Corbin, David R.; Keane Jr., Micheal; Abrams, Lloyd; Farlee, Rod D.; Bierstedt, Paul E.; Bein, Thomas
Designing zeolite catalysts for shape-selective reactions: Chemical modification of surfaces for improved selectivity to dimethylamine in synthesis from methanol and ammonia.
In: Journal of Catalysis, Vol. 124, No. 1: pp. 268-280
The relative contributions of external and intracrystalline acidic sites of small pore H-RHO zeolite for the selective synthesis of methylamines from methanol and ammonia have been studied. Nonselective surface reactions which produce predominantly trimethylamine can be eliminated by “capping” the external acidic sites with trimethylphosphite (TMP) and other reagents, thus improving the selectivity toward the formation of dimethylamine. For small pore zeolites, neither the zeolite pore size nor the internal acidic sites is significantly affected by this treatment. In situ infrared and MAS-NMR studies show that TMP reacts irreversibly with the zeolite acidic sites via a modified Arbusov rearrangement to form surface-bound dimethylmethylphosphonate.