Facile one-step synthesis of a versatile nitrogen-doped hydrochar from olive oil production waste, “alperujo”, for removing pharmaceuticals from wastewater

Abstract

In line with the principles of zero waste and recycling, alperujo (AL) was used in this study to produce a value-added product: hydrochar (HC) with high adsorption capacity. An optimization of the hydrothermal carbonization (HTC) conditions, such as temperature, residence time, and water/solid ratio, was carried out to maximize the adsorption capacity. Eight HCs were obtained, and an in-depth comparative characterization, as well as adsorption tests of two pharmaceuticals with very different physicochemical properties (fluoxetine (FLX) and cefazolin (CFZ)), were performed. This first step allowed for elucidation of the best candidates to carry out nitrogen grafting on their surface, resulting in the HC obtained at a higher water/solid ratio and temperature, and longer residence time: 3-220°C-2.5 h with a maximum uptake of 4.6 and 0.4 mg/g for FLX and CFZ, respectively. After that, a facile one-step, one-pot synthesis of nitrogen-doped hydrochars (N-HC) was developed to prepare a versatile bio-adsorbent with enhanced adsorption capacity. Two N–HCs were prepared using urea (U-HC) and polyethyleneimine (PEI-HC) and were intensively characterized to shed light on the adsorption mechanism. In both cases, amide groups were formed, which favored the adsorption process. PEI-HC acquired an outstanding maximum adsorption capacity of 983.84 mg/g for CFZ, and 29.31 mg/g for FLX, and the process was well described by the Freundlich isotherm and pseudo-second-order kinetic model. A co-adsorption test was performed using PEI-HC for both pharmaceuticals, finding that the adsorption process occurs in different active sites because there was no interference between the pollutants. This fact corroborates the versatility of the new bio-adsorbent synthesized.