The cyclohexanone peroxide reaction process, one of the eighteen hazardous chemical processes identified in China, is performed in indirectly cooled semibatch reactors. The peroxide reaction is added to a mixture of hydrogen peroxide and nitric acid, which form heterogeneous liquid–liquid systems. A simple and general procedure for building boundary and temperature diagrams of peroxide process is given here to account for the overall kinetic expressions. Such a procedure has been validated by comparison with experimental data. Thermally safer operating parameters were obtained at laboratory scale, and the scaled-up procedure was performed to give the minimum dosing time in an industrial plant, which is in favor of maximizing industrial reactor productivity. The results are of great significance for governing the peroxide reaction process apart from the thermal runaway region. It also greatly aids in determining optimization on operating parameters in industrial plants.
The low efficiency of peroxone (O 3 /H 2 O 2 ) at acidic and neutral pH restrained its application in water purification . To overcome this shortcoming, CeO X @SiO 2 with large surface area, abundant surface oxygen vacancies (V o ), Lewis sites (L sites) and high Ce(III)/Ce(IV) ratio were synthesized to change the traditional electron transfer pathway between O 3 and H 2 O 2 . V o was facile in absorbing H 2 O 2 to form V o -H 2 O 2 and L sites were capable of absorbing O 3 to form L-O 3 . The electron at V o could be donated to V o -H 2 O 2 and generate V o -HO 2 − , which then effectively triggered the decomposition of L-O 3 at CeO X @SiO 2 ’s interface and O 3 in bulk solution. The electron transfer at the solid-liquid interface with the help of Ce 3+ /Ce 4+ redox cycle and V o was pH independent and different from the traditional electron transfer of peroxone reaction. Nitrobenzene (NB) mineralization was promoted to 92.5% in CeO X @SiO 2 -peroxone, but only 63.8% TOC was removed in tradition peroxone process. Moreover, CeO X @SiO 2 -peroxone had a wide pH application range. NB’s degradation in CeO X @SiO 2 -peroxone process followed the co-oxidation mechanism of superoxide free (•O 2 − ) and hydroxyl radical (•OH). The finding of this study could broaden the popularization of peroxone in water treatment and provided a strategy for catalyst design.
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