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2432

J. Phys. Chem. B 2005, 109, 2432-2438

Methanation of CO over Nickel: Mechanism and Kinetics at High H2/CO Ratios†
Jens Sehested,* Søren Dahl, Joachim Jacobsen, and Jens R. Rostrup-Nielsen
Haldor Topsøe A/S, NymølleVej 55, DK-2800 Kgs. Lyngby, Denmark ReceiVed: March 23, 2004

The CO methanation reaction over nickel was studied at low CO concentrations and at hydrogen pressures slightly above ambient pressure. The kinetics of this reaction is well described by a first-order expression with CO dissociation at the nickel surface as the rate-determining step. At very low CO concentrations, adsorption of CO molecules and H atoms compete for the sites at the surface, whereas the coverage of CO is close to unity at higher CO pressures. The ratio of the equilibrium constants for CO and H atom adsorption, KCO/KH, was obtained from the rate of CO methanation at various CO concentrations. KH was determined independently from temperature programmed adsorption/desorption of hydrogen to be KH ) 7.7 × 10-4 (bar-0.5) exp[43 (kJ/mol)/RT] and hence the equilibrium constants for adsorption of CO molecules may be calculated to be KCO ) 3 × 10-7 (bar-1) exp[122 (kJ/mol)/RT]. Furthermore, the rate of dissociation of CO at the catalyst surface was determined to be 5 × 109 (s-1) exp[-96.7 (kJ/mol)/RT] assuming that 5% of the surface nickel atoms are active for CO dissociation. The results are compared to equilibrium and rate constants reported in the literature.
Kinetic Langmuir-Hinshelwood models (LH) for CO methanation were suggested by Yadav and Rinker,11 Ho and Harriot,12 van Meerten et al.,13 Klose and Baerns,14 and Coenen et al.,9 whereas Schoubye,15 Dalmon and Martin,16 and Hayes et al.17 found that LH models could not account for the experimental observations. Goodman et al.18-20 studied the methanation rate over well-defined surfaces. They found that the turnover frequencies on Ni(111) and Ni(100) were equal and that they compared well with methanation rates obtained on aluminasupported catalysts.6,21 The agreement was obtained for the preexponential factor and the activation energy as well. A similar strong linear decline of the methanation activity for small coverages of sulfur was found for both Ni(100)19 and a nickel alumina catalyst.6 This observation could be explained by statistical model for the chemisorption of sulfur.22 Alstrup8 proposed a microkinetic model with CH* + H* as the rate determing step. In the model the coverages of CO, hydrogen, and carbon were significant. To fit the experimental data, Alstrup had to treat the coverage of carbon as a free parameter in the model. The model reproduced the reported rate data of Goodmann and co-workers18 over nickel single crystals and of Polizzotti and Schwartz23 over polycrystalline nickel foils. Bengaard et al.24 calculated the energies by density functional theory at the closed packed Ni(111) and the stepped Ni(211) of the transition states and the stable intermediates in the elementary reactions involved in re-forming. Because re-forming is the reverse reaction of CO methanation, the energy diagram involved in this work can also be used to obtain information about the title reaction. Two conclusions may be drawn from this work: (i) Nickel steps are much more active than nickel terraces. (ii) The highest barrier is encountered for CO dissociation, suggesting that this reaction is the rate determining step. These results will be used as a guide for the kinetic model presented later. The work reported here is a study of the steady-state CO methanation kinetics over a nickel catalyst at moderate CO

1. Introduction Sabatier and Senderens1 discovered the CO methanation reaction already in the beginning of the last century. CO methanation over nickel is currently used in large ammonia plants to remove the last fraction of a percent of carbon oxides before the synthesis because the iron based ammonia catalysts are very sensitive to poisoning by oxygen. Methanation was subject to a number of studies during the 1970s2 because of an interest in producing substitute natural gas from naphtha3 and coal.4 The activation of carbon monoxide on nickel also plays a key role in metal dusting corrosion on surfaces of equipment exposed to CO-rich gases.5 There is evidence that the CO decomposition to carbon and the methanation reaction are interlinked.6 In the methanation reaction, CO and hydrogen are converted to methane and steam:

CO + 3H2 a CH4 + H2O
The reaction is the reverse steam re-forming reaction, which also proceeds over nickel catalysts.7 Therefore physical parameters as adsorption constants determined for the methanation reaction are relevant for steam re-forming. The kinetics of CO methanation have been studied intensively. Alstrup8 gave an overview of the kinetic models for CO methanation over nickel. In the seventies it was generally believed that methanation proceeds via a COHx intermediate. Coenen et al.9 found no isotopic scrambling when 13C16O and 12C18O together with hydrogen were used as the feed gas, suggesting that hydrogen or non hydrogen assisted CO dissociation is the rate determining step. Goodman et al.10 determined the rate of carbide formation in 31.6 mbar of CO and carbide hydrogenation in 131.6 mbar H2 to be similar to the rate of methanation in 157.9 mbar of CO:H2 ) 1:4 at 177 °C.
