Study of the alkylation of isobutane with n-butene over WO3/ZrO2 strong solid acid. 1. Effect of the preparation method, WO3 loading, and calcination temperature

A series of strong solid acids composed of WO3/ZrO2 were prepared. Their crystal structure, surface state, and acidity were determined by the methods of X-ray diffraction, thermal gravimetric and differential thermal analysis, temperature-programmed reduction, laser Raman, and acidity measurement. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in the tetragonal phase, the addition of WO3 plays an important role in stabilizing the tetragonal phase of ZrO2, and all of the samples possessed large surface areas. WO3 in WO3/ZrO2 is mainly monolayer dispersed, and a small amount crystallized on the ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, acting as the strong solid acid center. The catalytic properties of WO3/ZrO2 strong solid;acids for alkylation of isobutane with butene at different conditions were investigated. They had a better reaction performance than other strong solid acids; a parallel relationship could be drawn between the catalytic activity and the acid amounts as well as the acidic strength of the catalysts.

In situ preparation of Ir/ZSM-5/cordierite honeycombs and their application for NOx abatement

ZSM-5 zeolites were synthesized in situ onto cordierite honeycombs by vapor phase transport (VPT) for the first time. The as-synthesized ZSM-5/cordierite honeycombs were impregnated with IrCl3 and tested for NOx reduction with a simulated exhaust gas as the reducing agent. Under the conditions of excess oxygen, the Ir/ZSM-S/cordierite monolith catalyst exhibited NO reduction of 73% at a temperature of 573 K and a space velocity of 20,000 h(-1).

An investigation of the roles of surface aluminum and acid sites in the zeolite MCM-22

Ammonia adsorption studies reveal that the observed Lewis acidity in the zeolite MCM-22 is derived from at least two types of framework aluminum sites (Al(F)), that is, octahedral Al(F) and three-coordinate Al(F). Comparative ammonia or trimethylphosphine (TMP) adsorption experiments with MCM-22 confirm that octahedral Al species gives rise to the signal at delta(ISO) approximate to 0 in the (27)Al NMR spectrum; this is a superposition of two NMR signals from the different Al species on the water-re constructed zeolite surface. A sharp resonance assigned to framework Al reversibly transforms on ammonia adsorption to delta(ISO) (27)Al approximate to 55 from tetrahedral Al(F), while the broad peak is assigned to nonframework aluminium which results from hydrothermal treatment. This study also demonstrates the effectiveness of (27)Al magic angle spinning (MAS) and multiple quantum (MQ) MAS NMR spectroscopy as a technique for the study of zeolite reactions.

NMR study on the acidity of TS-1 zeolite

The acidic properties of TS-1 and Silicalite-I zeolites have been investigated by the solid-state MAS NMR technique capable of in situ sample pretreatment. As shown by a combination of the P-31 MAS NMR and H-1 MAS NMR techniques with trimethylphosphine, not only Bronsted acid sites but also Lewis acid sites exist in the TS-1 zeolites. Moreover, TS-1 zeolite is more acidic compared with Silicalite-1. The H-1, Si-29 MAS NMR spectra and the resonance related to Bronsted acid species in the P-31 MAS NMR spectra demonstrate clearly that the presence of titanium in the framework results in the formation of a new hydroxy group, titanols, which is more acidic than silanols of Silicalite-1. The P-31 MAS NMR measurements also illustrate convincingly the existence of at least two different Lewis acid species on the TS-1 zeolites. The conversion of propylene oxide into methoxypropanol catalyzed by TS-1 or Silicalite-I zeolite in methanol solution as a test reaction has also been described. With the increase of titanium in zeolite, TS-1 appears to have a higher activity during the reaction of propylene oxide to methoxypropanol.

A high-resolution solid-state NMR study on nano-structured HZSM-5 zeolite

Variations in the structure and acidity properties of HZSM-5 zeolites with reduction in crystal sizes down to nanoscale (less than 100 nm) have been investigated by XRD, TEM and solid-state NMR with a system capable of in situ sample pretreatment. As evidenced by a combination of Al-27 MAS NMR, Si-29 MAS, CP/MAS NMR and H-1 MAS NMR techniques, the downsize of the zeolite crystal leads to an obvious line broadening of the Al-27, Si-29 MAS NMR spectrum, an increasing of the silanol concentration on the external surface, and a pronounced alteration of the acidity distribution between the external and internal surfaces of the zeolite. In a HZSM-5 zeolite with an average size at about 70 nm, the nonacidic hydroxyl groups (silanols) are about 14% with respect to the total amount of Si, while only 4% of such hydroxyl groups exist in the same kind of zeolite at 1000 nm crystal size. The result of H-1 MAS NMR obtained using Fluorinert(R) FC-43 (perfluorotributyl amine) as a probe molecule demonstrates that most of the silanols are located on the external surface of the zeolite. Moreover, the concentration of Bronsted acid sites on the external surface of the nano-structured zeolite appears to be distinctly higher than that of the microsized zeolite.

