摘要
For simulating the real deactivation of hollow titanium silicalite(HTS) zeolite in commercial ammoximation process, HTS was treated by 10% NH_3·H_2O solution at 120 ℃ in stirred autoclave. It is found that a part of HTS zeolite crystals dissolved in the hot NH_3·H_2O solution, and the specific surface area and pore volume continuously decreased with the increase in NH_3 hydrothermal treatment time. Meanwhile, the transformation of framework Ti species into extraframework Ti species was detected by the spectroscopic methods. However, the extraframework Ti species were still in a highly dispersed state after the hydrothermal and thermal treatments as shown by TEM images, while the formation of new acid sites was not detected. Upon combining the results of characterization with catalytic performance of HTS, the main deactivation reason for this material had been determined, which might be attributed to the reduction of specific surface area and active centers after basic treatment and calcination of HTS samples. And then the possible mechanism of simulated deactivation of HTS zeolite was proposed, which could describe the elemental reaction steps much more visually and directly.
For simulating the real deactivation of hollow titanium silicalite（HTS） zeolite in commercial ammoximation process, HTS was treated by 10% NH_3·H_2O solution at 120 ℃ in stirred autoclave. It is found that a part of HTS zeolite crystals dissolved in the hot NH_3·H_2O solution, and the specific surface area and pore volume continuously decreased with the increase in NH_3 hydrothermal treatment time. Meanwhile, the transformation of framework Ti species into extraframework Ti species was detected by the spectroscopic methods. However, the extraframework Ti species were still in a highly dispersed state after the hydrothermal and thermal treatments as shown by TEM images, while the formation of new acid sites was not detected. Upon combining the results of characterization with catalytic performance of HTS, the main deactivation reason for this material had been determined, which might be attributed to the reduction of specific surface area and active centers after basic treatment and calcination of HTS samples. And then the possible mechanism of simulated deactivation of HTS zeolite was proposed, which could describe the elemental reaction steps much more visually and directly.
基金
financially supported by the National Basic Research Program of China(973 Program,2006CB202508)
the China Petrochemical Corporation(SINOPEC Group 20673054)
