Solid superacid catalyst as well as preparation method and application thereof
A solid superacid and catalyst technology, which is applied in the direction of catalyst activation/preparation, carboxylate preparation, chemical instruments and methods, etc., and can solve problems affecting catalytic activity, sintering of sulfated zirconia, etc.
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Embodiment 1
[0050] Synthesis of UiO-66: First, 1.16g (4.97mmol) of zirconium chloride and 0.825g (4.97mmol) of terephthalic acid (H 2 BDC) was dissolved in 60 mL of N,N-dimethylformamide (DMF) and 20 mL of acetic acid. Then ultrasonic treatment was used for 30 min to homogenize the solution, and after the ultrasonic treatment was completed, the reaction was carried out at 120° C. for 24 h. After the reaction, the mixture was centrifuged, washed three times with N,N-dimethylformamide (DMF) and methanol, and dried at 120° C. for 6 h to obtain UiO-66 nanocrystals.
Embodiment 2
[0052] Sulfated zirconia (SO 4 2- / ZrO 2 ) synthesis: UiO-66 was calcined at 500 °C for 3 h (heating rate 1 °C / min) to obtain ZrO 2 . According to the ratio of 1g:15mL ZrO at 30°C 2 Immersed in ammonium sulfate solution (3mol / L) for 1h, then filtered, dried at 100°C for 6h, then calcined at 500°C and kept for 3h (heating rate 1°C / min) to obtain SO 4 2- / ZrO 2 .
Embodiment 3
[0054] The solid superacid catalyst (SO 4 2- / ZrO 2 @Al 2 o 3 ) preparation method, as follows:
[0055] Dissolve 0.5 g of aluminum isopropoxide in 20 mL of ethanol and stir for 3 h to form a transparent solution for later use. Disperse 100mg UiO-66 nanocrystals in 30mL deionized water, sonicate for 10min, add 0.3g CTAB and stir for 5min. Then slowly add the aluminum isopropoxide solution into the UiO-66 dispersion, stir for 3 hours, filter under reduced pressure and wash with 95% ethanol and deionized water for 3 to 5 times, and dry at 100°C for 6 hours to obtain aluminum hydroxide-coated The product of UiO-66, denoted as UiO-66@Al(OH) 3 . UiO-66@Al(OH) 3 Calcined at 500°C for 3 hours to obtain calcined product of alumina-coated zirconia, denoted as ZrO 2 @Al 2 o 3 , and then placed in ammonium sulfate solution (1mol / L) at 30°C for 1h with stirring (dosage: 1g UiO-66: 15mL ammonium sulfate solution), then filtered and dried at 100°C for 6h. Calcined at 500 DEG C f...
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