Valorization of cow manure via hydrothermal carbonization for phosphorus recovery and adsorbents for water treatment.

The increased quantities of manure being generated by livestock and their extensive agronomic use have raised concerns around run-off impacting soil and groundwater quality. Manure contains valuable nutrients (especially phosphorus) that are critical to agriculture, but when directly land-applied the run-off of such nutrients contributes to eutrophication of waterways. This study investigates the hydrothermal carbonization of cow manure at two industrially feasible process extremes: 190 °C, 1 h and 230 °C, 3 h, to concentrate and then recover phosphorus from the solid hydrochar via acid leaching and precipitation. Up to 98 wt% of phosphorus initially present in the hydrochar (88% in the raw manure) can be recovered, with the dominant crystalline species being hydroxyapatite. Acid leached hydrochars were subsequently pyrolyzed at 600 °C for 30 min, and then evaluated as adsorbent materials for water remediation by using methylene blue as a model adsorbate. Although pyrolyzed hydrochars have surface areas an order of magnitude higher (160-236 m/g) than the non-pyrolyzed acid leached hydrochars (11-23 m/g), their adsorption capacity is three times lower. Furthermore, while the higher carbonization temperature leads to greater recovery of phosphorus, it likewise leads to higher heavy metal concentrations in the precipitate (ranging from 0.1 to 100 mg/g). As such, lower temperature carbonization followed by acid-extraction - without further solid processing - is a potential pathway to recover phosphorus and adsorbent materials.