h i g h l i g h t s• A co-treatment process for recovery of Co and Li and simultaneous detoxification of PVC in subcritical water was proposed.• PVC was used as a hydrochloric acid source.• More than 95% Co and nearly 98% Li were leached under the optimum conditions.• Neither corrosive acid nor reducing agent was used.• The co-treatment process has technical, economic and environmental benefits over the traditional recovery processes. a r t i c l e i n f o In this work, an effective and environmentally friendly process for the recovery of cobalt (Co) and lithium (Li) from spent lithium-ion batteries (LIBs) and simultaneously detoxification of polyvinyl chloride (PVC) in subcritical water was developed. Lithium cobalt oxide (LiCoO 2 ) power from spent LIBs and PVC were co-treated by subcritical water oxidation, in which PVC served as a hydrochloric acid source to promote metal leaching. The dechlorination of PVC and metal leaching was achieved simultaneously under subcritical water oxidation. More than 95% Co and nearly 98% Li were recovered under the optimum conditions: temperature 350• C, PVC/LiCoO 2 ratio 3:1, time 30 min, and a solid/liquid ratio 16:1 (g/L), respectively. Moreover, PVC was completely dechlorinated at temperatures above 350• C without any release of toxic chlorinated organic compounds. Assessment on economical and environmental impacts revealed that the PVC and LiCoO 2 subcritical co-treatment process had significant technical, economic and environmental benefits over the traditional hydrometallurgy and pyrometallurgy processes. This innovative co-treatment process is efficient, environmentally friendly and adequate for Co and Li recovery from spent LIBs and simultaneous dechlorination of PVC in subcritical water.
a b s t r a c tThis work investigated various supercritical water oxidation (SCWO) systems, i.e. SCWO1 (only water), SCWO2 (water + H 2 O 2 ) and SCWO3 (water + H 2 O 2 /NaOH), for waste printed circuit boards (PCBs) detoxification and recycling. Response surface methodology (RSM) was applied to optimize the operating conditions of the optimal SCWO3 systems. The optimal reaction conditions for debromination were found to be the NaOH of 0.21 g, the H 2 O 2 volume of 9.04 mL, the time of 39.7 min, maximum debromination efficiency of 95.14%. Variance analysis indicated that the factors influencing debromination efficiency was in the sequence of NaOH > H 2 O 2 > time. Mechanism studies indicated that the dissociated ions from NaOH in supercritical water promoted the debromination of brominated epoxy resins (BERs) through an elimination reaction and nucleophilic substitution. HO 2 Å , produced by H 2 O 2 could induce the oxidation of phenol ring to open (intermediates of BERs), which were thoroughly degraded to form hydrocarbons, CO 2 , H 2 O and NaBr. In addition, the alkali-silica reaction between OH À and SiO 2 induced the phase transformation of glass fibers, which were simultaneously converted into anorthite and albite. Waste PCBs in H 2 O 2 /NaOH improved SCWO system were fully degraded into useful products and simultaneously transformed into functional materials. These findings are helpful for efficient recycling of waste PCBs.
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