Part of the special issue “Michel Boudart Festschrift”. * Corresponding author: Tel.: +45 45 27 23 65. Fax: +45 45 27 29 99. E-mail: JSS@topsoe.dk.

10.1021/jp040239s CCC: $30.25 © 2005 American Chemical Society Published on Web 10/13/2004

the system was heated. As seen from the figure. Before each run. Results and Discussion 3. as determined by sulfur chemisorption according to Rostrup-Nielsen et al. To avoid diffusion limitations. Using a simple reaction mechanism with CO dissociation as the rate determining step.0 mm. While the same flow of 0. the 600-850 µm sieve fraction needs a higher CO level than the 300-600 µm sieve fraction to reach a plateau in the activity.4 bar. The total pressure in the reactor was maintained at 1. At high CO concentrations the reaction order in pCO is zero. First. and the reduction procedure were as described for the first setup. the methanation activity (from the change in CO concentration or from the CH4 concentration) gives equal results within experimental errors. 3. the rate of methanation was measured using inlet flows in the range 3. CO methanation activity of a Ni/MgAl2O4 catalyst in a CO/ H2 atmosphere at 1.27 The reactor. the activity increases with the CO pressure for low CO pressures and reaches a stable plateau at the higher concentrations.3-0. The Ni/MgAl2O4 catalyst had a nickel surface area of 4.1. In this section the rate of methanation of CO over the Ni/MgAl2O4 catalyst as a function of the CO pressure is described. KCO/ KH and the rate constant for CO dissociation at the nickel surface were obtained. methanation over nickel was studied using nickel threads with diameters of 4 and 22 µm supplied by Bekaerd. KH was determined by a fit to temperature programmed adsorption/desorption (TPA/TPD) curves for hydrogen. In the first setup.5-105 mL/min (NTP) of a gas mixture containing 2. Subsequently. No. at which the activity plateau is reached. Phys.15 At even higher CO concentrations a decrease in the activity and consequently negative reaction orders in pCO were reported. A pump delivered a recirculation flow rate of ca. the CH4 concentration in the exit gas (in the reactor) was used to determine the activity for methanation over the nickel threads. Following reduction a flow of 100 cm3/min (NTP) of a gas containing 0. Contrary. 2. as discussed in the Experimental Section. the reactor zone with its own oven. the H2 TPD was run by using a heating ramp of 8 K/min until a temperature of 773 K was reached. There could be at least two explanations for these experimental observations.6 mm) was held between wads of quartz wool.25 Methanation of CO over Ni/MgAl2O4 at low CO pressures suffered from diffusion restrictions. The temperature at the recirculation pump was approximately 75 °C. The second experimental setup was used in the H2 TPD/TPA experiments and consisted of a single pass reactor system described in detail in Fastrup et al. 109. A CO concentration regime where the reaction order in pCO is zero was also observed by Schoubye. 0. sufficient to maintain well-mixed conditions. which gave a catalyst bed height of 15-20 mm. The hydrogen pressure was in all experiments 1. increases with temperature. Second. The tube had an inner diameter of 4. The CO concentration in the reactor changed as the inlet flow of the CO/H2 gas mixture was varied. Nickel threads were used to eliminate diffusion restrictions.1% H2 was maintained in He. the loading of the catalyst. where methanation over the Ni/MgAl2O4 catalyst was investigated.05% CO in H2. 