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Jan Kopyscinski1 Tilman J. Schildhauer1 Serge M. A. Biollaz1

1

Research Article

Laboratory of Energy and Materials Cycles, Paul Scherrer Institut, Villigen, Switzerland.

Employing Catalyst Fluidization to Enable Carbon Management in the Synthetic Natural Gas Production from Biomass
By measurements of axial gas phase concentration profiles in a fluidized-bed methanation reactor for the production of synthetic natural gas, regeneration of the catalyst inside the fluidized-bed reaction system could be proven. Moreover, by varying space velocity, bed height, catalyst mass, flow rates, and dilution rates, it could be shown that both hydrodynamic as well as chemical boundary conditions can influence the surface coverage and therefore selectivity and deactivation processes.
Keywords: Bubbling fluidized beds, Carbon management, Methane, Synthetic natural gas, Wood Received: August 28, 2008; accepted: November 21, 2008 DOI: 10.1002/ceat.200800413

Introduction

Conversion of coal or biomass into clean fuels draws a lot of interest. The production of synthetic natural gas (SNG) via the methanation reaction is considered again. One main advantage is the existing distribution infrastructure such as pipelines and established end-use technologies, e.g. compressed natural gas (CNG) cars, heating, combined heat and power (CHP), and power stations. Today, sustainability and CO2 neutrality are motivations to produce SNG from biomass. The methanation of biomass-derived syngas has been demonstrated on the 10-kW scale [1]. The next step is the demonstration on the 1-MW scale [2]. Fluidized-bed reactors have been successfully applied to syngas methanation in several projects [1, 3, 4]. By in situ measurements of the axial gas phase concentration profiles, a regenerative effect of fluidization on the catalyst has been shown [5]. The profiles prove strong carbon exchange processes between the moving catalyst particles and the gas phase (Fig. 1). In the bottom region of the bed, carbon deposition (most probably adsorbed carbon atoms, Cads) due to the Boudouard reaction takes place and CO2 is formed. At about 5 mm, due to the high H2 concentration and the decreasing amount of CO, the reverse water gas shift reaction (WGSR) starts to dom-

inate. The CO2 concentration shows a minimum and then it increases again in equilibrium with the methanation reaction. At the same time, the adsorbed carbon atoms (Cads) are hydrogenated to methane. As a result, the CO2 and CH4 flows increase whereas H2 is consumed. At a height of 20 mm, the molar flow of CH4 has its maximum. In the upper part of the bed, the CH4 concentration decreases whereas the concentrations of both H2 and N2 increase due to the mass transfer between the bubble phase and the dense phase. As carbon on the catalyst surface is a necessary intermediate in the methanation reaction, and at the same time implies the risk of catalyst deactivation, an optimized carbon management is important to minimize the net carbon formation. Therefore, an understanding of the interaction of hydrodynamics and chemical reaction is essential. In several experiments, in which operating variables such as catalyst mass and superficial gas velocities were varied independently in a bench scale reactor, the axial gas phase concentration profiles were measured. Changing catalyst mass has an impact on both the chemical space velocity (molCO gcat1 s1) and the bed height-to-diameter ratio (H/D). By varying the gas flow rates for each catalyst mass, comparable points for the same space velocity were found and thus the hydrodynamic effects can be distinguished from reaction effects.

2
Correspondence: Jan Kopyscinski (jan.kopyscinski@psi.ch), Laboratory of Energy and Materials Cycles, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland.

Experimental

The scheme of the setup is shown in Fig. 2. This setup is designed for catalyst testing under realistic fluidized-bed conditions. It consists of a 50 mm diameter fluidized-bed reactor

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Figure 1. Profile of the dry axial gas concentration in the fluidized-bed methanation reactor.

Figure 2. Scheme of the setup.

(1) with a diffuser at the upper end to control the discharge of fines. The gas is introduced via a non-reactive porous metal plate. The temperature of the reactor is measured by a sidewise immersed fixed thermocouple about 5 mm above the porous metal plate (2) and controlled by cooling the outside reactor wall with air. Water produced by the methanation reaction is condensed and weighed (3). The core of the setup is a moveable sampling probe (4) with a 2 mm porous titanium plate at the tip. The probe is

