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with just two equilibrium parameters and two rate parameters to describe the MSR and WGS reactions
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that can be used by other researchers as a metric for comparison. Second, it demonstrates that the
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48 conversion falls with increasing pressure at low space velocity (high space time) as expected from
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51 thermodynamics, but increases with increasing pressure at high space velocity (low space time) from
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54 kinetic control. As far as we know, this interplay between thermodynamics and kinetics mediated by
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The catalyst employed in this research is Ni-based, which is the most commonly used metal, but
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11 employs a MgO-SiO2 support that has not been studied widely. Magnesium silicate can be made in
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14 high surface area and has been used as a catalyst [12] as well as a catalyst support [13]. It is strong,
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17 low cost, and offers sulfur tolerance, which is a desirable property with streams derived from natural
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20 gas. In addition, Ni on this support is easier to reduce than on Al2O3-based supports because
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23 aluminates are not formed. In this research a series of steam methane reforming measurements was
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26 conducted by varying the ratio of the inlet gas components, methane and water vapor as reactants and
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29 nitrogen as inert dilution gas at a pressure of 0.40 MPa.
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2. EXPERIMENTAL SECTION
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2.1 Experimental
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11 The gases used in this study were CH4 (99 % Toatsu Yamazaki Co., Ltd.), H2 (99.99 % Showa Denko
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14 Gas Products Co., Ltd.) and N2 (99.99 % Toatsu Yamazaki Co., Ltd.). A conventional Ni/MgO-SiO2
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17 catalyst (JGC Catalysts and Chemicals Ltd.) consisting of 53.0-58.0 wt% NiO, 8.1-11.1 wt% MgO and
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20 24.2-28.2 wt% SiO2 (supplier information) was selected. This commercial catalyst is used for naphtha
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23 reforming and is, hence, chemically sufficient stable enough at high pressure and temperature. The BET
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26 area was determined by N2 adsorption at 77 K using a volumetric apparatus (BELSORP-mini, Microtrac
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29 BEL Corp.). The H2 chemisorption uptake was measured using a pulse flow instrument (CHEMBET-
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32 3000, Quantachrome Instruments) at 313 K after 12 h reduction at 923 K in 5 % H2/Ar.
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36 Steam methane reforming was studied in a vertical concentric tubular reactor of a geometry suitable for
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39 future membrane reactors studies. The reactor consisted of an inner dense alumina tube, a quartz sleeve
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and an outer stainless steel shell and was heated by an external electric furnace, see Fig.1. An amount
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46 of 0.1 g of Ni/MgO-SiO2 catalyst diluted with 3.9 g SiO2 particles (Wako Pure Chemical Industries
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49 Ltd.) formed the catalyst bed of volume 3.0 cm3. For optimal heat transfer, the catalyst bed was placed
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52 in the outer annular region between the quartz tube and the dense alumina tube. It was held in the middle
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stainless steel tube covered the quartz tube for mechanical strength and rigid sealing, but an opening
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allowed pressure equalization between its inside and the outside of the quartz sleeve. The reactor
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11 pressure was controlled by a backpressure regulator connected at the reactor outlet and the reactor
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14 temperature was monitored by a thermocouple placed at the bottom of the catalyst bed. A total pressure
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17 of 0.40 MPa and a temperature of 923 K was used for the measurements. The catalyst particles were
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20 sieved to 400-630 m in diameter and the SiO2 particles used for dilution of the catalyst to 600-850 m.
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23 Upstream of the reactor, CH4 and N2 were mixed and introduced to a vaporizer heated at 473 K. Liquid
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26 water was fed using a pump (Hitachi L-7100) to the vaporizer and immediately vaporized and mixed
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32 condensation in the transfer lines. The inlet gas composition was varied by keeping the total flow rate
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35 at 270 mol s-1 (400 cm3 (NTP) min-1), corresponding to a constant gas-hourly space velocity of 2000
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38 h-1. The weight-hourly space velocity (WHSV) and space time (W/F0CH4) was 12000-72000 Ncm3 gcat-
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h-1 and 1.12 - 6.72 kgcat s mol-1 respectively with respect to CH4. The inlet flow composition varied in
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the range of 5-35 vol% for CH4 and 20-70 vol% for H2O, diluted with nitrogen. The space time is
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The outlet gas flow was analyzed by a gas chromatograph (GC-8A, Shimadzu Co.) equipped with a
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12 thermal conductivity detector (TCD) using a combination of Porapak-Q, Shincarbon and Molecular
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15 sieve 5A columns. However, it was difficult to accurately detect the precise amount of H2O with the
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18 TCD due to its large amount and the high affinity between H2O and the GC columns. The amount of
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2.2 Intrinsic kinetics regime verification
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Prior to the kinetic modelling, the Weisz-Prater and the Mears criteria were calculated to assess the
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CH4 conversion of 58% was obtained with 40 kPa CH4, 200 kPa H2O and 160 kPa N2., W = 100 mg,
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vtot = 400 cm3 (NTP) min-1.
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5 Table 1. Quantities in the Mears and Weisz-Prater Criteria
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H Heat of the reaction of SMR -2.04x105 J mol-1
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12 RCH4 Net rate of formation of CH4 0.169 mol kgcat-1 s-1
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14 d Specific length of the reactor 2.5x10-3 m
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17 h Heat transfer coefficient 770 J m-2 K-1 s-1
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19 T Temperature 923 K
