Supported polytertiary amines: highly efficient and selective SO2 adsorbents.

Tertiary amine containing poly(propyleneimine) second (G2) and third (G3) generation dendrimers as well as polyethyleneimine (PEI) were developed for the selective removal of SO2. N-Alkylation of primary and secondary amines into tertiary amines was confirmed by FTIR and NMR analysis. Such modified polyamines were impregnated on two nanoporous supports, namely, SBA-15PL silica with platelet morphology and ethanol-extracted pore-expanded MCM-41 (PME) composite. In the presence of 0.1% SO2/N2 at 23 °C, the uptake of modified PEI, G2, and G3 supported on SBA-15PL was 2.07, 2.35, and 1.71 mmol/g, respectively; corresponding to SO2/N ratios of 0.22, 0.4, and 0.3. Under the same conditions, the SO2 adsorption capacity of PME-supported modified PEI and G3 was significantly higher, reaching 4.68 and 4.34 mmol/g, corresponding to SO2/N ratios of 0.41 and 0.82, respectively. The working SO2 adsorption capacity decreased with increasing temperature, reflecting the exothermic nature of the process. The adsorption capacity of these materials was enhanced dramatically in the presence of humidity in the gas mixture. FTIR data before SO2 adsorption and after adsorption and regeneration did not indicate any change in the materials. Nonetheless, the SO2 working capacity decreased in consecutive adsorption/regeneration cycles due to evaporation of impregnated polyamines, rather than actual deactivation. FTIR and (13)C and (15)N CP-MAS NMR of fresh and SO2 adsorbed modified G3 on PME confirmed the formation of a complexation adduct.

Molecular-level insights into the oxidative degradation of grafted amines.

The oxidative degradation of CO2 adsorbents consisting of amine-grafted pore-expanded mesoporous MCM-41 silica was investigated. The adsorbents were treated under flowing air at various temperatures, and the degree of deactivation was evaluated through the measurement of their CO2 adsorption capacity prior and subsequent to exposure to air. To decipher the chemical structure of surface species upon air-deactivation of grafted amines, a solvent extraction procedure was developed using a deuterated basic solution. The obtained solutions were analyzed by a variety of 1D and 2D NMR spectroscopy techniques, such as (29)Si, (13)C, (1)H, [(1)H,(15)N] HMBC, [(1)H,(13)C] HMQC, COSY and DOSY. The surface species generated by oxidative degradation of amine-grafted silica were found to contain functional groups such as imine, amide and carboxylic groups. Several structural units were conclusively demonstrated.

Zeolitic bagasse fly ash as a low-cost sorbent for the sequestration of p-nitrophenol: equilibrium, kinetics, and column studies.

PURPOSE: The purpose of the research is to investigate the application of bagasse fly ash, a sugar industry solid waste for the synthesis of zeolites and their behavior for the sorption of p-nitrophenol (p-NP). METHODS: Zeolitic materials were prepared from bagasse fly ash using alkaline hydrothermal (CZBFA) and fusion (FZBFA) treatment. Comparative batch sorption studies of prepared zeolitic material and virgin material were undertaken to determine their capacities for removal of p-nitrophenol. RESULTS: PXRD patterns revealed that zeolite P and analcime were the dominant contents of synthesized zeolitic material. Chemical composition, morphology, and crystalline nature of CZBFA and FZBFA were characterized by XRF, FTIR, and SEM. The Langmuir, Freundlich, Dubinin Redushkwich, and Temkin sorption isotherms were applied to compare the sorption nature and capacity of synthesized CZBFA and FZBFA with virgin BFA. For each sorbent-p-NP system, a pseudo-second-order kinetic model described the sorption kinetics accurately. The thermodynamics of the p-NP-sorbent systems exhibit an exothermic sorption process. Intraparticle diffusion model shows that the sorption rate was controlled by film diffusion followed by pore diffusion. Regeneration of sorbents was carried out by desorption studies with HCl, NaOH, and SDS detergent. The column studies were performed for the practical utility of sorbents, and breakthrough curve were obtained, which exhibit higher sorption capacity than batch method. CONCLUSION: The sorption capacities of the synthesized zeolites had improved sorption capacities for the sequestration of p-NP and can be utilized as low-cost sorbents for treatment of p-nitrophenolic wastewater.