ABSTRACT
The separate collection and treatment of urine allows for an environmentally friendly and cost-efficient management of the nutrients contained in urine. The primary goal should be to recover all these nutrients. However, in some cases it will be economically or ecologically more sensitive to recover only the phosphorus, while nitrogen is removed together with organic substances (measured as chemical oxygen demand, COD) and pathogens. In this study, we investigated the use of galvanostatic electrolysis for the removal of nitrogen and COD from real stored urine. Non-active type boron-doped diamond (BDD) and active type thermally decomposed iridium oxide film (TDIROF) anodes were evaluated using batch experiments. On both anodes, ammonia was exclusively removed by indirect oxidation with active chlorine (AC:Cl2, HClO, and ClO-). As a consequence, ammonia was not completely removed, if chlorine was consumed by competing processes. While COD was present, ammonia removal was faster on TDIROF (227 ± 16 gN m-2 d-1 at 20 mA cm-2) than on BDD (43 ± 20 gN m-2 d-1 at 20 mA cm-2). The reason for the slower ammonia removal on BDD was the enhanced reaction of AC with organic molecules. In fact, hydroxyl radicals broke organic molecules down to shorter chain molecules which reacted with most of the AC leaving only little AC for the oxidation of ammonia. This preferential oxidation of organics resulted in very high COD removal rates on BDD (above 420 gCOD m-2 d-1 at 20 mA cm-2 for COD concentrations above 1000 mgCOD L-1). A main drawback of electrolysis with both anodes was the high energy demand (BDD: 55 W h gCOD-1 and 766 W h gN-1 for 90% and 6% removal, respectively. TDIROF: 67 W h gCOD-1 and 77 W h gN-1 for 30% and 40% removal. All at 20 mA cm-2). It can be concluded that BDD and TDIROF anodes could be combined in series for a fast, complete, and more energy efficient electrochemical urine treatment: COD could be removed on BDD before the residual ammonia would be removed on TDIROF.
ABSTRACT
Chlorination byproducts (CBPs) are harmful to human health and the environment. Their formation in chlorine mediated electro-oxidation is a concern for electrochemical urine treatment. We investigated the formation of chlorate, perchlorate, and organic chlorination byproducts (OCBPs) during galvanostatic (10, 15, 20 mA · cm(-2)) electro-oxidation of urine on boron-doped diamond (BDD) and thermally decomposed iridium oxide film (TDIROF) anodes. In the beginning of the batch experiments, the production of perchlorate was prevented by competing active chlorine and chlorate formation as well as by direct oxidation of organic substances. Perchlorate was only formed at higher specific charges (>17 Ah · L(-1) on BDD and >29 Ah · L(-1) on TDIROF) resulting in chlorate and perchlorate being the dominant CBPs (>90% of initial chloride). BDD produced mainly short chained OCBPs (dichloromethane, trichloromethane, and tetrachloromethane), whereas longer chained OCBPs (1,2-dichloropropane and 1,2-dichloroethane) were more frequently found on TDIROF. The OCBPs were primarily eliminated by electrochemical stripping: On BDD, this pathway accounted for 40% (dichloromethane) to 100% (tetrachloromethane) and on TDIROF for 90% (1,2-dichloroethane) to 100% (trichloromethane) of what was produced. A post-treatment of the liquid as well as the gas phase should be foreseen if CBP formation cannot be prevented by eliminating chloride or organic substances in a pretreatment.