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21 Ea Activation energy of SMR 1.5x105 J mol-1
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24 R Gas constant 8.31 J mol-1 K-1
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28 dp Catalyst pellet diameter 5.16x10-4 m
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CCH4,b Bulk gas concentration of CH4 5.51 mol m-3
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Parameter estimation
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The Iteratively Reweighted Least Squares (IRLS) method has been used as regression procedure for model
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12 parameter estimation 15. This procedure consists of minimizing the sum of squares of the residuals e, i.e.,
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18 experimental error with respect to the model parameters in which the variance-covariance matrix D
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24 experimental error, i.e., its variance depends on the operating conditions and weighs each of the elements
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S ( ) = D ( ) Eq. 6
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convergence.
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The tubular reactor is simulated as an ideal plug flow reactor, operated in steady state. The set of continuity
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equations for all components forms the reactor model, shown by Eq. 8 with Ri the net rate of formation of
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26 corresponding outlet molar flow rates of the same components. In total, 37 experiments, including 14
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29 repetition experiments, were taken into account for the regression.
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squares and the pure-error sum of squares (Eq. 9). The former is calculated as the difference between the
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residual sum of squares and the latter as the pure-error sum of squares of the variance of repeated
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48 observations 17. The test is based on the null hypothesis that the model is adequate and states that Fa is
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a confidence level of 0.95 is selected, corresponding with a tabulated F value in the range of 2 5, the
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exact value being determined by dfLOF and dfPE. It should be noted that the adequacy test is a severe test
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of 100.
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14 The model in this work was regressed to the experimental data and analyzed with the MicroKinetic Engine
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17 (KE) 18. The KE is a software tool for the simulation and regression of chemical kinetics and has been
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20 developed at the Laboratory for Chemical Technology at Ghent University. Two deterministic regression
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3. RESULTS AND DISCUSSION
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3.1 State-of-the-art and catalyst choice
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13 This study employed a Ni/MgO-SiO2 catalyst. The BET surface area was 105 m2g-1 and the hydrogen
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16 uptake, Vads, was 90 mol g-1. The hydrogen uptake (Vads) can be used to calculate the particle size 19
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19 from the formula, d = 6c/VadswNA where c is the supported Ni metal weight % (43.2wt%), is the
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22 bulk Ni density (8.91 g cm-3), is the surface Ni atom density (0.0649 nm2/atom), w is the weight of
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25 catalyst, and NA is Avogadros number. The calculated particle size was 41 nm. The dispersion of the
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28 catalyst can be obtained from the hydrogen uptake and the Ni content of the catalyst, D = VadsMWNi/c,
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31 and is found to be 1.2%, which is consistent with the large particle size. Measurements on the catalyst
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34 were carried out for more than two weeks, while verifying reproducibility of points. This sets the
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Recent developments in the area of catalytic SMR were described in a 2013 review 20. Here, the latest
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catalysis studies since then are summarized. Using conventional SMR reactors 21, most of the papers
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summarized in Table 2 at reaction conditions that are similar to those used in the present investigation.
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As can be seen, some of the experimental results are at or close to equilibrium. The present studies are
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16 Table 2. Summary of recent results in steam methane reforming
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19 WHSV (space
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T P XCH4 Equil.XCH4
22 Catalyst Ni content H2O/CH4 Ncm3CH4 h-1 CO2/CO Stability Ref.
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24 gcat-1 (kgcat s
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27 Ni/CaO-Ca5Al6O14 15 wt% Ni 923 0.10 4 230 (350.83) 95 95 0.48 NR 22
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29 Ni/-Al2O3 20 wt% Ni 928 0.10 3 15000 (5.38) 88 98 NR NR 23
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31 Ni/K2TixOy-Al2O3 11 wt% Ni 973 0.10 2.5 15000 (5.38) 86 96 NR >100 h 24
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NiAl2O4
36 33 wt% Ni 923 0.10 3 38000 (2.12) 80 96 0.70 NR 26
37 (spinel structure)
38
39 Ni/TiO2 10 wt% Ni 773 0.10 1 6000 (13.45) 27 29 2.4 > 96 h 27
40
41
10 wt%
42 Ni/SiO2 973 0.10 0.5 12000 (6.72) 20 83 NR NR 28
43 NiO
44
45 Ni/ZrO2 15 wt% Ni 873 0.10 1 39000 (2.07) 20 71 1.2 4h 29
46
47 64 wt%
48 Ca-Ni/Al2O3 873 0.10 4 NR 85 95 0.36 NR 30
49 NiO
50
51 Ni/SBA-15 25 wt% Ni 823 0.10 2 NR 21 48 NR NR 31
52
53 56 wt%
54 Ni/MgO-SiO2 923 0.40 2 48000 (1.68) 40 61 2.1 > 200 h *
NiO
55
56
57 NR: Not reported, * This work
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4
A more extended range of operating conditions has been investigated as part of the present work. Of
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course, some repetition experiments have been performed, i.e., 10 experiments with feeds consisting of
9
10
11 CH4 20 %, H2O 40 %, N2 40 %, 2 experiments with CH4 20 %, H2O 60 %, N2 20 % and 2 experiments
12
13
14 with CH4 25 %, H2O 60 %, N2 15 %. The relationship between the methane conversion and the WHSV
15
16
17 is plotted in Fig. 2 for the studies reported in Table 1. As can be seen, the data can be categorized in two
18
19
20 regions, each exhibiting a decreasing conversion with increasing WHSV. The measurements with a
21
22
23 H2O/CH4 ratio exceeding 2 resulted in a higher CH4 conversion than those with a H2O/CH4 ratio below
24
25
26 2. Variation of the points from the trend lines is expected as there is some variation in temperature and
27
28
29 H2O/CH4 ratio, even though the reported studies all used a pressure of 0.10 MPa. The results obtained
30
31
32 as part of the present work with a H2O/CH4 ratio equal to 2 and with a higher pressure of 0.40 MPa are
33
34
35 situated in the middle of the two regions. The filled square shows a simulated result, which will be
36
37
38 discussed later, see section 3.
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4 Space time / kgcat s mol-1CH
5 4

