Adsorption equilibria and kinetics are two sets of properties crucial to the design and simulation of adsorption based gas separation processes. The adsorption equilibria and kinetics of N2 and CH4 on commercial activated carbon Norit RB3, zeolite 13X, zeolite 4A and molecular sieving carbon MSC-3K 172 were studied experimentally at temperatures of (273 and 303) K in the pressure range of (5 to 120) kPa. These measurements were in part motivated by the lack of consistent adsorption kinetic data available in the literature for these systems, which forces the use of empirical estimates with large uncertainties in process designs. The adsorption measurements were carried out on a commercial volumetric apparatus. To obtain reliable kinetic data, the apparatus was operated in its rate of adsorption mode with calibration experiments conducted using helium to correct for the impact of gas expansion on the observed uptake dynamics. Analysis of the corrected rate of adsorption data for N2 and CH4 using the non-isothermal Fickian diffusion (FD) model was also found to be essential; the FD model was able to describe the dynamic uptake observed to better that 1 % in all cases, while the more commonly applied isothermal Linear Driving Force model was found to have a relative root mean square deviation of around 10 %. The measured sorption kinetics had no dependence on gas pressure but their temperature dependence was consistent with an Arrhenius-type relation. The effective sorption rates extracted using the FD model were able to resolve inconsistencies in the literature for similar measurements.
Lithium (Li)-doped polycyclic aromatic hydrocarbons showed a high potential for N2 removal from natural gas. Li doping significantly increases the gas adsorption energies resulting in considerable N2 adsorption selectivity.
Nitrogen is a ubiquitous impurity
in natural gas that has to be
removed for the production of liquefied natural gas (LNG). The most
widely used technology for N2 rejection, cryogenic distillation,
is a capital and energy intensive process. In this work, a nitrogen
selective K[RuII(EDTA)] aqueous solution was prepared and
tested for nitrogen sorption with the aim of reducing the N2 rejection costs by using a continuous recirculation absorption process
analogous to the acid gas removal process in LNG production. The overall
equilibrium amount of N2 sorption in the K[RuII(EDTA)] solution was obtained at 20 °C (0.075 mol N2/L solution at 2860 kPa), 30 °C (0.061 mol N2/L solution
at 2873 kPa), and 40 °C (0.052 mol N2/L solution at
3049 kPa) using a custom-built volumetric sorption measurement apparatus.
The corresponding specific N2 sorption amounts were 0.54
mol N2/mol Ru at 20 °C and 2860 kPa; 0.43 mol N2/mol Ru at 30 °C and 2873 kPa; and 0.34 mol N2/mol Ru at 40 °C and 3049 kPa. These specific N2 sorption
amounts exhibited similar values to the specific loading of carbon
dioxide in monoethanolamine (MEA) which is one of the most widely
used chemicals for acid gas removal in LNG production industry. The
heat of N2 absorption in the K[RuII(EDTA)] solution
was in the range of 30–60 kJ/mol N2, suggesting
the regeneration of the K[RuII(EDTA)] solution would require
less energy than that required for CO2 scrubbing using
MEA aqueous solution. The N2/CH4 selectivity
in the K[RuII(EDTA)] aqueous solution is in the range of
1.7 to 2.4 depending on the pressure of the gas, which is the highest
N2/CH4 selectivity known for a liquid based
N2 and CH4 separation system. The comparable
specific N2 sorption capacity to CO2-amine system
and the high N2/CH4 selectivity of the K[RuII(EDTA)] aqueous solution exhibit a great potential of the
solution for nitrogen rejection from natural gas.
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