Synthesis of NaA zeolite membranes from clear solution

NaA zeolite membranes were successfully synthesized on a porous alpha -Al2O3 support from clear solution. The synthesis parameters, such as surface seeding, synthesis time, synthesis stages, etc. were investigated. Surface seeding can not only accelerate the formation of NaA zeolite on the support surface, but can also inhibit the transformation of NaA zeolite into other types of zeolites. A continuous NaA zeolite membrane formed on the seeded support after 2 h of synthesis. Gas permeation results showed that a synthesis time of 3 h produced the best NaA zeolite membrane. When the synthesis time was longer than 4 h, the NaA zeolite on the support surface began to transform into other types of zeolites, and the quality of the NaA zeolite membrane decreased. The quality of the NaA zeolite membrane can be improved by employing the multi-stage synthesis method. The NaA zeolite membrane with a synthesis time of 2 h after a two-stage synthesis showed the best gas permeation performance. The permeances of H-2, O-2, N-2, and n-C4H10 decreased as the molecular kinetic diameter of the gases increased. which showed the molecular sieving effect of the NaA zeolite membrane. The permselectivities of H-2/n-C4H10 and O-2/N-2 were 19.1 and 1.8, respectively. These values are higher than the Knudsen diffusion ratios of 5.39 and 0.94. However, the permeation of n-C4H10 also indicated that the NaA zeolite membrane had certain defects with diameters larger than the pore size of NaA zeolite. A synthesis model was proposed to clarify the effect of surface seeding. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis of NaA zeolite membrane by microwave heating

The synthesis of NaA zeolite membrane on a porous alpha -Al2O3 support by microwave heating (MH) was investigated. The formation of a NaA zeolite membrane was drastically promoted by MH. The synthesis time was reduced from 3 h for conventional heating (CH) to 15 min for MH. Surface seeding cannot only promote the formation of NaA zeolite on the support, but also inhibit the transformation of NaA zeolite into other types of zeolites. The thickness of the NaA zeolite membrane synthesized by MH was about 4 mum, thinner than that of NaA zeolite membrane synthesized by CH. The permeance of NaA zeolite membrane synthesized by MH was four times higher than that of the NaA zeolite membrane synthesized by CH, while their permselectivities were comparable. Multi-stage synthesis resulted in the transformation of NaA zeolite into other types of zeolites, and the perfection of the as-synthesized membrane decreased.

Synthesis and perfection evaluation of NaA zeolite membrane

The synthesis of NaA zeolite membrane on a porous alpha -Al2O3 support from clear solution and the evaluation of the perfection of the as-synthesized membrane by gas permeation were investigated. When an unseeded support was used, the NaA zeolite began to transform into other types of zeolites before a continuous NaA zeolite membrane formed. When the support was coated with nucleation seeds, not only the formation of NaA zeolite on the support surface was accelerated, but also the transformation of NaA zeolite into other types of zeolites was inhibited. A continuous NaA zeolite membrane can be formed. Perfection evaluation indicated that the NaA zeolite membrane with the synthesis time of 3 h showed the best perfection after a one-stage synthesis. The perfection of NaA zeolite membrane can be improved by employing the multi-stage synthesis method. The NaA zeolite membrane with a synthesis time of 2 h after a two-stage synthesis showed the best gas permeation performance, The permselectivity of H-2/n-C4H10 and O-2/N-2 were 19.1 and 1.8, respectively, higher than those of the corresponding Knudsen diffusion selectivity of 5.39 and 0.94, which showed the molecular sieving effect of NaA zeolite. However, the permeation of n-C4H10 also indicated that the NaA zeolite membrane had certain defects, the diameter of which were larger than the NaA zeolite channels. (C) 2001 Elsevier Science B.V. All rights reserved.