6 -- 8.07 4.03 2.69 2.02 1.61

7 100
8 (20)
(19) (22)
9
10 80 (21)
(23)
CH4 conversion / %
11
12 H2O/CH4 = 2.5 ~ 4
13 60
14 This work
15 H2O/CH4 = 2
16
17 40
18
19 H2O/CH4 = 0.5 ~ 1
20 20 (19)
21 (25) (26)
22
23
24
0
25
0 10000 20000 30000 40000 50000
3 -1 -1
26 WHSV / Ncm CH4
h g cat
27
28
29
Fig. 2. Relationship between the conversion of methane and WHSV/space time in recent studies on
30
31 steam methane reforming with Ni-based catalysts. Reference numbers are indicated by each point and
32
33 correspond to Table 1. The lines are a guide for the eye. : H2O/CH4 > 2, : H2O/CH4 < 2, : this
34
35 work (H2O/CH4/N2 = 2/1/2, total inlet flow 400 Nml min-1, 0.4 MPa, 923 K), : simulated result
36
37 (H2O/CH4/N2 = 2/1/2, total inlet flow 400 Nml min-1, 0.10 MPa, 923 K), by solving the set of Eq. 8
38 with the net rates of formation given by Eqs. 19 to 23. The rate and equilibrium coefficients are
39
40 estimated by a weighted regression and are shown in Table 2.
41
42
43
44 3.2 Reaction description and model construction
45
46
47
48 In this study, SMR is described with a simple model consisting of four steps, which are defined as (1)
49
50
51 CH4 adsorption on the catalyst surface, (2) H2O adsorption on the catalyst surface, (3) the oxidation of
52
53
54 CH4 towards CO and H2 and (4) the water-gas shift reaction. This combination of steps was chosen
55
56
57 as the simplest possible set from a kinetic standpoint, and is not meant to represent an actual mechanism
58
59 18
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with elementary steps. In fact it is unlikely for methane and water to adsorb molecularly, and the

adsorbed species shown are just representations of species such CHx, C, CO, or H As such the

parameters of the reaction will be called equilibrium coefficients and rate coefficients, rather than

equilibrium constants and rate constants.

Simple Model

Reaction (1)

Reaction (2)

Reaction (3)

Reaction (4)

We have also considered a case where Reaction (4), the water-gas shift reaction, is reversible. This

will be discussed below and the results presented in the Supplementary Information.

The asterisk indicates adsorbed species or empty sites. In this model the products CO, CO2 and H2 are

assumed to desorb from the catalyst instantaneously, i.e., no adsorption is taken into account for the

products. The model combines a surface reaction for the reforming step with a gas-surface reaction

for the water-gas shift reaction. The latter does not imply a mechanism and is formulated simply to
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avoid an explicit term containing adsorbed CO.
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9
Aside from the equilibrium adsorption steps, the other steps are considered to be irreversible, with the
10
11
12 reverse reactions not being involved. This is a simplification, made in order to reduce the number of
13
14
15 fitting parameters in this model. Since much of the data are at relatively low conversion, this is
16
17
18 permissible. The effect of the reverse reaction is incorporated into the reaction rate parameters, which
19
20
21 will have lower values than if the back reaction were explicitly considered. This will be discussed
22
23
24 later.
25
26
27
28 The equilibrium coefficients for Reaction (1) is K1 and for Reaction (2) is K2. Eq. 11 and 12 show the
29
30
31 net reaction rate of step (3) and (4) with k3 and k4 the corresponding rate coefficients. The reactant
32
33
34 concentrations are expressed in terms of surface concentrations because, contrary to the products, CH4
35
36
37 and H2O react from the adsorbed state.
38
39
40 r3 = k 3CCH * C H' O* Eq. 11
41 4 2

42
43 r4 = k 4 pCO C H O* Eq. 12
44 2

45
46
47 When two surface species are involved in a reaction step as in Reaction (3), the surface species cannot
48
49
50 occupy just any sites, but these sites need to be next to each other for the reaction to take place. This
51
52
53 adjacent site requirement has been treated in a textbook 33, and is accounted for in the rate expression
54
55
56 of the reaction step, using the number of adjacent neighbors z and Ctot the total concentration of
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active sites as shown in Eqs. 13 and 14. When properly accounting for the dual site mechanism in the
5
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8
rate expression of the reforming step, the reaction rate varies linearly with the total concentration of
9
10
11 active sites, and not quadratically. 34
12
13
14 The new rate expressions r3 and r4 , shown in Eq. 14 and Eq. 15, are obtained by writing the
15
16
17 concentration of the surface species in terms of the surface coverage 35.
18
19
20 C H O*
21 C H' O* = z 2
= z H 2O Eq. 13
2
Ctot
22
23
24 r3 = k 3 zCCH * H 2O = k 3 zCtot CH 4 H 2O Eq. 14
25 4

