Zeolite catalyst acidic sites

Unlike to zeolite catalysts acidic sites hardly play any role in the C-methylation of 2-Et-A on oC-Fe Oj or GeOg-FegO since germanium promotion induces a considerable increases in the 2-Et-6-Me-A yield and selectivity while acidity remains practically unchanged. Regarding that the yield of the N-alkyl derivatives is only slightly influenced by germanium the participation of the weak basic or acidic sites in the N-methylation can not be ruled out. 

Fig. 8.21 Schematic representation of catalytic cycle for standard SCR reaction over metal-exchanged zeolite catalysts. Acid sites are associated with Lewis or Br0nsted sites at ion-exchanged metal ot flee proton sites. Redox sites are associated with oxo-metal (isolated or binuclear) ion-exchanged sites...

The sodium in the E-cat is the sum of sodium added with the feed and sodium on the fresh catalyst. A number of catalyst suppliers report sodium as soda (Na20). Sodium deactivates the catalyst acid sites and causes collapse of the zeolite crystal structure. Sodium can also reduce the gasoline octane, as discussed earlier. 

The introduction of zeolites into the FCC catalyst in the early 1960s drastically improved the performance of the cat cracker reaction products. The catalyst acid sites, their nature, and strength have a major influence on the reaction chemistry. 

Vanadium and sodium neutralize catalyst acid sites and can cause collapse of the zeolite structure. Figure 10-5 shows the deactivation of the catalyst activity as a function of vanadium concentration. Destruction of the zeolite by vanadium takes place in the regenerator where the combination of oxygen, steam, and high temperature forms vanadic acid according to the following equations ... 

Microporous and, more recently, mesoporous solids comprise a class of materials with great relevance to catalysis (cf. Chapters 2 and 4). Because of the well-defined porous systems active sites can now be built in with molecular precision. The most important catalysts derived from these materials are the acid zeolites. The acid site is defined by the crystalline structure and exhibits great chemical and steric selectivities for catalytic conversions, such as fluid catalytic cracking and alkane isomerization (cf. Chapter 2). In Section 9.5 we discuss the synthesis of zeolites and, briefly, of mesoporous solids. 

In some cases, the membrane material is inherently catalytic and the membrane serves as both catalyst and separator, controlling the two important functions of the reactor simultaneously as shown in Figure 1.12(d). A number of meso- and microporous inorganic membrane materials have catalytic properties, such as titania and zeolites with acid sites. As an example, mesoporous Ti02... 

In the case of solid catalysts, any atomic (ionic) group at the surface that can donate a proton is a Brdnsted acid while any place where one empty electron orbital exists is Lewis acid. For example, in the case of zeolites, Brdnsted acid site is a part of microporous aluminosilicate framework—a bridging [= Si (OH) A1 =] configuration which is able to donate a proton to an acceptor while Lewis acid site is either tri-coordinated A1 atom or charge-balancing cation Me " " which are able to accept the electron pair. Accordingly to the same theories, any place at the solid surface which can accept proton is a Brdnsted base while any place which can donate electron(s) is a Lewis basic site. For example, in the case of MeOjt (metallic oxides), the oxygen ions (0 ) behave as Brpnsted bases (because they are proton acceptors) while cations at the surface possess Lewis acidity (they are electron acceptors) [27, 28],... 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable. Incorporating zeolites (crystalline alumina-silica) with the silica/alumina catalyst improves selectivity towards aromatics. These catalysts have both Fewis and Bronsted acid sites that promote carbonium ion formation. An important structural feature of zeolites is the presence of holes in the crystal lattice, which are formed by the silica-alumina tetrahedra. Each tetrahedron is made of four oxygen anions with either an aluminum or a silicon cation in the center. Each oxygen anion with a -2 oxidation state is shared between either two silicon, two aluminum, or an aluminum and a silicon cation. 

Zeolites as cracking catalysts are characterized hy higher activity and better selectivity toward middle distillates than amorphous silica-alumina catalysts. This is attrihuted to a greater acid sites density and a higher adsorption power for the reactants on the catalyst surface. 

Efficient contacting of the feed and catalyst is critical for achieving the desired cracking reactions. Steam is commonly used to atomize the feed. Smaller oil droplets increase the availability of feed at the reactive acid sites on the catalyst. With high-activity zeolite catalyst, virtually all of the cracking reactions take place in three seconds or less. 

Alkaline earth metals in general, and sodium in particular, are detrimental to the FCC catalyst. Sodium permanently deactivates the catalyst by neutralizing its acid sites. In the regenerator it causes the zeolite to collapse, particularly in the presence of vanadium. Sodium comes from two prime sources ... 

Sodium decreases the hydrothermal stability of the zeolite. It also reacts with the zeolite acid sites to reduce catalyst activity. In the regenerator, sodium is mobile. Sodium ions tend to neutralize the strongest acid sites. In a dealuminated zeolite, where the UCS is low (24.22°A to 24.25°A), the sodium can have an adverse affect on the gasoline octane (Figure 3-7). The loss of octane is attributed to the drop in the number of strong acid sites. 

An active matrix provides the primary cracking sites. The acid sites located in the catalyst matrix are not as selective as the zeolite sites, but are able to crack larger molecules that are hindered from entering the small zeolite pores. The active matrix precracks heavy feed molecules for further cracking at the internal zeolite sites. The result is a synergistic interaction between matrix and zeolite, in which the activity attained by their combined effects can be greater than the sum of their individual effects [2J. 

A rare-earth-exchanged zeolite increases hydrogen transfer reactions. In simple terms, rare earth forms bridges between two to three acid sites in the catalyst framework. In doing so, the rare earth protects... 

Improved crystallinity by producing more uniform zeolite crystals, FCC catalyst manufacturers have greater control over the zeolite acid site distribution. In addition, there is an upward trend in the quantity of zeolite being included in the catalyst. 

The synthesis of ethylenediamine (EDA) from ethanolamine (EA) with ammonia over acidic t3pes of zeolite catalyst was investigated. Among the zeolites tested in this study, the protonic form of mordenite catalyst that was treated with EDTA (H-EDTA-MOR) showed the highest activity and selectivity for the formation of EA at 603 K, W/F=200 g h mol, and NH3/ =50. The reaction proved to be highly selective for EA over H-EDTA-MOR, with small amounts of ethyleneimine (El) and piperazine (PA) derivatives as the side products. IR spectroscopic data provide evidence that the protonated El is the chemical intermediate for the reaction. The reaction for Uie formation of EDA from EA and ammonia required stronger acidic sites in the mordenite channels for hi er yield and selectivity. 

Spectroscopy. In the methods discussed so far, the information obtained is essentially limited to the analysis of mass balances. In that re.spect they are blind methods, since they only yield macroscopic averaged information. It is also possible to study the spectrum of a suitable probe molecule adsorbed on a catalyst surface and to derive information on the type and nature of the surface sites from it. A good illustration is that of pyridine adsorbed on a zeolite containing both Lewis (L) and Brbnsted (B) acid sites. Figure 3.53 shows a typical IR ab.sorption spectrum of adsorbed pyridine. The spectrum exhibits four bands that can be assigned to adsorbed pyridine and pyridinium ions. Pyridine adsorbed on a Bronsted site forms a (protonated) pyridium ion whereas adsorption on a Lewis site only leads to the formation of a co-ordination complex. 

Krossner, M., Sauer, J., 1996, Interaction of Water With Brpnsted Acidic Sites of Zeolite Catalysts. Ab Initio Study of 1 1 and 2 1 Surface Complexes , J. Phys. Chem., 100, 6199. 

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