6. The conversion of CO to CO2 was in all cases negligible (<3%) compared to conversion of CO to methane. Clearly. A blank test at 500 °C using 1% CO in hydrogen showed that the reactor system itself had no significant methanation activity. Experimental Section Materials. In Figure 2 the activities for methanation over two different sieve fractions of catalyst particles are plotted as a function of the CO concentration in the reactor.4 bar total pressure plotted as a function of pCO for six temperatures. the loss of activity at low CO concentrations could be due to the intrinsic kinetic behavior of the nickel surface.27 and will only be described briefly here. A standard gas containing 1000 ppm CH4 was used for calibration of the mass spectrometer. and both apparatuses are described in detail elsewhere26. Vol. the H2 TPA was run using a cooling ramp of 8 K/min until a temperature of 273 K was reached. 2005 2433 Figure 1.3-0.1% H2 in He was passed over the catalyst while it was allowed to cool to 240 K.15 The data in Figure 1 show that the CO concentrations.Methanation of CO over Nickel concentrations and over nickel threads at very low CO pressures. Finally. Two experimental setups were used in the present work. the ratio of the equilibrium constants. a recirculating reactor system rather than a singlepass reactor was used because a homogeneous gas phase over the nickel catalyst or nickel thread is desired. Chemical analysis of the threads showed that they contained nickel as the only component Experimental Setups. and the rest with a heated box. Chem. the equilibrium constants and the rate constant are compared to data from the literature. This means that the two ways of determining J. The catalytic reactor consisted of a removable U-shaped glass-lined stainless steel tube in which either 200 mg of nickel catalyst with a particle size of 0. In these experiments large conversions of CO were observed and the methanation activity was determined from the consumption of CO in the reactor. In the first set of experiments. The diffusion restrictions are most important at high activities and low CO concentrations due to the high conversions of CO in these cases. In these experiments the conditions were chosen so that the CH4 concentration was kept below 400 ppm.6 mm or 200-400 mg of nickel thread (4 or 22 µm) together with 70 mg of inert MgAl2O4 (0. This means that the decrease in activity . With the exception of the recirculation pump. CO Methanation over a Ni/MgAl2O4 Catalyst. The rate of methanation of CO determined from the conversion of CO in the reactor is plotted as a function of the CO pressure in the reactor in Figure 1.36 m3/h (NTP). B. The total gas flows were 100-150 mL/min (NTP) of a mixture of 2. A Ni/MgAl2O4 catalyst was used for the temperature programmed adsorption/desorption of hydrogen and the first set of the methanation experiments.05% CO/H2 and pure H2. the nickel catalyst or the nickel thread was reduced in flowing H2 (50 mL/ min NTP) at 525 °C for 10 h.7 m2 Ni g-1.4 bar in all experiments and the reactor effluent was monitored with a mass spectrometer and BINOS infrared CO and CO2 detectors. diffusion restrictions at high conversions of CO could decrease the observed activity of the catalyst at low CO concentrations.

7 × 1019 surface nickel atoms per gram of catalyst. no significant change in the activity was observed after the recirculation pump was stopped: Hence.7 kJ/mol and the TOF for CO methanation over nickel determined here is in good agreement with those determined by Polizzotti and Schwarz23 over polycrystalline nickel foils. CO methanation activity in a CO/H2 atmosphere of a Ni/ MgAl2O4 catalyst at 250 °C for particles in the ranges 300-600 and 600-850 µm. Phys.7 (kJ/mol)/RT] (1) where Ns is the number of active sites per gram of catalyst and TOF is the turnover frequency. a density of 2. the Weisz-Prater criterion28 (Φ < 2 for a zero order reaction) was evaluated for an activity of 100 mmol g-1 h-1. The calculations therefore support the conclusion made above.3 g/cm3.5 × 107 (mol g-1 h-1) exp[-96. The plateau in the activity observed at higher CO concentrations is not subject to any significant diffusion restrictions. a particle radius of 0. As expected for nonporous