26
27
28
r4 = k 4 pCO Ctot H 2O Eq. 15
29
30
31 After substituting the surface coverages with observable quantities, i.e., the partial pressures of the
32
33
34 components, the final expression of the reaction rate equations is obtained. The site balance (Eq. 16)
35
36
37 and the expressions for quasi equilibrium of the adsorption/desorption steps (Eq. 17 and 18), allow to
38
39
40 write the rate expression in terms of the partial pressure of methane, water and carbon monoxide (Eq.
41
42
43 19 and 20).
44
45
46 1 = * + CH 4 + H 2O Eq. 16
47
48
49 k1+
50 CH = pCH 4 * = K1 pCH 4 * Eq. 17
51
4
k1
52
53
k 2+
54 H O = p H O * = K 2 p H 2O * Eq. 18
55 2
k 2 2
56
57
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59 21
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3
k 3 K 1 K 2 zC tot p CH 4 p H 2O k 3' K 1 K 2 p CH 4 p H 2O
4 r3 = =
5 (1 + K 1 p CH 4 + K 2 p H 2O )2
(1 + K 1 p CH 4 + K 2 p H 2O )
2 Eq. 19
6
7 k 4 K 2 C tot p CO p H 2O k 4' K 2 p CO p H 2O
8 r4 = = Eq. 20
9 1 + K 1 p CH 4 + K 2 p H 2O 1 + K 1 pCH 4 + K 2 p H 2O
10
11
12 In order to solve the plug flow reactor model, see Eq. 8, the rate expressions are substituted in the net
13
14
15 rate of formation Ri for each component (Eqs. 21 to 5).
16
17
18 RCH 4 = r3 Eq. 21
19
20
21 RH 2 O = r3 r4 Eq. 22
22
23
24 RCO = r3 r4 Eq. 23
25
26
27 RCO2 = r4
28 Eq. 24
29
30
RH 2 = 3r3 + r4 Eq. 25
31
32
33
34 3.3 Model and parameter estimates assessment and discussion
35
36
37 Fig. 3a,b) show the same data of CH4 conversion as a function of the H2O inlet partial pressure for CH4
38
39
40 inlet partial pressures amounting to 40 kPa, 80 kPa, and 120 kPa. The lines represent the results of the
41
42
43 weighted regression. As expected, the CH4 conversion was higher when its inlet partial pressure was lower.
44
45
46 The CH4 conversion increased with increasing H2O partial pressure, although at high H2O inlet partial
47
48
49 pressure the CH4 conversion tended to decline. This behavior can be explained by the CH4 inhibition on
50
51
52 the catalyst surface by adsorbed H2O.
53
54
55
56 The numbers in Fig. 3a represent the equilibrium quotients for the MSR reaction, defined as
57
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59 22
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2
3
4 2 3 1
= 2
Eq. 26
5 4 2
6
7
8
At equilibrium at 923 K, QSMR is equal to the equilibrium constant, K = 2.76. All the points are in a
9
10
11 state far away from equilibrium.
12
13
14 The numbers in Fig. 3b represent the equilibrium quotients for the WGS reaction, defined as
15
2 2
. Eq. 27
16
17 =
2
18
19
20 At equilibrium QWGS is equal to the equilibrium constant, K= 2.04. No point was in the equilibrium
21
22
23 state, but some were relatively close.
24
25
26
27
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32
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4 65
5 0.0053 0.0033
a) 0.0054
6 0.0083

CH4 conversion / %
7 55
8 0.012
9 0.0006 0.0004
10
11 45
12 Numbers:
13 QSMR 0.0093 0.0067
14 35 0.015 0.012
15
0.011
16
0.013
0.011
17 25
18 40 80 120 160 200 240 280 320 360
19
20 H2O inlet partial pressure / kPa
21
22
23 65
1.17
24 b) 1.31 1.21 Value of QWGS
25 1.24
CH4 conversion / %