equipped with a thermocouple (5) at the tip to measure the ambient temperature. Driven by a linear motor, this probe is immersed axially from the top of the reactor into the catalyst bed. Spacers at two different heights assure the radial position of the probe. By means of a gas pump, a continuous flow of 10 mL/min is transported to the micro gas chromatograph (l-GC) via an MgSO4 adsorber for removal of the moisture (6). Gaseous products are analyzed online by the l-GC with two columns (Varian CP 4900; detector TCD; columns MSA5, PPU). For the experiments, 100, 140 and 200 g of a commercial Ni/c-Al2O3 catalyst were used. The reactor temperature was kept between 320 and 330 C and the pressure at 1.3 barabs. The inlet gas mixture consisted of H2 and CO, with a stoichiometric ratio H2/CO = 3, and N2 (see Tab. 1). A typical experiment consisted of up to six runs where the sampling probe was moved up- and downwards. If the reaction conditions were stable and three runs of one operation condition were congruent, the data was considered as reliable. Before each set of experiments, the l-GC was calibrated with calibration mixtures ( 2 % relative uncertainty) at three to five concentration levels per gas species (H2/CO/CO2/CH4/ N2). Only experiments on consecutive days were compared to minimize effects due to potential catalyst ageing and changes of the GC performance. At the start of each experiment and each run, the sampling probe was immersed with a backflush of N2 to prevent particles from blocking the probe, and moved down to the porous plate (level zero). Then, the N2 backflush was stopped and the pump and the l-GC were started. In the following, the sampling probe was moved up and down automatically by the linear motor (precision 0.125 mm).

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Table 1. Experimental parameters.

No. Mass gcat 1 2 3 4 5 6 7 100 140 200 100 200 100 100 10.0 10.0 10.0 14.0 14.0 8.1 16.2 R H2 CO N2 Space velocity LN(CO)/(gcat min) 2.0 2.0 2.0 2.8 2.8 4.1 8.2 0.020 0.014 0.010 0.028 0.014 0.010 0.020

LN/min (inlet flow) 6.0 6.0 6.0 8.4 8.4 3.0 6.0 2.0 2.0 2.0 2.8 2.8 1.0 2.0

Results and Discussion

In a first set of experiments (see Tab. 1, Nos. 13), the amount of catalyst was varied twice by a factor of 1.4 from 100 to 140 g and 200 g at an inlet gas flow of 6 LN/min H2, 2 LN/min CO and 2 LN/min N2. This way, the height-to-diameter ratio (H/D) of the bed increased while the chemical space velocity decreased. As shown in Fig. 3, there is little difference between the axial gas concentration profiles for the three experiments. Near the entrance, the maxima for N2 (at around 10 mm) and CH4 (at around 20 mm), and the minimum of CO2 (between 5 and 8 mm), seem to be similar for all catalyst masses.

The profile for the experiment with 100 g catalyst (Fig. 3a) shows xCO Outlet flow a clear step in the concentrations of H2, CH4 and N2 at a height of LN/min about 90 mm where the end of the 0.2 6.2 catalyst bed is expected and confirmed by temperature measure0.2 6.2 ments. The sudden change of mea0.2 6.2 sured concentrations between bed 0.2 8.7 and freeboard indicates that the measured gas concentrations repre0.2 8.7 sent mainly the dense phase and 0.12 6.2 that significant concentration differences between dense phase and 0.12 12.4 bubble phase exist. For the experiments with deeper beds (see Fig. 3b, c), the step change in concentration between bed and freeboard is smaller. This can be explained by the fact that the bubbles travel longer through the bed and, therefore, there is more time for mass transfer between the dense phase and the bubble phase. All measured profiles of the experiments with 200 g catalyst show a reproducible wiggle pattern at around 3070 mm bed height. This might indicate local back mixing due to the formation of a second recirculation cell because of the doubled height-to-diameter ratio of the bed. In the second set of experiments (Tab. 1, Nos. 4 and 5), the gas flow rates were increased by a factor 1.4 from 10 to 14 LN/ min, once with 100 g and once with 200 g catalyst. In Figs. 4 and 5, only the first 30 mm are shown. Here, significant

Figure 3. Measured axial gas concentration profile during the methanation reaction of (a) 100 gcat, (b) 140 gcat and (c) 200 gcat for an inlet flow of 10 LN/min (6:2:2 = H2/CO/N2) and a bed temperature Tbed = 320 C.

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Figure 4. Axial gas concentration for 100 gcat with (a) 10 LN/min and (b) 14 LN/min inlet flow.