materials. that diffusion restrictions are not important at high CO pressures. When the CO concentration is increased . and a pore radius of 40 nm. a temperature of 300 °C. The methanation rates for the two types of nickel thread have been scaled to match at high CO concentrations.2. a tortuosity factor of 3. Rates of CO methanation at 300 °C as a function of the CO concentrations in the reactor are plotted in Figure 4 for nickel threads with 4 and 22 µm diameters. it was concluded that the results are not influenced by diffusion limitations and that the conversion at low CO pressures is a fingerprint of the intrinsic kinetics of the nickel surface.026 cm2/s estimated from the formulas in Satterfield. where the reaction order in CO is zero and the hydrogen pressure is nearly constant. In this section possible diffusion restrictions are first examined. Logarithm of the CO methanation activity of a Ni/MgAl2O4 catalyst at high CO pressures plotted as a function of 1000/T. 6.31 The deactivation was fastest at high temperatures and high CO concentrations. TOF is then given by TOF ) 2.4.03 cm.5 × 107 (mol g-1 h-1) exp[-96. Using these values the Φ modulus is calculated to be 0.5. If the system was film diffusion limited. The reaction rate for methanation of CO over nickel in this concentration regime is determined to be Ns•TOF ) 9.30. then deactivation due to carbon formation is inspected. respectively. To support this conclusion. No. have equal activity. Deactivation of the nickel surface was observed at temperatures above 350 °C. Assuming that all nickel sites The activation energy of 96. plotted as a function of the partial pressure of CO in an atmosphere of hydrogen. This is done in the Arrhenius plot in Figure 3. 400 °C.3 × 108 (s-1) exp[-96. which is below the value of 2 where pore diffusion is important. It is of interest to determine the temperature dependence of the zero order rate constant for the CO methanation at high levels of CO. Vol. As an additional check for film diffusion the recirculation pump of the system was closed and the reactor system behaved as a plug flow reactor. 2005 Sehested et al. Figure 5 gives the time dependence of the CH4 and the CO concentrations in the reactor at the highest temperature used in this study. The deactivation is clearly observed and is most pronounced for high CO pressures. 109. observed at low CO concentrations is due to diffusion restrictions in the catalyst particles. Figure 4. B. CO Methanation over Ni Thread. the trends in these curves are similar.2434 J.7 m2 g-1 and the average area of a surface nickel atom of approximately 6. Figure 2. The data were corrected for the deactivation using the following method: The increase in the methane concentration just after CO is admitted into the reactor is measured. indicating the absence of diffusion restrictions. The deactivation is probably related to carbon formation and physical blocking of the surface. To avoid the diffusion restrictions at low CO concentrations. The accumulation of less reactive carbonaceous deposits is a wellknown phenomena in methanation studies. 3. CO methanation activity at 300 °C for nickel threads with diameters of 4 and 22 µm.7 (kJ/mol)/RT].18 at nickel single crystals. the CO methanation rate was measured over nickel threads. However. an effective diffusion constant of 0.7 (kJ/mol)/RT] (2) Figure 3. The slope of the plot gives a zero-order rate constant of 9. Chem. and those obtained by Goodmann et al.29 a porosity of 0.5 × 10-20 m2 7 to be ca. the number of active sites can be determined from the surface area of the catalyst of 4. those reported by Vannice21 at supported nickel catalysts. a decrease in the activity should be observed upon a decrease of the flow through the reactor at the conditions used here. plotted as a function of pCO in an atmosphere of hydrogen. and finally the results are presented and discussed.