26 55
27
1.15
28 1.56 1.37
29 45
30
31 1.43
32 0.96 1.17
35 1.16
33
34 1.06 1.02
35 1.06
36 25
37 40 80 120 160 200 240 280 320 360
38 H2O inlet partial pressure / kPa
39
40
41 Fig. 3. Simple model results for CH4 conversion as a function of the H2O inlet pressure. Points:
42 experimentally observed, lines: calculated by solving the set of Eq. 8 with the net rates of formation
43
44 given by Eqs. 19 to 23. Results are for at a total pressure of 0.40 MPa and a temperature of 923 K. The
45 rate and equilibrium coefficients are obtained by a weighted regression and are shown in Table 2. , full
46
47 line, black - 40 kPa CH4 inlet partial pressure (p0CH4) or a space time of 3.36 kg s mol-1, , dashed line,
48 red - 80 kPa p0CH4 or 1.68 kg s mol-1, , dotted line, blue - 120 kPa p0CH4 or 1.12 kg s mol-1.
49
50 a) The numbers shown are the equilibrium quotients for the methane steam reforming, QSMR, with a
51
52
value at equilibrium of 2.76. Conditions are far from equilibrium.
53 b) The same data are shown but now the numbers show the equilibrium quotients for the water-gas shift
54
55 reaction, QWGS, with a value at equilibrium of 2.04. Conditions are closer to equilibrium.
56
57
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4
Because the data for the WGS reaction were relatively close to equilibrium, calculations were carried
5
6
7 out to ascertain whether the reverse reaction could influence the results of the fitting of the present data.
8
9 Details are reported in the Supplementary Information. The analysis indicates that there was no
10
11
12 significant influence on the results. Calculated values for the kinetic parameters are shown in Table 3,
13
14 to be discussed later.
15
16
17 Fig. 4 shows the selectivity to CO and CO2 as a function of the H2O inlet partial pressure for a CH4 inlet
18
19 partial pressure amounting to 80 kPa. The model is able to simulate the correct trend for the selectivities
20
21
22 with varying H2O partial pressure. Nevertheless there is a systematic deviation between the experimentally
23
24 observed and calculated data.
25
26
27 35 85
28
29
30

Selectivity to CO2 / %
30 80
Selectivity to CO / %

31
32
33
34
35 25 75
36
37
38
39
40 20 70
41
42
43
44 15 65
45 160 200 240 280
46
47
H2O inlet partial pressure / kPa
48
49 Fig. 4. Selectivity to CO and CO2 as a function of the inlet partial pressure of H2O at a total pressure of
50
51 0.4 MPa, a temperature of 923 K, a space time of 1.44 kg s mol-1 and conversions between 40 % and 44 %.
52 Points: experimentally observed, lines: calculated by solving the set of Eq. 8 with the net rates of formation
53
54 given by Eqs. 19 to 23. The rate and equilibrium coefficients are estimated by a weighted regression and
55 are shown in Table 2. , full line, black - selectivity to CO, , dashed line, red - selectivity to CO2.
56
57
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59 25
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5
6
7 Fig. 5 shows the CO and CO2 selectivity as a function of CH4 conversion at a H2O inlet partial pressure
8
9
10 of 160 kPa. Most of the data only exhibit a minor dependence on the CH4 conversion. The two empty
11
12
13 symbols deviate more strongly from the simulated lines and are considered as outliers. They were obtained
14
15
16 with a CH4 inlet partial pressure of 20 or 40 kPa which were the lowest pressures used, so produced the
17
18
19 lowest amounts of CO and CO2. Therefore, these points were retained in this figure, but omitted in the
20
21
22 regression analysis.
23
24
25 100
26
27
28
29 80
Selectivity / %

30
31
32 60
33
34
35
36 40
37
38
39 20
40
41
42
43 0
44 30 40 50 60
45 CH4 conversion / %
46
47
48 Fig. 5. Selectivity to CO and CO2 as a function of the conversion for the simple model at 0.40 MPa and
49 923 K, a catalyst mass of 0.1 g, a H2O inlet partial pressure of 160 kPa and a CH4 inlet partial pressure
50
51 between 20 and 100 kPa. Points: experimentally observed, lines: calculated by solving the set of Eq. 8
52 with the net rates of formation given by Eqs. 19 to 23. The rate and equilibrium coefficients are estimated
53
54 by a weighted regression and are shown in Table 2. , full line, black - selectivity to CO, , dashed line,
55 red - selectivity to CO2.
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5
Fig. 6 shows a parity diagram for each of the responses for the simple model. The weighted regression
6
7 shows an excellent agreement between model simulated and experimentally measured CH4 outlet molar
8
9
flow rates, a good agreement for H2O, CO, and CO2, and moderate agreement for H2. The closure of the
10
11
12 carbon balance of the experimental data, as explained in the procedures, has led to a slight but consistent
13
14
overestimation of the H2 outlet molar flow rate and corresponding underestimation of the CO2 outlet molar
15
16
17 flow rate in the experimental dataset. The non-zero average value of the error of two out of five model
18
19 responses, i.e., the outlet flow rate of H2O and H2, is attributed to the non-closure of the hydrogen and
20
21
22 oxygen balance in the experimental data.
23
24
25 100 220
26
Predicted FCH / 10-6 mol s-1

Predicted FH O / 10-6 mol s-1

27 80 180
28
29
60 140
30
31
4

32 40 100
2

33
34 20 60
35
36 0 20
37 0 20 40 60 80 100 20 60 100 140 180 220
38 -6 -1 -6 -1
Observed FCH / 10 mol s Observed FH O / 10 mol s
39 4 2

40
41 10 24
42
Predicted FCO / 10-6 mol s-1
-1

22
Predicted FCO / 10 mol s

43 8
44 20
45
-6

6
46 18
47 16
2

4
48
49 14
50 2
12
51
52 0 10
53 0 2 4 6 8 10 10 12 14 16 18 20 22 24
-6 -1 -6 -1
54 Observed FCO / 10 mol s Observed FCO / 10 mol s
2
55
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3
4 140
5

