Selective recovery of Co(II), Mn(II), Cu(II), and Ni(II) by multiple step batch treatments with nanocellulose products

The recovery of Co(II), Mn(II), Ni(II), and Cu(II) from black mass e-waste solutions through cellulose nanofibers (CNFs) and nanocrystals (CNCs) was investigated. These materials were synthetized by TEMPO-oxidation followed by high-pressure homogenization, and acid hydrolysis, respectively. The NC characterization included the measurement of consistency, cationic demand, carboxylic content, dissolved amorphous cellulose, and transmittance at λ = 600 nm. These parameters revealed a high transmittance of the NC solutions and a large presence of anionic groups on the surface. The high surface area and charge of the NC justify their high interaction with the cationic metals. Results indicate that short contact times (even 1 min) and low sorbent doses (10 mg/L) at acidic pHs (2 to 4) implied remarkable sorption capacities in most cases with more than 1 g/g of sorption capacity of Co(II), Mn(II), and Cu(II) in single-step sorption tests. Such levels of sorption capacities exceed by at least one order of magnitude most of the literature values of metal recovery applying cellulosic materials. Isotherm modeling through a combination of Langmuir and Freundlich models suggested that both sorption and surface precipitation occurred. A novel procedure following multiple-step batch operation was applied for Mn(II) sorption. This new method was applied as a five-step process, leading to a fourfold and 18-fold increase of sorption capacity onto CNCs and CNFs, respectively, compared to the single-step process. Therefore, this process shows an innovative way to implement the multiple-step batch sorption with NC as an efficient and environmentally friendly solution for critical metal recovery from e-waste leachates.