Large ZSM-5 Crystals Research Articles

Fluoride-free synthesis of mesoporous [Al]-[B]-ZSM-5 using cetyltrimethylammonium bromide and methanol-to-olefin activity with high propene selectivity

Large ZSM-5 crystals containing [B]-sites and mesopores with 2.5 nm pore sizes are synthesized in a fluoride-free, low OH− medium using cethyltrimethylammonium bromide as mesoporogen and 1,6-diaminohexane as structure directing agent. Absence of extra-framework Al sites and low concentrations of silanol sites are evidenced by 27Al MAS-NMR and in-situ FTIR analysis. The low-defect containing [Al]-[B]-ZSM-5 (Mes-[Al]-[B]-ZSM-5) is evaluated for catalyzing the methanol-to-olefins reaction and found to result in low coke formation (4.1 mg g-1 h-1) and very low alkane and aromatic formation rates. The propene to ethene ratio of 4.3 observed using Mes-[Al]-[B]-ZSM-5 is found to be superior to that (1.9) of a nano-sized [Al]-[B]-ZSM-5 (crystal sizes around 36 nm). Small particle sizes for nano-sized [Al]-[B]-ZSM-5 is found to be effective for supplying a higher coke tolerance, but insignificant for olefin product selectivity.

Selective Toluene Disproportionation to Produce Para-Xylene over Modified ZSM-5

Industrial demand for p-xylene has been increasing in recent years and the major production is by toluene disproportionation. This research studied the effect of crystal size and the modification by silica deposition on the surface of the zeolite. Shape selective catalysts have been prepared by modifying two different ZSM-5 zeolites with different crystal sizes (0.5 µm, 5 µm) by chemical liquid deposition (CLD) using TEOS (tetraethyl orthosilicate) to deposit inert silica layers. The large ZSM-5 crystals modified with two cycles of silica showed high p-xylene selectivity at typically 84 % with very low conversion. Pressure effect on the reaction was investigated. Selectivity achieved was 40 – 66 % at conversions typically 4-20 % at 10 bar.

CTAB resulted direct synthesis and properties of hierarchical ZSM-11/5 composite zeolite in the absence of template

ZSM-11/5 composite zeolite was successfully synthesized through the addition of cetyltrimethylammonium bromide (CTAB) and seed, but in the absence of template. However, without the addition of CTAB, pure large hexagonal ZSM-5 crystals were formed in the presence of ZSM-11 as seed. The products were characterized by SEM, XRD, XRF, 27Al NMR, 27Si NMR, N2 physical adsorption and NH3-TPD. The SEM images imply that large ZSM-5 crystals gradually evolve from imperfect to perfect crystals, rather than forming small crystals first, and then gradually growing. The ZSM-11/5 composite zeolite exhibited hierarchical characteristics with higher specific surface areas, higher external surface areas, higher mesopore volumes and more acid sites than the sample synthesized by the conventional method with tetrabutylammonium as template. The ZSM-11/5 composite zeolite also exhibited excellent catalytic properties in the reaction of methanol to hydrocarbons.

Effect of ZSM-5 crystal size on its catalytic properties for conversion of methanol to gasoline

Four-sized monodispersed ZSM-5 crystals, being 70, 200, 400 and 650 nm, were hydrothermally synthesized by changing the H2O/Si molar ratio in the synthesis gel, and characterized with XRD, TEM, BET and NH3-TPD techniques. The crystal size effect of ZSM-5 on its catalytic performance for conversion of methanol to gasoline (MTG) was investigated. It was shown that the external surface area of the sample decreased with its crystal size, while the acid site amount firstly increased, and then kept almost constant. Nevertheless, 650 nm ZSM-5 crystals attaching small particles exhibit large external surface area and strong acidity. The catalytic stability and the liquid hydrocarbon yield decreased with increasing crystal size. The sample with a crystal size of 70 nm shows a catalytic lifetime of 96 h and a gasoline yield of 30.8%. The large external surface area and relatively strong acidity endow the sample with a crystal size of 650 nm also has a catalytic lifetime of 91 h, indicating that synthesis of large ZSM-5 crystals with small crystallites adhered to their surface could be a potential way to improve the catalytic performance.