Predicted FH / 10-6 mol s-1

6 120
7
8 100
9
10

2
80
11
12
60
13
14
15 40
40 60 80 100 120 140
16
17
Observed FH / 10-6 mol s-1
2

18
19 Fig. 6. Parity diagram for the simple model of the molar outlet flow rate FCH4, FH2O, FCO, FCO2 and FH2 for
20
21 the weighted regression at a temperature of 923 K and a total pressure of 0.4 MPa. The estimated rate and
22 equilibrium coefficients are shown in Table 2.
23
24
25
26
27
28 Table 3 compares results of the simple model and a model that considers the reversibility of the WGS
29
30
31 reaction. Shown are the parameter estimates and the corresponding 95 % confidence intervals; K1 for
32
33
34 CH4 adsorption, K2 for H2O adsorption, k3 for steam methane reforming and k4 for the water-gas shift
35
36
37 reaction. The K1, K2, and k3 parameters are close in both models, indicating no major deviations in their
38
39
40 interpretation. The k4 values are necessarily different because of the assumption of reversibility, which
41
42
43 k 4+ K S
44 introduces the equilibrium constant for the WGS in the calculations ( K 4 = = ).
45
k 4 K 2
46
47
48 For the simple model all parameters are statistically significant as shown by the narrow confidence
49
50
51 intervals. For the results of this paper, the tabulated Fa value for model adequacy is 1.48. The calculated
52
53
54 Fa value of 2.39 is very close to the tabulated one, indicating that the model is on the edge of being
55
56
57 adequate.
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The tabulated F value with respect to the global significance is 2.42. The calculated Fs value of the
5
6
7
8
weighted regression of 1.02x104 greatly exceeds this value and hence the performed regression is globally
9
10
11 significant. The maximum binary correlation coefficient amounts to -0.9043 between the equilibrium
12
13
14 coefficient K1 and the rate coefficient k3.
15
16
17 For the simple model with consideration of the reverse WGS reaction the tabulated Fa value for model
18
19
20 adequacy is 1.48. The calculated Fa value of 2.84 is very close to the tabulated one, indicating that the
21
22
23 model is also on the edge of being adequate.
24
25
26 The tabulated F value with respect to the global significance is 2.42. the calculated Fs value of the weighted
27
28
29 regression of 7.81x103 greatly exceeds this value and hence the performed regression is globally
30
31
32 significant. The maximum binary correlation coefficient amounts to -0.93 between the equilibrium
33
34
35 coefficient K2 and the rate coefficient k3.
36
37
38 Overall, both models are adequate. The simple model has narrower parameter confidence intervals while
39
40
41
the simple model with the reverse WGS reaction has a larger Fs value.
42
43
44
45
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4 Table 3. Calculated model parameters at 923 K for the weighted regressions with 95 % confidence interval
5
6
7
8 Simple model with
Simple model Units
9 reversible water-gas shift
10
11
12
K1 30.3 0.3 28.8 4.8 MPa-1
13
14
15 K2 13.5 0.1 12.5 2.5 MPa-1
16
17 k 3' = k 3 zC tot 1.7 0.1 1.63 0.17 mol kgcat-1 s-1
18
19 k 4' = k 4 C tot 74.0 0.5 1.11 0.03 mol MPa-1 kgcat-1 s-1
20
21 Fs 1.02x104 7.81x1043 -
22
23 Fa 2.39 2.84 -
24
25
26
27
28
29
30 Fig. 7 shows the calculated coverages of the catalyst surface obtained with the simple sequence by species
31
32 derived from CH4 (CH4), H2O (H2O), and empty sites (*), as well as the product of CH4 and H2O as a
33
34
35 function of the H2O partial pressure at a CH4 partial pressure amounting to 80 kPa and calculated from K3
36
37 and K4 obtained from the weighted regression, see Table 2, and Eqs. 16-18. With increase of the partial
38
39
40 pressure of H2O, the catalyst surface coverage by CH4 decreased, as the coverage by H2O increased. As
41
42 was discussed in the description of the reaction sequence, the coverages denote species associated with
43
44
45 methane (CH4) and species associated with water (H2O), not necessarily the reactants themselves, as these
46
47 would probably not be on the surface at high coverages. Consideration of actual species would greatly
48
49
50 complicate the analysis, introducing many additional parameters, that is unwarranted from the data. The
51
52 product of both coverages reaches a maximum with increasing H2O inlet partial pressure. This reflects the
53
54
55 behavior of the CH4 conversion versus the H2O inlet partial pressure, see Fig. 3. Indeed, Eq. 14 shows that
56
57 the CH4 consumption rate in SMR (r3) is proportional to the product of the coverage of CH4 and H2O.
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4
5
Therefore, the model follows this trend, Fig. 3. It can be noted that the fraction of free sites on the surface
6
7 decreases as the H2O partial pressure increases, but falls slightly less than the coverage in CH4 derived
8
9
products.
10
11
12
13
14
15
16 1.0 0.20
17
18 CH x H O
4 2
19 0.8
20 0.15

