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Abstract: The thermolysis of urea-water solution and its product, HNCO hydrolysis is investigated in a dual-reactor system. For the thermal decomposition below about 1073 K, the main products are ammonia (NH₃) and isocyanic acid (HNCO) whereas at higher temperatures the oxidation processes take effect and the products include a low concentration of nitric oxide (NO) and nitrous oxide (N₂O). The gas HNCO is quite stable and a high yield of HNCO is observed. The ratio of NH₃ to HNCO increases from approximately 1.2 to 1.7 with the temperature. The chemical analysis shows that H radical is in favor of HNCO hydrolysis by instigating the reaction HNCO+H·→·NH₂+CO and high temperature has positive effect on H radical. The hydrolysis of HNCO over an alumina catalyst made using a sol-gel process (designated as γ;-Al₂O₃) is investigated. The conversion of HNCO is high even at the high space velocities (6×10⁵ h⁻¹) and low temperatures (393–673 K) in the tests with catalysts, which enhances HNCO hydrolysis and raises the ratio of NH₃ to HNCO to approximately 100. The pure γ;-Al₂O₃ shows a better catalytic performance than CuO/γ;-Al₂O₃. The addition of CuO not only reduces the surface area but also decreases the Lewis acid sites which are recognized to have a positive effect on the catalytic activity. The apparent activation energy of the hydrolysis reaction amounts to about 25 kJ/mol in 393–473 K while 13 kJ/mol over 473 K. The overall hydrolysis reaction rate on catalysts is mainly determined by external and internal mass-transfer limitations.

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