Separation of impurities (CO₂ and N₂) from CH₄ is an important issue for natural gas alternatives (such as coalbed gas, biogas, and landfill gas) upgrading. It is notably challenging to synthesize high N-doped porous carbon with an appropriate porous structure. In this work, high N content (14.48 wt %) porous carbon with micropore size of 0.52 and 1.2 nm and specific surface area of 862 m² g⁻¹ has been synthesized from potassium hydroxide (KOH) activated waste wool upon the urea modification. Pure component adsorption isotherms of CO₂, CH₄, and N₂ are systematically measured on this enhanced N-doped porous carbon at 0 and 25 °C, up to 1 bar, to evaluate the gases adsorption capability, and correlated with the Langmuir model. These data are used to estimate the separation selectivities for binary mixtures of CO₂/CH₄ and CH₄/N₂ at different mixing ratios according to the ideal adsorbed solution theory (IAST) model. At an ambient condition of 25 °C and 1 bar, the predicted selectivities for equimolar CO₂/CH₄ and CH₄/N₂ are 3.19 and 7.62, respectively, and the adsorption capacities for CO₂, CH₄, and N₂ are 2.91, 1.01, and 0.13 mmol g⁻¹, respectively. This report introduces a simple pathway to obtain enhanced N-doped porous carbon with large adsorption capacities for gas separation of CO₂/CH₄ and CH₄/N₂.

In this work, N-doped hierarchical porous carbon has been successfully fabricated by KOH activation of waste wool. The optimal sample exhibits good CO₂ adsorption capacity under atmospheric pressure (1 bar), as well as excellent CO₂/N₂ selectivity.

Addressing the pressing demand for biogas and landfill-gas upgrading within the global energy transition, this work strategically combines thermodynamic and kinetic separation principles to identify, from a cooperative-separation perspective, the effective pore-size range that governs carbon molecular sieve (CMS) performance. Thirty anthracite-derived CMS samples with distinct pore structures were synthesized and employed as a statistical set to link pore architecture with dynamic adsorption performance. The results clarify the effective pore-size range and mechanism for enhanced CMS selectivity: CH₄ uptake depends exclusively on ultramicropores (20 Å), whereas CO₂ uptake is less sensitive to pore-size distribution. CO₂/CH₄ separation performance improves linearly with the volume fraction of mesopores >20 Å, defining a 20–60 Å mesopore window as optimal for cooperative CMS. Mechanistic studies show that a high mesopore fraction significantly slows CH₄ adsorption while maintaining a fast CO₂ uptake, thereby amplifying their intrinsic adsorption-rate difference. This work breaks from the conventional purely thermodynamic or kinetic sieving paradigm and offers new design criteria for CMS tailored to on-site biogas and landfill-gas purification.