CH4 and CO pressures during methanation at 400 °C over 22 µm nickel threads plotted as a function of time. The CH4 pressures have been corrected for deactivation of the nickel surface observed during the measurements. interactions between the adsorbants are neglected in the following. or CO species. Using the equilibrium constants for reactions 3 and 4. KH. negative reaction orders in CO could be included in the model by assuming that CO adsorb at type 2 sites at high CO pressures. is the number of moles of CO molecules converted per gram of catalyst per time unit.23 However. The curves all showed increasing activity at low CO concentrations and stabilization of the activity at high CO concentrations. At intermediate CO pressures. With this assumption eq 8 may be written . the carbon atom from the CO molecule dissociating at the step site arrives at the 5-fold coordinated site at the bottom of the atomic step. B. The corrected methane concentrations calculated from the data in Figure 5 and the derived activities are plotted in Figure 6. the largest increase in the methane concentration is determined (∆CH4) and divided by the fraction of the nickel surface that is still active (R). the rate of reaction increases linearly with pCO. Hence. and hence it is always free of other adsorbants. It should be mentioned that the calculated barrier for CO dissociation calculated by Bengaard et al.5H2 + * a H* CO* + # f O* + C# Act. k5 is the rate constant for reaction 5. At low CO pressures.5 (9) Equation 8 depends on three parameters: KCO. the number of type 1 and type 2 sites may equal to the number of step sites. which are always free at the conditions used here. The smooth line through the data points is a fit to the data using eq 10. the activity is given by CO + * a CO* 0. respectively. The number of free type 1 sites is given by KCO KH (3) (4) (5) (6) (7) rate determining step fast fast C# + 2H2 f CH4 + # O* + H2 f H2O + * Reaction 5 is the rate determining step.24 In this work a much lower dissociation barrier for CO dissociation was found at nickel step θ* ) 1 1 + KCOpCO + KHpH20. and Nsk5. In addition. CH4 pressures and activities at 400 °C during methanation over 22 µm nickel threads plotted as a function of pCO. Furthermore. This mechanism is very simple and does not describe the negative reaction orders in CO observed at high CO pressures by Schoubye15 and Polizotti and Schwarz. Ns is the number of active (type 1 and 2) sites per gram. The ratio of the equilibrium constants for CO molecules and H atoms will be determined from the experimental data in the following. Hence. further. sites (Ni(211)) than at nickel terrace sites (Ni(111)). as observed in Figures 4 and 6. 1). From the experimental data only two parameters can be obtained. The next step is to find a kinetic expression that can describe the activity data. The best fit was obtained using a mechanism where CO molecules compete with hydrogen atoms for type 1 sites (*) at the nickel surface and CO dissociates to a type 2 site (#). No. The reactions involved may be written Figure 6. KCO and KH. At high CO concentrations the rate of reaction is independent of the CO concentration. At this site only carbon will adsorb. The type 1 and the type 2 sites in the reaction mechanism above may therefore be step edges and 5-fold coordinated sites. Vol. 6. Some theoretical justification for the two-site model is found in the work of Bengaard et al. θ*. the detailed reaction mechanism may be more complicated than that described here but the kinetics of the reaction reduces to that used here at our experimental conditions. 2005 2435 Figure 5. ) Nsk5θCO*θ# ) Nsk5KCOpCOθ* ) KCOpCO (8) Nsk5 1 + KCOpCO + KHpH20. This shape is a consequence of the kinetics of the methanation reaction. The 5-fold coordinated site is not energetically favorable for any other CHx (x ) 0-3). and Act. which is assumed to be unity. A series of curves of the activity versus the CO concentration similar to that in Figure 6 was obtained for temperatures in the range 275-400 °C. and reactions 6 and 7 are so fast that the coverages of C# and O* are negligible. Chem. the reaction order of CO is positive and less than one. 109.Methanation of CO over Nickel J. ∆CH4/R is then added to the previously determined CH4 concentration to obtain the methane concentration in the case of no deactivation. In this way the effect of the deactivation is reduced to the short periods of time during which the CO and CH4 concentration increases are taking place. We choose here to limit the number of parameters by assuming that the combined surface coverages of CO and H are always much higher than the fraction of free active sites. Phys. OHx (x ) 0. R is calculated by dividing the observed methane concentration with the calculated methane concentration in the case of no deactivation.5 θCO* and θ* are the coverages of CO molecules and free sites at type 1 sites and θ# is the coverage of free sites at type 2 sites.24 is higher than that obtained in the following. reactions 3 and 4 are so fast that CO* and H* are in equilibrium with the gas-phase species CO and H2.