impacts of the experimental conditions on the concentration profiles can be observed, while the upper parts of the bed are quite similar. The profiles of these two experiments (Figs. 4b and 5b) are compared to the ones for 100 and 200 g at the lower gas flow rate (Figs. 4a and 5a). The most striking differences are the much steeper gradients observed for the higher flow rates (Figs. 4b and 5b), indicating higher reaction rates as well. As the space velocity is 1.4 times higher but the concentrations are the same as for the low flow rates, one would expect the opposite, namely slower reaction rates. A possible explanation can be found when the CO2 concentrations near the reactor entrance are compared. For the low flow rate (Figs. 4a and 5a), molar fractions of up to 8 % are found, whereas only 5 % or no CO2 can be found for the higher flow rate (Figs. 4b and 5b). If we keep in mind that CO2 is formed near the entrance by the Boudouard reaction (2 CO , Cads + CO2), it can be assumed that also less adsorbed CO and solid carbon Cads is present on the surface, thus allowing more H2 adsorption and higher reaction rates for methanation. A possible explanation of the lower coverage by CO and Cads could be the better particle mixing and the lower residence time of the catalyst particles near the gas distributor due to the higher gas flow rates. The hypothesis that less coverage of the surface by CO and Cads should increase the rates is supported by the findings of the last set of experiments (see Tab. 1, Nos. 6 and 7) where the dilution by N2 was varied. As can be seen from the experiments above, the main H2 and CO conversion and thus the volume reduction (up to 38 %) take place within the first 1020 mm of the catalyst bed. By contrast, the upper part of the bed is mainly used for catalyst regeneration, where the volume reduction is very small in contrast to the bottom region. To compare experiments with the same hydrodynamic behavior, it was aimed for constant outlet flows. Therefore, the N2 dilution was increased to maintain the volumetric flow rate at the outlet condition (see Tab. 1, Nos. 1 and 6). The catalyst amount was 100 g and the gas flows were 3.0 LN/min of H2, 1.0 LN/min of CO, and 4.1 LN/min of N2 and 6.0 LN/min of H2, 2.0 LN/min of CO, and 8.2 LN/min of N2, respectively. These flow rates correspond to a 50 % N2

Figure 5. Axial gas concentration for 200 gcat with (a) 10 LN/min and (b) 14 LN/min inlet flow.

Figure 6. Measured axial gas concentration for 100 gcat with 10 LN/min (for comparison, N2 is not considered in the calculation of the molar fractions).

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Conclusion

Figure 7. Measured axial gas concentration for 100 gcat with 8.1 LN/min (for comparison, N2 is not considered in the calculation of the molar fractions).

By measurements of axial gas phase concentration profiles in a fluidized-bed methanation reactor for SNG production, an internal regeneration of the catalyst could be proven, which is based on the catalyst recirculation through CO-rich and COlean parts of the catalyst bed driven by bubble formation. Moreover, by varying space velocity, bed height, catalyst mass, flow rates, and dilution rates, it could be shown that both hydrodynamic and chemical boundary conditions can influence the surface coverage and therefore selectivity and deactivation processes. Moving of the catalyst particles is the key to enable carbon management on the catalyst surface during the methanation reaction. The complete understanding of these phenomena will be supported by modeling, which will allow the optimization of the process and may lead to decreased catalyst deactivation rates.

Acknowledgement
The financial support of Novatlantis is gratefully acknowledged. The authors have declared no conflict of interest.

References
[1] M. C. Seemann, S. M. A. Biollaz, M. Schaub, C. Aichernig, R. Rauch, H. Hofbauer, R. Koch, in Proc. of the 14th European Biomass Conference & Exhibition, Biomass for Energy, Industry, and Climate Protection, Paris, France 2005. [2] European Union Project Demonstration of the Production and Utilization of Synthetic Natural Gas (SNG) from Solid Biofuels (Bio-SNG), Project No TREN/05/FP6EN/S07.56632/ 019895. www.ie-leipzig.de/Bio-SNG/Index.htm. [3] G. Friedrichs, P. Proplesch, G. Wismann, W. Lommerzheim, Methanisierung von Kohlenvergasungsgasen im Wirbelbett Pilot-Entwicklungsstufe, Forschungsbericht Universitt Karlsruhe T 85-106, Karlsruhe 1985. [4] K. Hedden, A. Anderlohr, J. Becker, H. P. Zeeb, Y. H. Cheng, Gleichzeitige Konvertierung und Methanisierung von COreichen Gasen, Forschungsbericht Universitt Karlsruhe T 86044, Karlsruhe 1986. [5] M. C. Seemann, T. J. Schildhauer, S. M. A. Biollaz, S. Stucki, A. Wokaun, Appl. Catal. A: Gen. 2006, 313, 14.

Figure 8. Measured axial gas concentration for 100 gcat with 16.2 LN/min (for comparison, N2 is not considered in the calculation of the molar fractions).

dilution of a 6:2:2 (10 LN/min) and a 12:4:4 (20 LN/min) mixture of H2/CO/N2, respectively. Figs. 7 and 8 show again only the first 30 mm of the profiles of these two runs while Fig. 6 shows the base case. Again, similar or steeper gradients (and much lower CO2 fractions) are observed compared to the base case, although one would expect lower rates due to the dilution. This can be explained by the fact that the limiting step of the Boudouard reaction is of second order and therefore suffers relatively more from the dilution. In consequence, the coverage of the surface by CO and Cads is decreased, thus allowing faster H2 adsorption and methanation.

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