CH x H O / -
Coverage / -

21
H O

2
22 0.6
23 2

24 0.10
*

4
25 0.4
26
27
28 0.05
0.2
29
30
CH
4

31
0.0 0.00
32
100 200 300
33
34 H2O partial pressure / kPa
35
36
37 Fig. 7. Coverage of catalyst surface by species related to H2O (H2O), CH4 (CH4), empty sites (*) and the
38 product of H2O and CH4 as a function of the partial pressure of H2O. Partial pressure of CH4: 80 kPa,
39
40 Temperature: 923 K, Total pressure: 0.40 MPa. The coverages are calculated with Eqs. 14 to 16. The
41 equilibrium coefficients are estimated by a weighted regression and are shown in Table 2. Full line, black
42
43 - H2O x CH4, dashed line, red - H2O, dotted line, green - *, dash-dot line, blue - CH4.
44
45
46
47
48 The kinetic model with the model parameters estimated by the weighted regression is subsequently used
49
50
51 to simulate the CH4 conversion at a WHSV of 48000 Ncm3 h-1 gcat-1, a H2O/CH4 ratio of 2 and a total
52
53
54 pressure of 0.1 MPa, see filled square in Fig. 2. By decreasing the total pressure from 0.4 MPa to 0.1
55
56
57 MPa, the conversion drops as indicated by the arrow in Fig. 2. This is an interesting result, as the
58
59 31
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equilibrium conversion decreases with increasing pressure due to the stoichiometry of the SMR reaction,
5
6
7
8
see Eq. 1. The increase in conversion with pressure is due to enhanced kinetics, with rates increasing
9
10
11 with higher coverages of reactants as given by Eqs. 11 and 12. This will be discussed subsequently.
12
13
14
15 An important result from the model developed in this work is presented in Fig. 8 which illustrates the
16
17
18 effects of total pressure and space time on the CH4 conversion. The currently developed model did
19
20
21 not include thermodynamic constraints as it assumed an irreversible reaction, hence, an additional
22
23
24 software package (NASA, Chemical Equilibrium with Applications) was used to determine the
25
26
27 equilibrium conversion. As expected, the CH4 conversion decreases with increasing inlet CH4 flow rate.
28
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30 At low space velocity the conversion is lower at higher pressure because of thermodynamic equilibrium.
31
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33 This is, of course, because the increase in moles in the SMR dictates that conversion will be lower at
34
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36 higher pressure by Le Chateliers principle. However, at higher space velocity a transition is made to
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39 the kinetic regime. Thus, a higher total pressure leads to a higher reaction rate, because adsorption rates
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are higher, as long as the reaction is not close to thermodynamic equilibrium. These results are not
44
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46 due to the suppression of the back reaction, as the model used here assumes an irreversible reaction
47
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49 step. Those results rationalize why SMR is practiced industrially at high pressure, despite the
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52 unfavorable equilibrium. The decrease in conversion with space velocity is reported in other
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55 studies24,25,36,37, but the crossover has not been noted.
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4 Space time / kgcat s molCH -1
5 4

6 -- 8.07 4.03 2.69 2.02 1.61

7 100
8 0.10 MPa (Xeq= 86.7%)
9
10 80 0.20 MPa(Xeq= 74.3%)
CH4 conversion / -

11
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13 0.40 MPa(Xeq= 60.6%)
14 60
15
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17 40
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19
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21 20
22
23
24
Thermodynamic control Kinetic control
25
0
26 0 10000 20000 30000 40000 50000
3 -1 -1
27 WHSV / Ncm CH4
g h
cat
28
29
30
31 Fig. 8. Simulation result of CH4 conversion change as a function of the WHSV/space time of CH4 at
32
various pressures. The points are the result of the calculation with Eq. 19 and Eq. 20 and the lines are
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34 drawn by B-spline through the points including the equilibrium points, temperature: 923 K, inlet gas
35
36
composition: H2O/CH4/N2 = 2/1/2, total inlet flow of 400 Nml min-1. The dashed lines show the
37 equilibrium CH4 conversion for each reaction condition. The rate and equilibrium coefficients are
38
39 estimated by a weighted regression and are shown in Table 2. Full line, black 0.1 MPa, dash-dot line -
40 red, 0.2 MPa, dashed line, blue 0.4 MPa.
41
42
43
44
Fig. 9 shows the effect of changing the H2O/CH4 ratio on the CH4 conversion as a function of WHSV.
45
46
47 The CH4 conversion is higher for higher H2O/CH4 ratios and decreases with increasing WHSV. These
48
49
50 trends are similar to those seen in Fig. 2 for both higher and lower H2O/CH4 ratio and can be understood
51
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53 based on the analysis of the surface coverages as shown in Fig. 7. Thus, the model developed in this
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56 work is able to describe general trends found from analysis of literature data.
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4 Space time / kgcat s molCH -1
5 16.14 13.45 11.53 4
10.09
6 100
7
8 3.0
9 80
10 CH4 conversion / - 2.0
11
12 1.5
60
13
14 1.0
15 40
16 H2O/CH4 = 0.5
17
18
19
20
20
21
22 0
23 5000 6000 7000 8000
24
WHSV / Ncm3CH h-1 gcat-1
4