Understanding these results will therefore be difficult compared to the interpretation of the data reported here. A value of KH is determined in the following section. we arrive at a preexponential factor for reaction 5 of ca.10. B. ≈ Nsk5 ) Nsk5 (10) 0.5) exp[79 (kJ/mol)/RT]. When the hydrogen TPD and TPA experiments are analyzed.8 As discussed in the Introduction a lot of kinetic models and mechanisms have been proposed for CO methanation over nickel. The KCO/KH ratios determined by Alstrup are significantly lower (factors of 2. This preexponential factor may still seem low.33 respectively.2436 J.5 KCO pCO KCOpCO + KHpH2 1+ KH p 0. This is close to the value obtained below of 3 × 10-7 bar-1. the activities versus the CO concentrations were fitted using eq 10 and values of the KCO/ KH ratio were determined. The fit of eq 10 to the activity data in Figure 6 is given as a smooth line.5 × 103 bar-1 s-1. as discussed previously. 3.5 at 400 °C and the value of the Nsk5 fit is 0.45 kJ/mol). the fit to the data is excellent.4 × 103 (bar-1 s-1) exp[25 (kJ/ mol)/RT] assuming that only 5% of the nickel area is active in accordance with the number of active iron sites in a commercial ammonia catalyst. N2 is dissociating over a ruthenium or iron step site like CO is dissociating over a nickel step site. The KCO/KH ratios used by Alstrup8 and Aparicio26 are plotted for comparison. Goodman et al. and 3:1. The data form a straight line given by KCO/KH ) 4 × 10-4 (bar-0.33 Assuming that 5% of the nickel surface is active for CO dissociation. The data in Figure 6 may be fitted by eq 10 using Nsk5 and KCO/KH as free fitting parameters.5) exp[77 (kJ/mol)/RT]. it is assumed that the surface hydrogen is in equilibrium with the gas-phase hydrogen.24 This effect has been observed experimentally for N2 dissociation over ruthenium32 and iron. The value of KCO/KH obtained from the fit is 639 bar-0. respectively. as observed.18 Preexponential factors for surface reactions are normally expected to be of the order of 1013 s-1. This is significantly lower that the calculated energy barriers reported by Bengaard et al. there is excellent agreement between the activation energy determined here and those reported over supported catalysts. as discussed in the work of Bengaard et al. The reason for this difference is unknown.40.5 ratios is equal to Nsk5 where k5 is identical to the TOF determined previously of k5 ) TOF ) 2. 2005 Sehested et al. TPD and TPA traces are determined from KH by assuming that the reactor is well described as a differential reactor where the H2 pressure is an average of the inlet and outlet pressure. from the following series of arguments it may be seen that the observed preexponential factor is reasonable: Alstrup8 used statistical mechanics and literature values of vibrations and rotations to calculate the equilibrium constant for CO adsorption.3 × 108 (s-1) exp[-96. Hydrogen Adsorption/Desorption Experiment. This change is relatively small and no attempt was made to correct for this difference. The logarithm of the KCO/KH ratios are plotted in Figure 7 as a function of 1000/T.18 Polizzotti and Schwartz.33 The preexponential factor for KCOk5 may be compared to the preexponential factors for N2 dissociation over ruthenium and iron of ca.4 bar. Equilibrium constant ratio KCO/KH plotted as a function of 1000/T. .10 found that the rates of CO dissociation and hydrogenation of nickel carbide on Ni(100) compete at 177 °C. From the work of Alstrup. In most other experimental work reported in the literature. θCO ≈ 0. Vol. From KCO and k5 the overall rate constant in the case of low CO and H2 concentrations is calculated to be KCOk5 ≈ 1. 