The influence of temperature and ageing of initial aluminophosphate gels on their chemical and phase composition was studied. The hydrated oxide (boehmite) was used as the source of aluminum to prepare gels containing ammonium phosphate, undissolved pseudoboehmite and amorphous aluminophosphate in different proportions. The gel with predominant amorphous aluminophosphate was shown to provide selective crystallization of high phase purity AlPO4-11 with the crystallinity degree close to 100 %. The developed method for preparation of these disperse molecular aluminophosphate sieves AlPO4-11 is a step to crystallization of silicoaluminophosphates SAPO-11 that are promising Russian catalysts for industrial processes of hydroisomerization of n-paraffins used for manufacturing of Arctic diesel fuel, III group oils and isomerization of butenes.
The one-dimensional channel pore system and the moderately strong acid centers inherent in aluminophosphate (AlPO4-11) and silicoaluminophosphate (SAPO-11) molecular sieves make them promising catalyst for hydroisomerization of higher n-paraffins. However, the mechanism of crystallization of these materials is not well understood as yet. XRD,27Al and31P MAS NMR, lowtemperature adsorption-desorption of nitrogen, and SEM techniques were used for the first time for studying the stage crystallization of aluminophosphate AlPO4-11 for commercial boehmite based aluminium source. AlPO4-11 was shown to form via an intermediate phase based on layered crystalline aluminophosphate. It was established that highly crystalline and phase-pure AlPO4-11 was formed at 200 °C during 6 to 24 hours. When the crystallization at 200 °C lasted for more than two days, AlPO4-11 turned into non-porous cristobalite. The results obtained will be used for developing methods for deliberate control of the phase composition and crystallinity of industrially important silicoaluminophosphate sieves SAPO-11 with required properties to develop promising catalysts based thereon for large-scale processes of hydroisomerization of n-paraffins.
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