25
26
27 Fig. 9. Comparison of simulated CH4 conversions as a function of WHSV/space time of CH4 varying
28 H2O/CH4 ratios at 923 K, 0.10 MPa, total inlet flow of 400 Nml min-1, inlet flow CH4 80 Nml min-1. The
29
30 lines are drawn by B-spline through each points. The rate and equilibrium coefficients are estimated by a
31
weighted regression and are shown in Table 2. Full line, magenta - H2O/CH4 = 3.0, green - H2O/CH4 =
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33 2.0, blue- H2O/CH4 = 1.5, red - H2O/CH4 = 1.0, black - H2O/CH4 = 0.5.
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4 4. CONCLUSIONS
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7 A Ni/MgO-SiO2 catalyst was used to study the catalytic steam methane reforming in a tubular reactor
8
9
10 at 0.40 MPa and 923 K. The CH4 and H2O partial pressure effects were measured and analyzed by a
11
12
13 combined simple reaction model that considered the adsorption of the reactants and the surface reaction
14
15
16 of their derived species, as well as the water-gas shift reaction . Values for the rate and equilibrium
17
18
19 coefficients in this model were obtained by regression and resulted in a good agreement with
20
21
22
experimental results as well as generally reported trends in the literature. Consideration of the
23
24
25
26
reversibility of the water-gas shift reaction did not significantly improve the simple model.
27
28
29 Particularly interesting was that the space velocity (space time) effect on the methane conversion
30
31
32 revealed a cross-over with total pressure due to transition from thermodynamic to kinetic control. Due
33
34
35 to the molar expansion during reaction, increasing the total pressure will lead to a decrease in conversion
36
37
38 when operating in the thermodynamic controlled regime. In the kinetic controlled regime, the reactant
39
40
41 surface coverages monotonically increase with total pressure, resulting in higher methane conversions.
42
43
44 Model predictions at lower total pressures correspond to experimental observations reported in the
45
46
47 literature, confirming that the developed model, although extremely simple, conveys the most essential
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50 features for SMR.
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4 NOMENCLATURE
5
6
7 Roman
8 A matrix A -
9
10 b estimated model parameter -
11
CA concentration of A mol m-3
12
13 concentration of A adsorbed on
14 CA* mol kg-1
15
surface
16 total concentration of active
17 Ctot mol kg-1
18 sites
19 C dimensionless concentration -
20
21 dp catalyst pellet diameter m
22 De effective gas-phase diffusivity m2 s-1
23
24 e residual mol s-1
25 Fa F value for adequacy -
26
27 Fs F value for significance -
28 FA molar flow rate of A mol s-1
29
30 H0 standard reaction enthalpy kJ mol-1
31
32
i.d. inner diameter m
33 k reaction rate coefficient reaction dependent
34
35 kc mass transfer coefficient m s-1
36 K equilibrium coefficient Pa-1
37
38 n reaction order -
39 o.d. outer diameter m
40
41 p pressure Pa
42 r specific reaction rate mol kgcat-1 s-1
43
44 RA specific production rate of A mol kgcat-1 s-1
45 R universal gas constant J mol-1 K-1
46
47 T temperature K
48
W catalyst mass kg
49
50 X independent variable -
51
52
X conversion %
53 y measured quantity mol s-1
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55 z number of neighbors -
56 Greek
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4 model parameter -

5 experimental error mol s-1

6
7 A surface coverage of A -
8 density kg m-3
9
10 Subscripts
11
12
b bulk -
13 cat catalyst -
14
15 eq equilibrium -
16 Superscripts
17
18 0 standard, inlet -
19 * active site -
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4 AUTHOR INFORMATION
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6 Corresponding authors
7
8
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10 S. Ted Oyama Email oyama@vt.edu
11
12 Joris Thybaut Email joris.thybaut@ugent.be
13
14 Notes
15
16
17
18 The authors declare no conflicting interests.
19
20
21 ACKNOWLEDGEMENTS:
22
23
24
25
26
This work was supported by a doctoral fellowship from the Fund for Scientific Research Flanders
27
28
29 (FWO), the European Research Council under the European Unions Seventh Framework Programme
30
31
32 (FP7/2014-2019) / ERC grant agreement n 615456 and the Long Term Structural Methusalem
33
34
35 Funding by the Flemish Government. NK is grateful for support from Kagaku Jinzai Ikusei Program.
36
37
38 STO received support from the director, National Science Foundation under grant CHE-1361842. AT
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40
41 and STO also received assistance from Fuzhou Univ., College of Chemical Engineering. The catalyst
42
43
44 was kindly supplied by JGC Catalysts and Chemicals Ltd.
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46
47
48
49 SUPPORTING INFORMATION
50
51 Brief description of the simple model fit augmented by reversibility of the water-gas shift reaction.
52
53
54 Comparison of results of the simple model and the model with reversibility of the WGS reaction.
55
56
57 Details of the calculation of the Mears Criterion for lack of heat transfer limitations.
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5 Crossover of CH4 conversion curves with WHSV/space time due to a transition between
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7 thermodynamic to kinetic control.
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11 Space time / kgcat s molCH -1
4
12 -- 8.07 4.03 2.69 2.02 1.61
13 100
14
15 0.10 MPa (Xeq= 86.7%)
16
80 0.20 MPa(Xeq= 74.3%)
CH4 conversion / -

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19 0.40 MPa(Xeq= 60.6%)
20 60
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24 40
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27 20
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30 Thermodynamic control Kinetic control
31 0
32 0 10000 20000 30000 40000 50000
33 3 -1 -1
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WHSV / Ncm CH4
g h
cat
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