Dispersion and Orientation of Zeolite ZSM‐5 Crystallites within a Fluid Catalytic Cracking Catalyst Particle

Confocal fluorescence microscopy was employed to selectively visualize the dispersion and orientation of zeolite ZSM-5 domains inside a single industrially applied fluid catalytic cracking (FCC) catalyst particle. Large ZSM-5 crystals served as a model system together with the acid-catalyzed fluorostyrene oligomerization reaction to study the interaction of plane-polarized light with these anisotropic zeolite crystals. The distinction between zeolite and binder material, such as alumina, silica, and clay, within an individual FCC particle was achieved by utilizing the anisotropic nature of emitted fluorescence light arising from the entrapped fluorostyrene-derived carbocations inside the zeolite channels. This characterization approach provides a non-invasive way for post-synthesis characterization of an individual FCC catalyst particle in which the size, distribution, orientation, and amount of zeolite ZSM-5 aggregates can be determined. It was found that the amount of detected fluorescence light originating from the stained ZSM-5 aggregates corresponds to about 15 wt %. Furthermore, a statistical analysis of the emitted fluorescence light indicated that a large number of the ZSM-5 domains appeared in small sizes of about 0.015-0.25 μm(2), representing single zeolite crystallites or small aggregates thereof. This observation illustrated a fairly high degree of zeolite dispersion within the FCC binder material. However, the highest amount of crystalline material was aggregated into larger domains (ca. 1-5 μm(2)) with more or less similarly oriented zeolite crystallites. It is clear that this visualization approach may serve as a post-synthesis quality control on the dispersion of zeolite ZSM-5 crystallites within FCC particles.

Localization of p-Nitroaniline Chains Inside Zeolite ZSM-5 with Second-Harmonic Generation Microscopy

For the first time, second-harmonic generation microscopy (SHGM) has been employed to study zeolites. Large ZSM-5 crystals filled with p-nitroaniline (PNA) dipoles have been visualized. It is shown that SHGM can discriminate between the straight b-pores and the sinusoidal a-pores of this zeolite, thus revealing the intergrown structure of these crystals. Moreover, it is shown that dipole chains are formed not only in the b-pores but also in the a-pores. PNA only assembles into dipole chains of parallel orientation in those pores that are directly accessible from the outer surface. The area in which this PNA ordering prevails is limited to a strip near the outer surface of the zeolite crystal. A rationalization for these two observations is offered.

Morphology of Large ZSM-5 Crystals Unraveled by Fluorescence Microscopy

Understanding the internal structure of ZSM-5 crystallites is essential for improving catalyst performance. In this work, a combination of fluorescence microscopy, AFM, SEM, and optical observations is employed to study intergrowth phenomena and pore accessibility in a set of five ZSM-5 samples with different crystal morphologies. An amine-functionalized perylene dye is used to probe acid sites on the external crystal surface, while DAMPI (4-(4-diethylaminostyryl)- N-methylpyridinium iodide) is used to map access to the straight channels in MFI from the outer surface. The use of these dyes is validated by studying the well-understood rounded-boat type ZSM-5 crystals. Next coffin-shaped ZSM-5 crystals are considered; we critically evaluate the seemingly conflicting 2-component and 3-component models that have been proposed to account for the hourglass structure in these crystals. The data prove that observation of an hourglass structure is essentially unrelated to a 90 degree rotation of the pyramidal crystal components under the (010) face. Hence, in perfectly formed coffin-shaped crystals, the straight channels can be accessed from (010). However, in other crystal batches, sections with a 90 degrees rotation can be found; they are indeed located inside the crystal sections under (010) but often only partially occupy these pyramidal components. In such a case, both straight and sinusoidal pores surface at the hexagonal face. The results largely support the 3-component model, but with the added notion that 90 degree rotated sections (as proposed in the 2-component model) are most likely to be formed inside the defect-rich, pyramidal crystal sections under the (010) faces.