2.7 kJ/mol. It therefore seems reasonable that CO dissociation is the rate determining step at the experimental conditions used here. The activation energy for CO dissociation at the active nickel site is 96.5 H2 KCO pCO KH p 0.33 The experimentally observed fraction of sites at iron that are active for ammonia synthesis is approximately 5%.24 of 218 kJ/mol.2 bar0. hence it is expected that the entropy changes from the gas-phase molecule to the transition state are similar.60. θ* is only partly fulfilled. the preexponential factor of k5 is also correct. If the temperature independent parts of KCO and KCOk5 are reasonable. Estimating the KCO/KH ratio using eq 8 and the value of KH determined in the following section as opposed to eq 10 gives KCO/KH ≈ 8 × 10-4 (bar-0. KCOpCO H2 Act. Goodman et al. 6. However. The reason for the low preexponential factor of k5 is probably that the transition state for CO dissociation is immobile. In ammonia synthesis. one can show that θH ≈ 0.5 The validity of the assumption is discussed below. Phys. 103 bar-1 s-1 32 and ca. 5 × 109 s-1. pH20. Part of the reason for the low preexponential factor obtained here may be that only a few special sites (step sites) are expected to be active for CO dissociation.5) exp[79 (kJ/mol)/RT]. However. The KCO/KH ratios derived by Alstrup8 and Aparicio26 from surface science studies and theoretical calculations are plotted in Figure 7 for comparison. the kinetis may be more complicated and more than one rate determining step may be active. 1:1-30:1. The values of Nsk5 were not used for anything because the initail deactivation of the nickel surface influences the values of Nsk5.5 because pH2 ) 1. at 441 °C of 9 × 10-8 bar-1 is derived.73 mmol g-1 h-1.30 at pCO ) 0. The slope of the plot is 4 × 10-4 (bar0.5-5 times) than those obtained here whereas the KCO/KH ratios reported by Aparicio are in good agreement with those measured here. For each set of experiments. For example. One could speculate that at the experimental conditions used by many authors with high CO:H2 ratios. and θ* ≈ 0.21 nickel foils.3. The experimental conditions used here with high hydrogen and low CO pressures favor hydrogenation of carbon at the nickel surface.23 and Vannice21 used H2:CO ratios of 4:1. 109. whereas the low CO pressures tend to slow the rate of CO methanation.. Interestingly.23 and single crystals. Thus it is the equilibrium constant KH as a function of temperature that can be determined from the experiments. No. From eq 8 it is seen that the activity at high pCO/pH20.7 (kJ/mol)/ RT]. whereas the frustrated translations of CO at nickel have relative low energies (0.8 a temperature independent factor of the CO adsorption constant Figure 7.37 mbar and T ) 400 °C and hence the assumption made above that θH + θCO . The relative small changes in the H2 pressure observed (Figure 8) makes this a good approximation. See text for details. low H2:CO ratios were used. and using this value. Chem.5 ≈ 1. As seen from the figure.

B. 64. 317.5) exp[43 (kJ/mol)/RT]. even with a distribution of heats of adsorptions. Better agreement between experiment and predictions could be obtained by assuming that two or more types of sites with different KH exist on the nickel surface. Finally. 109.. Jørn.. M.. H2 adsorption/desorption experiment over a Ni/MgAl2O4 catalyst. Anderson.5) exp[43 (kJ/mol)/RT]. 7. In Catalysis. 78 (15). 5. 25. KCO were derived from Takagi et al. R. For example. R. J. Science and Technology.34 and Takagi et al. H. Kelley. M..8 The equilibrium constant from Stuckless et al.. 134. Appl. Acad. (6) Rostrup-Nielsen. the initial sticking coefficient at 350 K(0. E. From KCO/KH and KH.1% H2 in He. J.6 × 1014 s-1).. D.7 × 10-4 (bar-0. 1986. R. F. Boudart. Anderson. C. A. M. R. (3) Bresler.. 1984. bar-0. The fact that it is possible to describe the TPA and the TPD experiment means that the assumption of gas-phase surface equilibrium is reasonable. J. J. p 139. We thank Said Rokni and Claus Thomsen for technical assistance. 1998.8 Aparicio gives the equilibrium constants directly. 151. 395. A. Figure 8. Madey. J. A. which is judged to give the best agreement with the experimental results. The lower experimental curve gives the hydrogen concentration in the same gas and the inverted temperature ramp. Catal. . J. 3. KH were determined using a hydrogen adsorption/desorption experiment to be 7.35 and data estimated from surface science experiments and used for mikrokinetic modeling of the re-forming reaction26 and the CO methanation reaction. Acknowledgment. Mater. A. the preexponential factor for desorption (3 × 1014 s-1). In Catalysis. T. The upper experimental curve gives the concentration of hydrogen in the exit gas during a temperature ramp of 8 °C/min in the presence of 100 mL/min (NPT) of 0..7 (kJ/mol)/ RT] assuming that 5% of the