AlPO-11 and SAPO-11 are synthesized using microwave heating. The effects of precursor volume, reaction temperature, reactor geometry, stirring, applicator type and frequency on the microwave synthesis of SAPO-11 and AlPO-11 are studied. The nucleation time and crystallization rate are determined from crystallization curves for SAPO-11 (and/or AlPO-11), for the various parameters investigated. Increasing volume of the reacting material decreases the reaction rate of SAPO-11 at 160 degrees C. In particular, the nucleation time increases with increase in the reaction volume. Increasing the reaction temperature increases the crystallization rate and decreases the nucleation time, however it decreases the particle size. Nucleation of SAPO-11 and AlPO-11 under microwave heating is strongly dependant on the reaction temperature. Using wider geometry vessel (33 mm compared to 11 mm diameter) enhances the reaction rate, producing larger crystals in the same reaction time, even though the crystallization rate is decreased. The crystallization rate is enhanced by applicator type in the following order CEM MARS-5 oven>CEM Discover "focused" system>monomode waveguide. Stirring the reacting solution during heating affects primarily the nucleation time. The effect of microwave frequency on the nucleation and growth of SAPO-11 shows a dependence on the applicator type more than the specific frequency, for the frequency range 2.45-10.5 GHz. The difference between the crystallization rate observed at higher frequencies and that at 2.45 GHz maybe due to the multimode nature of the waveguide at frequencies above 2.45 GHz. Sweeping the microwave frequency linearly between 8.7 and 10.5 GHz at rates of 10 min(-1) and 100 min(-1) shows an intermediate crystallization curve to that for fixed frequencies of 2.45 GHz and that for 5.8, 8.7 and 10.5 GHz.

The effect of microwave and conventional heating methods on the nucleation and growth of SAPO-11 molecular sieve was investigated. Microwave synthesis enhances both the nucleation and growth of SAPO-11. The rate of heating primarily influences the nucleation time for both microwave and conventional heating. A more uniform morphology and narrower size distribution are formed using microwave heating compared to conventional. This suggests that rapid and even nucleation is the enhancement mechanism. Crystallization by conventional heating can be accelerated by immersion in the pre-heated fluid due to the faster heating rate and improved thermal conduction. Microwave synthesis of SAPO-11 occurs in minutes and, thus, significant energy savings can be realized compared to the hours required for conventional synthesis.

We have measured the nucleation conditions of n-propanol, n-butanol, and n-pentanol in a supersonic Laval nozzle, and estimated that the maximum nucleation rate J is 5 x 10(16) cm(-3) s(-1) with an uncertainty factor of 2. Plotting the vapor pressures p(J(max) ) and temperatures T(J(max) ) corresponding to the maximum nucleation rate as ln(p) versus 1T, produces a series of well separated straight lines. When these values are scaled by their respective critical parameters, p(c) and T(c), the data lie close to a single straight line. Comparing the experimental data to the predictions of classical nucleation theory reveals much higher experimental rates, and the deviation increases with increasing alcohol chain length and decreasing temperature. A scaling analysis in terms of Hale's scaled nucleation model [Phys. Rev. A 33, 4156 (1986); Metall. Trans. A 23, 1863 (1992)], clearly shows that our data are consistent with experimental nucleation rates measured using other devices that have characteristic rates many orders of magnitude lower.

While microwave enhancement of chemical syntheses has been demonstrated for a broad variety of chemical reactions, there is no accepted universal mechanism. Is the enhancement due to more efficient heating, to overheating, to nonuniform heating, or to nonthermal effects? Analyses are complicated due to the often significant spatial and temporal temperature variations in microwave reactor systems, particularly within microwave ovens. To address this, we employ multiple fiber-optic temperature probes throughout a cylindrical reactor with a focus on zeolite synthesis solutions being the dielectric medium. First, we vary the modes of power delivery (pulsed versus continuous) to quantify differences in local temperatures within a reaction vessel with water being the dielectric medium. The temperature distribution at steady state in the center of the water increased by 10 degrees C in pulsed delivery mode compared to the temperature distribution obtained in continuous delivery mode at the same average power. Then, we measured the temperature distributions for several zeolite synthesis solutions (NaY, silicalite, and SAPO-11) and water under microwave heating to investigate the temperature variations within these dielectric media. These measured temperature variations were found to be significant, depending on the dielectric permittivities of the reaction medium and their changes with temperature. Temperature profiles also depend on the microwave delivery mode and reactor configuration, i.e., the microwave reactor engineering. NaY synthesis solution exhibited the smallest penetration depth (2.6 mm at room temperature and 2.45 GHz); as a result, the solution temperature near the wall increased by 65 degrees C over the target temperature when the temperature at the center of the solution was targeted to 60 degrees C. To demonstrate the effect of overheating on zeolite synthesis, we synthesized NaY zeolite at 95 degrees C by controlling the temperature of the reaction near the wall, close to the penetration depth, and in the center away from the penetration depth. Controlling the center temperature results in greater overheating and consequently reduced nucleation time by 80 min, from 130 to 50 min.