Zeolite thermal stability

W. Schmidt, F. Schuth, H. Reichert, K. Unger, and B. Zibrowius, VPI-5 and Related Aluminophosphates Preparation and Thermal Stability. Zeolites, 1992, 12, 2-8. 

Therapy, adjuvants Thermal activation, clinoptilolite Thermal analysis, ETS-4 Thermal behavior, clinoptilolite Thermal desorption Thermal stability, FAU Thermal stability, MOR Thermal stability, zeolites Thermal treatment, MFl... 

Indeed the FCC process as early as the late fifties started to use catalyst formulations based on the incorporation of thermally-stabilized zeolites in a suitable matrix. The advantages were increased rates, increased liquid products, increased tolerance to poisons and larger operating flexibility as compared to former silica-alumina based catalysts. 

In a great number of cases, zeolites are used as auxiliary elements. They may act either as a framework to stabilize the sensor material, as filter layers (either catalytic or size restrictive) to enhance selectivity of a sensitive film, or as a preconcentrator of specific analytes from diluted solutions. For example, due to excellent chemical and thermal stability, zeolites can be used as a substrate to prepare compounds and devices with desirable fundamental physical and chemical properties (Xu et al. 2006). For example, inorganic or organic compounds, metal and metal-organic compounds, and their clusters can be assembled into the pores and cages in zeohtes. Some nanosized metal or metal oxide particles have been successfully inserted into the caves and the pores or highly dispersed on the external surface of zeohtes. 

For microporous compounds with special compositions, calcination effects are even more severe. As compared with zeolites, these compounds have lower thermal stability. Strictly speaking, most of them are nonporous since removal of the occluded guest molecules by calcination usually results in collapse. This is due to strong H-bonds with the framework, coordination bonds, and sometimes the templating molecule is shared with the inorganic polyhedra. Relevant examples of low-stability microporous compounds with interesting structural features are zeolitic open-framework phosphates made of Ga [178], In [179], Zn [180], Fe [181],... 

Although hollow fibers are thought to be an excellent candidate to be used as support-they are cheap and have a very high surface area to volume (>1000 m m ) - very few reports on hollow-fiber-supported zeolite membranes exist in the open literature. For zeohte membranes, ceramic hollow fibers are preferred because of their mechanical and thermal stability. Recently, Alshebani... 

This paper is concerned with the synthesis of Y zeolite with Si02/Al203 ratio of 4.5 from kaolin taken in Yen Bai-Vietnam and their catal3dic activity for the cracking of n-heptane. The synthesized sample (NaYl) showed the Y zeolite crystallinity of 53% and PI zeolite crystallinity of 32%, and exhibited good thermal stability up to 880 C. The activity and the stability of HYl turned out to be lower than those of standard sample (HYs), but the toluene selectivity was higher. The conversion of n-heptane to toluene might be due to the metal oxide impurities, which was present in the raw materials and this indicates the potential application of this zeolite for the conversion of n-parafRn to aromatics. 

A zeolite membrane, where the pores originate from the structure, presents only one type of (ultramicro)pore and therefore seems to be a good candidate for CMRs application. Moreover the structural origin of the pores should induce a much better thermal stability of the... 

It was shown by EXAFS that the structure and dispersion of the Mo sulfide species in MoSx/NaY were unaltered by a prolonged sulfidation of 20-h at 673 Kina stream of H,S/Hj. This fact indicates that highly dispersed Mo sulfide species are thermally stable. On the other hand, with MoSx/AljOj prepared by using Mo(CO) [12], a considerable agglomeration of highly dispersed Mo sulfide species was observed at a shorter treatment time. It is considered that highly dispersed Mo sulfide clusters are thermally stabilized in zeolite cavities. 

Taking into consideration the preparation procedures, the Mo content of 2.1Mo/SC, and the Co/Mo atomic ratio of ca. unity at the maximum HDS activity, highly dispersed Co-Mo binary sulfide clusters, possibly COjMOjSx, in the supercage of the NaY zeolite are suggested for catalytically active species. The HDS activity of the CoSx-MoSx/NaY was not changed even after a 20-h treatment at 673 K in a stream of HjS/H (Fig.3), demonstrating a high thermal stability of the active species. 

Low temperature CO sorption experiments monitored with the IR spectroscopy were used to determine the nature of active (acid) sites present in the Fe-TON zeolites. It is well known that CO is a useful probe molecule for Lewis acid sites. Narrow and well resolved bands appear in the region 2135 - 2150 cm"1. The IR spectra of CO sorbed in amount sufficient to cover all Lewis sites in the Fe-TON of different Si/Fe ratios are presented in Figure 2A. The samples of a high iron content (Si/Fe=27, 36) showed a significantly lower thermal stability. The activation of the NFL form of these Fe-TON... 

The aim of this study is to follow in situ the dehydration mechanism of the zeolite ECR1, in its as-synthesized and NH4-cxchangcd form in order to determine its thermal stability and whether the structure undergoes phase transition during dehydration. 

The chemical and thermal stability of these solid catalysts is also an important advantage for their use, making them resistant to higher reaction temperatures and to a variety of chemical attacks. Moreover, the ease of handling and recovering of the zeolite by a simple filtration, with the possibility of reusing it, are valuable features for a catalysis-based reaction. 

Some investigations have focused on the influence of the Si/Al ratio in zeolite BEA. Corma et al. (140) used various BEA samples synthesized with different Si/Al ratios and found a higher thermal stability towards dealumination with increasing Si/Al ratio. The most stable catalyst was also the most active one. Weitkamp et al. (141) compared the selectivities of four H-BEA samples with Si/Al ratios ranging from 12 to 90. The octane number selectivities ran through a maximum at a Si/Al ratio of 19, whereas the TMP/DMH ratio decreased... 

Stability. Being a fairly high-silicious zeolite, mordenite generally has high thermal stability. It was reported (77) that progressive acid dealumination results in an increase in thermal stability, followed by a decrease. Maximum stability was reached for a Si09/Al90 ratio of about 19. 1 1 J... 

Many types of zeolites are known but only a rather small number of zeolites are used in catalysis. In this section, the most important zeolites will be introduced. We will focus on the most commonly used types which are Zeolite X, Zeolite Y, ZSM-5, and Zeolite Beta. Apart from these, a couple of other zeolites, e.g., Mordenite or Zeolite L, are also used for specific reactions but they are produced on a smaller scale. Most of these zeolites have a remarkable thermal stability and can be heated to a temperature of 600°C without structural damage some of them resist even temperatures of 800 to 1000°C. 

However, some characteristics of the reactant and product (and solvent) molecules used in the reactions of fine chemical synthesis have to be considered their large size, their low thermal stability, and their polarity. The small size of the micropores limits the use of zeolites to the synthesis of relatively small molecules solutions to overstep this limitation have been found with the development of larger (mesoporous) molecular sieves and of nanocrystallite zeolites, the reaction then occurring on the large external surface. The low thermal stability of the molecules leads to operation at a low ternperamre, often in the liquid phase. Last, as will be shown in the first example (Section 12.2.3.1), the differences in polarity between reactant(s), product(s), and solvent molecules have to be considered for optimizing both the zeolite catalyst and the operating conditions. 

Figure 4.43 Thermal stability differences for three different zeolites all treated at various temperatures for 1 h In air. Zeolites 2 and 3 have very poor high temperature thermal stability when compared to zeolite 1.

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