nickel surface atoms are active. D.7 × 10-4 (bar-0. P. a value of KCO ) 3 × 10-7 (bar-1) exp[122 (kJ/mol)/RT] is determined. M. 216.35 using the heat of adsorption of 127 kJ/mol. bar-1 2 × 10-5 exp[115 (kJ/mol)/RT] 9 × 10-8 exp[117 (kJ/mol)/RT] 3 × 10-7 exp[122 (kJ/mol)/RT] 5 × 10-7 exp[130 (kJ/mol)/RT] 10-6 exp[127 (kJ/mol)/RT] TABLE 1: Comparison between the Values of KH and KCO Obtained Here and Data from the Literature ref 26 8 this work 34 35 The results from the TPD and the TPA experiment are depicted in Figure 8 together with the predictions obtained when KH ) the values of KCO and KH used by Aparicio are more than an order of magnitude higher than those reported here. C. (8) Alstrup. E. B. Chapter 1. J. 479. 1972... Boudart...8 4. Vol. KCO is calculated to be 3 × 10-7 (bar-1) exp[122 (kJ/ mol)/RT]. Sci. This is the background for what Boudart almost 50 years ago termed the “paradox of heterogeneous catalysis”.. Vol. Chem... Science and Technology. Comparison of KCO and KH with Data from the Literature. T. F. M. van Meerten. and preexponential factor for desorption (1. H. Phys. 1980. J. M. No. 3.37 stating that irrespective of the complexity of the catalytic surface. 1. White. J. References and Notes (1) Sabatier. Z. 59.8 × 10-2 exp[25 (kJ/mol)/RT] 7. One may question the justification of using the Langmuir approach for deriving the kinetic expression used here. D. 49. W. 1.8 However. van Nisselroy.. The first-order rate constants for CO* dissociation at the catalyst surface were 5 × 109 (s-1) exp[-96. P.5H2 + * a H*). Eds..5 (kJ/mol)/RT] 1. 6. the equilibrium constants in the literature represent values at low coverages of CO and there was no hydrogen present in measurements of Stuckless et al.. Corr. The equilibrium constant for CO adsorption determined here is lower than all the other equilibrium constants apart from that determined by Alstrup. K. The adsorption constant ratio KCO/KH was determined from the CO methanation experiments over nickel thread to be 4 × 10-4 (bar-0. (9) Coenen. 1982.35 Even though the KCO/KH ratio determined by Aparicio26 is in excellent agreement with that obtained here.7 × 10-4 exp[43 (kJ/mol)/RT] -3 J. 514. 94.9). See text for details. Springer-Verlag: Berlin. Oil Gas.. de Croon.36 Nevertheless. Springer: Berlin. Vol. J. the hydrogen adsorption constant at 300 °C estimated by Aparicio26 is approximately 20 times higher than that reported here and that estimated by Alstrup. H. J. Ireland.5) exp[79 (kJ/mol)/RT]. the resulting kinetics may be close to that obtained here by assuming that the reaction takes place on only the most active sites. (5) Grabke.4. Chem.. Skov. B. Catal. I. From the values of KH and KCO/KH. Conclusions CO methanation and hydrogen adsorption/desorption over a Ni/MgAl2O4 catalyst and CO methanation over nickel threads were studied. Pedersen. 1980. P. and the initial calorimetric heat of adsorption (130 kJ/mol) at Ni(111). In Table 1 the equilibrium constants KH and KCO are compared to selected experimental data from the literature34.5 × 10 exp[47. 1995. The values of KCO and KH obtained in this work are in general agreement with the adsorption constants reported in the literature. M. R.5 5. 2005 2437 KCO (CO + * a CO*). The smooth lines are fits to the experimental data. (2) Vannice.72). Ho ¨ hlein. Alstrup8 only gives the enthalpy of the reaction and the preexponential factors were obtained from the calculated coverages of hydrogen atoms and CO molecules at 120 Torr total pressure and 441 °C given by Alstrup. R. (10) Goodmann.Methanation of CO over Nickel KH (0. knowing the complexity of real surfaces and that different sites are involved in the kinetic sequence. E. Eng. A. The CO methanation experiments over Ni/ MgAl2O4 catalysts were subject to diffusion restrictions at low CO concentrations and high conversions whereas diffusion restrictions were not important in the CO methanation over nickel threads. Senderens.34 was derived from the initial sticking coefficient at 27 °C (0. very often kinetic data can be represented by a Langmuir isotherm even though assumptions are far from reality. van Dooren. 1979. (7) Rostrup-Nielsen. (4) Harms. Catal. Eds. J. Paris 1902. S. J. J. 120. Catal. R. W.

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