Microstructures formed by secondary growth of fired ZSM-5 seed crystals

Oriented ZSM-5 seed crystals on an α-Al2O3 porous substrate were hydrothermally treated in a raw sol. The ZSM-5 membranes were fabricated via secondary growth of the seed crystals. For some samples, the seed-applied substrate was fired at 300 or 600 °C before the secondary growth in order to enhance adhesion between the substrate and the seed crystals. The influence of the firing on the subsequent secondary growth of the seed crystals was examined by XRD, SEM, and TEM. The TEM images of the sample fired at 300 °C showed that the resulting membrane was continuous, and in the membrane, large ZSM-5 particles were distributed in a porous matrix. The ZSM-5 particles were slightly smaller than the used seed crystals. HR-TEM observations showed that the porous matrix is comprised of ZSM-5 micro-crystals, and the part adjacent to the large ZSM-5 crystals has the same crystallographic orientation as the large crystals. The TEM images of the sample fired at 600 °C showed that the resulting layer is comprised of particles with a core-shell structure. The core consisted of ZSM-5 micro-crystals, whereas the shell was composed of large ZSM-5 rod-like crystals. It is inferred that the formation of these interesting microstructures is related to the degradation of the template agent, NPr4OH, in the seed crystals by firing at 300 and 600 °C. The part including no template is dissolved by a hydrothermal treatment, and the dissolved species is re-crystallized via reaction with a template agent in the used raw sol, resulting in the formation of interesting microstructures.

Synthesis of Large ZSM-5 Crystals under High Pressure

ABSTRACTThe synthesis temperature for silicalite-I (MFI) can be raised to 300°C by applying high pressure to stabilize the structure-directing organic template. The elevated temperature and pressure favor theformation of crystals with improved quality. Prismatic silicalite-I crystals with a uniform size of about 0.7× 0.2 × 0.2 mm have been obtained by heating a gel prepared from TMA-silicate solution, TPABr andsodium hexafluorosilicate at 250°C under a pressure of 80 MPa. The influence of synthesis conditions on the crystal sizes has been studied by systematically changing temperature, pressure and gel compositions. Underthe specific conditions of 250°C and 80 MPa, a strong correlation was found between the crystal size andthe F/Si mole ratio of the starting gel, which enables the preparation of uniform crystals of silicalite-I with preset dimensions.

Analysis of Active-Site Distribution in ZSM-5 Crystals by Infrared Microscopy

The acid Site distribution over large ZSM-5 crystals was analyzed using FTIR microscopy. Results of the analysis of the OH-stretching vibrations and of vibrations of pyridine adsorbed on Brønsted and Lewis acid sites were found to be in good agreement. The resolution which can be obtained using this novel technique is about 10-20 μm. This limits the application to large crystals as analyzed in this study. Comparison of the results of IR microscopy with aluminum distributions obtained by electron microprobe analysis revealed that IR microscopy cannot resolve inhomogeneities on a scale smaller than the above-stated limits. The results of both methods on a larger scale, however. are in very good agreement. Using a combination of both techniques, it is possible to obtain a clearer picture of the distribution of acid sites in large zeolite crystals, where electron microprobing gives the higher resolution, and IR microscopy allows the determination of the types of aluminum site present in the zeolite spatially resolved.

Aluminium distribution in large ZSM-5 crystals

The surface and interior compositions of large single and twinned ZSM-5 crystals were studied by electron microprobe analysis. The aluminium distribution across an individual crystal plane surface is found to be uniform. The morphology of the crystal is closely related to the aluminium incorporated in the ZSM-5 framework. Large fault-free single crystals have a very low interior aluminium content.