Mathematical analysis of the effect of process conditions on the porous structure development of activated carbons derived from Pine cones.

This paper presents the results of a study on the influence of the degree of impregnation and activation temperature on the formation of the porous structure of activated carbons (ACs) obtained from Pine cones by the chemical activation process using potassium hydroxide as an activator. The advanced new numerical clustering based adsorption analysis (LBET) method, together with the implemented unique numerical procedure for the fast multivariant identification were applied to nitrogen and carbon dioxide adsorption isotherms determined for porous structure characterization of the ACs. Moreover, the Quenched Solid Density Functional Theory (QSDFT) method was chosen to determine pore size distributions. The results showed a significant influence of the primary structure of Pine cones on the formation of the porous structure of the developed ACs. Among others, it was evidenced by a very high degree of surface heterogeneity of all the obtained ACs, irrespective of the degree of impregnation with potassium hydroxide and the activation temperature. Moreover, the analysis of carbon dioxide adsorption isotherms showed, that the porous structure of the studied ACs samples contains micropores accessible only to carbon dioxide molecules. The results also showed a significant advantage of the LBET method over those conventionally used for porous structure analysis based on Brunauer-Emmett-Teller (BET) and Dubinin-Raduskevich (DR) equations, because it takes into account surface heterogeneities. The novel analyses methods were more fully validated as a reliable characterization tool, by extending their application to the isotherms for ACs developed from the same precursor by phosphoric acid activation, and for samples arising from these ACs, further subjected to additional post-treatments. The effect of the raw material used as precursor was moreover analysed by comparison with previous reported results for other ACs. The complementarity of the results obtained with the LBET and QSDFT methods is also noteworthy, resulting in a more complete and reliable picture of the analyzed porous structures.

Tailoring activated carbons from Pinus canariensis cones for post-combustion CO2 capture.

Activated carbons (ACs) from Pinus canariensis cones were developed by KOH chemical activation. The effect of the impregnation KOH/carbonized cones ratio (IR = 1, 2, or 3) and temperature (873, 973, 1073 K) on main chemical, textural, and morphological characteristics of the resulting ACs was systematically examined. CO2 adsorption capacity from gaseous streams was evaluated by gravimetric adsorption tests, and the analysis of breakthrough curves was determined in a packed-bed column at 303 K and atmospheric pressure. Comparison of CO2 adsorption capacities of the ACs at 273 K and 303 K at equilibrium showed that those samples developed at 973 K with IR = 3 (BET surface area ~ 1900 m2 g-1) attained the highest values (6.4 mmol g-1 and 1.9 mmol g-1, respectively), even though the ACs obtained at 1073 K with the same IR exhibited the largest surface area (2200 m2 g-1). Thermodynamic parameters evaluated from CO2 adsorption isotherms determined in the range 273-333 K for the former sample pointed to a physisorption, spontaneous, and exothermic process; isosteric heat of adsorption was also estimated for the range of surface coverage of the equilibrium isotherms. The kinetics of CO2 adsorption onto all the ACs was successfully described by the linear driving force model. The breakthrough curves were properly represented by the Thomas' model, the longest breakthrough time and highest adsorption capacity being also attained for the bed packed with the ACs developed at 973 K with IR = 3. Higher CO2 adsorption capacities of the ACs were directly related to the presence of narrow micropores (< 0.9 nm) induced by the stronger activation conditions. However, an excessively severe combination of the IR and activation temperature exerted a negative influence on CO2 adsorption onto the ACs, likely due to micropores widening.

Graphene oxide/alginate beads as adsorbents: Influence of the load and the drying method on their physicochemical-mechanical properties and adsorptive performance.

Graphene oxide/alginate beads were prepared from lab-synthesized graphene oxide, varying its content within the beads (0.05, 0.125, and 0.25wt.%). Ethanol-drying and lyophilization were compared as drying methods to obtain suitable adsorbents which were later tested to the removal of a model organic molecule (methylene blue). The morphological and textural properties of all the beads were characterized by scanning electron microscopy and N2 adsorption/desorption isotherms at -196°C, respectively. Limited porosity was obtained for all cases (SBET<60m2/g). Uniaxial compression tests were performed to assess the mechanical properties of the beads. Ethanol-dried ones exhibited higher Young's elasticity modulus (E=192kPa) than the lyophilized samples (twice at 0.25wt.% graphene oxide loading), which disclosed breakage points at lower deformation percentages. Adsorption experiments were conducted and dye adsorption isotherms were obtained for the beads with the best removal performance. The experimental data were better fitted by the Langmuir model. The highest maximum adsorption capacity (4.25mmol/g) was obtained for the lyophilized beads with the highest graphene oxide content. Mechanical properties were found to be affected also by the dye adsorption.

Batch and dynamic sorption of Ni(II) ions by activated carbon based on a native lignocellulosic precursor.

Vinal-derived Activated Carbon (VAC) developed by phosphoric acid activation of sawdust from Prosopis ruscifolia native wood was tested for the adsorption of Ni(II) ions from dilute solutions in both batch and dynamic modes, comparing it with a Commercial Activated Carbon (CAC). Batch experiments were performed to determine adsorption kinetics and equilibrium isotherms for both carbons. It was possible to remove near 6.55 mg Ni g(-1) VAC and 7.65 mg Ni g(-1) CAC after 5 h and 10 h contact time, respectively. A pseudo second order equation fitted well with the kinetics of the process, and Langmuir adsorption model was used to adjust the experimental results concerning the adsorption isotherm. The parameters obtained indicate a stronger interaction between sorbent and sorbate for VAC (K = 26.56 L mmol(-1)) than for CAC (K = 19.54 L mmol(-1)). Continuous experiments were performed in a fixed-bed column packed with the investigated carbons, evaluating the influence of operational parameters such as flow rate, bed height and feed concentration on the breakthrough curves obtained. The breakthrough occurred more slowly for low concentrations of the metal ion in the feed, low flow rates and high bed height. The breakthrough curves were properly represented by Hall's model for both carbon types. Regeneration of the vinal activated carbon in column was tested, obtaining the same breakthrough curve in a new cycle of use. Finally, vinal-derived activated carbon can effectively be used to treat wastewater having until 30 ppm Ni(II).