(395af) Multi-Component Gas Adsorption On MSC5A By Chromatographic Method and Simulation Study

Nomoto, M., Meiji University
Chihara, K., Meiji University
Koide, S., Meiji university

1. Introduction

The combination
of chromatographic method and moment analysis of the response peaks is one of
the useful techniques to study adsorption equilibrium and adsorption rate.
Perturbation chromatography with the mixed multi component adsorbent gas carrier (two adsorbates)
has been applied to several studies on adsorption. In this work, perturbation
chromatography with multi component gas carrier (two adsorbates
with inert gas) and non-equilibrium thermodynamics liner law was applied for
discussion of the interference effect and the displacement effect (those are
cross effects) on mass transfer in multi component gas adsorption as previous study  for different gas mixture (He, CO2, C2H4, CH4 , N2). The study of mixed gases (C2H4+CO2,CH4+N2,CO2+CH4)
were done in temperature of 313K, 323K,333K. Moment analysis method and stop & go simulation
method were utilized to obtain each mass transfer parameters of adsorbate gases.

2. Experiment

The apparatus was similar to a conventional gas
chromatograph. Adsorbent particles (molecular sieving carbon 5A, 20/30 mesh, Japan Enviro
Chemical Ltd.,) were packed
in a column. Carrier gas was a mixture of two or three components among He, CO2, C2H4,N2,CH4. Perturbation pulse was
introduced into the carrier gas stream. Introduction of pulses was performed by
6-way valve. The pulse size was 1cc, which meant injection period was 1.4 sec. Then
pulse response was detected by TCD cell. Output signal of TCD was transmitted
to a personal computer through RS232C. This signal was
also transmitted to the personal computer. Simulated chromatogram by a personal
computer can be overlapped on experimental chromatogram shown in the monitor
screen. Further, moment of pulse response, which is shown in the monitor
screen, can be automatically calculated by the personal computer. Also this simulated chromatogram can be compared with experimental
chromatogram to determine the equilibrium and the adsorption kinetic
parameters. Here Markham-Benton equation as for adsorption equilibrium and
linear driving force (LDF) approximation as for adsorption kinetics were
adapted for numerical calculation, which was based on stop & go method.
Overall mass transfer coefficients (Ksav) for LDF model were determined.

3. Result and Discussion

shows an example of comparison of experimental chromatogram with simulated
chromatogram for MSC5A to obtain Ksav
for LDF model. Experimental conditions were 333 K, column pressure 5 atm, flow rate 25 cm/sec and He + CO2 mixed gas carrier with CO2 pulse. Here CO2 concentration in the carrier gas was changed 10, 30, 50, 70 and 90 %. Retention time of simulation peak depend on langmuir parameter. Therefore experimental peaks
differ from simulation peaks because of amount adsorbed from experiment and langmuir parameter differed.

 Fig.2 shows experiment and simulation results in an example case of
binary adsorbate carrier mixed with He and an adsorbate pulse. Experimental
conditions were 333 K, column pressure 5 atm, flow rate 25 cm/sec and
He(10%)+CO2(30%)+CH4(60%) mixed gas carrier with CO2pulse. Simulation peak needs compensation becouse TCD signals different
behavior from simulation's preassure change.


Fig. 1   Comparison of experimental

peaks with simulation of He +CO2 mixed gas carrier with CO2 pulse at 333 K.


Fig. 2   Comparison of experimental

peaks with simulation of He(10%)+CO2(30%)+CH4(60%) mixed gas carrier with CO2 pulse at 333 K.


4. Conclusion

Good agreements between experimental chromatogram and
simulated chromatogram, which were based on the modeling of Stop & Go
method, were observed in case of peturbation chromatography with mixed
adsorbate gas carrier. And micropore diffusivities obtained were interpreted by
chemical potential driving force consideration based on non-equilibrium
thermodynamics law.



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