Sequential Ammonia and Carbon Dioxide Adsorption on Pyrolyzed Biomass to Recover Waste Stream Nutrients

Abstract

The amine-rich surfaces of pyrolyzed human solid waste (py-HSW) can be "primed" or "regenerated" with carbon dioxide (CO₂) to enhance their adsorption of ammonia (NH₃) for use as a soil amendment. To better understand the mechanism by which CO₂ exposure facilitates NH₃ adsorption to py-HSW, we artificially enriched a model sorbent, pyrolyzed, oxidized wood (py-ox wood) with amine functional groups through exposure to NH₃. We then exposed these N-enriched materials to CO₂ and then resorbed NH₃. The high heat of CO₂ adsorption (<i>Q</i> _st) on py-HSW, 49 kJ mol^-1, at low surface coverage, 0.4 mmol CO₂ g^-1, showed that the naturally occurring N compounds in py-HSW have a high affinity for CO₂. The <i>Q</i> _st of CO₂ on py-ox wood also increased after exposure to NH₃, reaching 50 kJ mol^-1 at 0.7 mmol CO₂ g^-1, demonstrating that the incorporation of N-rich functional groups by NH₃ adsorption is favorable for CO₂ uptake. Adsorption kinetics of py-ox wood revealed continued, albeit diminishing NH₃ uptake after each CO₂ treatment, averaging 5.9 mmol NH₃ g^-1 for the first NH₃ exposure event and 3.5 and 2.9 mmol NH₃ g^-1 for the second and third; the electrophilic character of CO₂ serves as a Lewis acid, enhancing surface affinity for NH₃ uptake. Furthermore, penetration of ¹⁵NH₃ and ¹³CO₂ measured by NanoSIMS reached over 7 μm deep into both materials, explaining the large NH₃ capture. We expected similar NH₃ uptake in py-HSW sorbed with CO₂ and py-ox wood because both materials, py-HSW and py-ox wood sorbed with NH₃, had similar N contents and similarly high CO₂ uptake. Yet NH₃ sorption in py-HSW was unexpectedly low, apparently from potassium (K) bicarbonate precipitation, reducing interactions between NH₃ and sorbed CO₂; 2-fold greater surface K in py-HSW was detected after exposure to CO₂ and NH₃ than before gas exposure. We show that amine-rich pyrolyzed waste materials have high CO₂ affinity, which facilitates NH₃ uptake. However, high ash contents as found in py-HSW hinder this mechanism.