技术应用

Effects of Post-Pyrolysis Air Oxidation of Biomass Chars on Adsorption of Neutral and Ionizable Compounds

Environmental Science & technology

Feng Xiao

This study was conducted to understand the effects of thermal air oxidation of biomass  chars experienced during formation or production on their adsorptive properties towards  various compounds, including five neutral nonpolar and polar compounds and seven  weak acids and bases (pKa, 3−5.2) selected from among industrial chemicals and the  triazine and phenoxyacetic acid herbicide classes. Post-pyrolysis air oxidation (PPAO) at 400 o  C of anoxically-prepared wood and pecan shell chars for up to 40 min enhanced the  mass-normalized adsorption at pH ~7.4 of all test compounds, especially the weak acids  and bases, by up to 100-fold. Both general and specific effects were identified. The  general effect results from ‘reaming’ of pores by the oxidative removal of pore wall  matter and/or tarry deposits generated during the pyrolysis step. Reaming creates new  surface area and enlarges nanopores, which helps relieve steric hindrance to adsorption.  The specific effect results from creation of new acidic functionality that provides sites for  formation of very strong, charge-assisted hydrogen bonds (CAHB) with solutes having  comparable pKa. The CAHB hypothesis was supported by competition experiments and  the finding that weak acid anion adsorption increased with surface carboxyl content,  despite electrostatic repulsion from the growing negative charge. The results provide  insight into the effects of air oxidation on pollutant retention.

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