Zeolites exchange capacity

Figure C2.12.1. Origin of ion exchange capacity in zeolites. Since every oxygen atom contributes one negative charge to the tetrahedron incoriDorated in the framework, the silicon tetrahedron carries no net charge while the aluminium tetrahedron carries a net charge of-1 which is compensated by cations M.

It may be noted that the ion exchange capacity is directly connected with the Al-content (each Al provides one negative charge). The zeolite used in detergent formulations (over 10 t/a) is NaA with Si/Al = 1, so with maximum exchange abi ity. 

DRIFT spectroscopy was used to determine Av0h shifts, induced by adsorption of N2 and hexane for zeolite H-ZSM-5 (ZSM-a and ZSM-b, Si/Al=15.5 and 26), H-mordenite (Mor-a and Mor-b, Si/AI— 6.8 and 10) and H-Y (Y-a and Y-b, Si/Al=2.5 and 10.4) samples. Catalysts were activated in 02 flow at 773 K in situ in the DRIFTS cell and contacted than with N2 at pressures up to 9 bar at 298 K or with 6.1% hexane/He mixture at 553 K, i.e., under reaction conditions. Catalytic activities of the solids were measured in a flow-through microreactor and kapp was obtained as slope of -ln(l-X0) vs. W/F plots. The concentration of Bronsted acid sites was determined by measuring the NH4+ ion-exchange capacity of the zeolite. The site specific apparent rate constant, TOFBapp, was obtained as the ratio of kapp and the concentration of Bronsted acid sites. 

It has already been mentioned that the formation of ultrastable Y zeolites has been related to the expulsion of A1 from the framework into the zeolite cages in the presence of steam (8,9), and the filling of framework vacancies by silicon atoms (11,12). This results in a smaller unit cell size and lower ion- exchange capacity (6). It also results in a shift of X-ray diffraction peaks to higher 20 values. Ultrastable Y zeolites prepared with two calcination steps (USY-B) have a more silicious framework than those prepared with a single calcination step (USY-A). Furthermore, since fewer aluminum atoms are left in the USY-B framework, its unit cell size and ion-exchange capacity are also lower and most of the nonframework aluminum is in neutral form (18). 

Aluminum-deficient Y zeolites prepared by partial removal of aluminum with a chelating agent (e.g. EDTA) also show improved thermal and hydrothermal stability compared to the parent zeolite. The optimum stability was found in the range of 25 to 50 percent of framework A1 extraction (8). However, the maximum degree of dealumination is also affected by the SiO /Al O ratio in the parent zeolite a higher ratio appears to allow more advanced dealumination without loss of crystallinity (8,25,45). Above 50 or 60 percent dealumination, significant loss of crystallinity was observed. Calcination of the aluminum-deficient zeolite resulted in a material with a smaller unit cell size and lower ion-exchange capacity compared to the parent zeolite. 

The characteristics of aluminophosphate molecular sieves include a univariant framework composition with Al/P = 1, a high degree of structural diversity and a wide range of pore sizes and volumes, exceeding the pore sizes known previously in zeolite molecular sieves with the VPI-5 18-membered ring material. They are neutral frameworks and therefore have nil ion-exchange capacity or acidic catalytic properties. Their surface selectivity is mildly hydrophilic. They exhibit excellent thermal and hydrothermal stability, up to 1000 °C (thermal) and 600 °C (steam). 

Zeolite type Channel system Pore openings (A hydrated form) Typical Sl02 Al203 mole ratio Theoretical ion exchange capacity (meq/g Na form, anhydrous)... 

Ion exchange capacity is a measure of the quantity of cahons adsorbed or removed by the zeolihc adsorbent. As described in Section 6.5.1.3, the total capacity of a zeolite is a function of its Si02/Al203 mole raho. Theorehcal ion exchanged capacities of some common zeolites are calculated and summarized in Table 6.4. 

The DB zeolite has a greatly reduced ion-exchange capacity, which... 

The use of surfactant-modified zeolite (SMZ) as a permeable barrier sorbent may offer several unique advantages when dealing with mixed contaminant plumes. Zeolites are hydrated aluminosilicate minerals characterized by cage-like structures, high internal and external surface areas, and high cation exchange capacities. Both natural and synthetic zeolites find use in industry as sorbents, soil amendments, ion exchangers,... 

Zeolite surface chemistry resembles that of smectite clays. In contrast to clays, however, natural zeolites can occur as millimeter- or greater-sized particles and are free of shrink-swell behavior. As a result, zeolites exhibit superior hydraulic characteristics and are suitable for use in filtration systems (Breck 1974) and as permeable barriers to dissolved chemical migration. Internal and external surface areas up to 800 m2 g have been measured. Total cation exchange capacities in natural zeolites vary from 250 to 3000 meq kg 1 (Ming and Mumpton 1989). External cation exchange capacities have been determined for a few natural zeolites and typically range from 10 to 50 percent of the total cation exchange capacity (Bowman et al. 1995). 

Zeolites and inorganic ion-exchange catalysts have been treated in reactive milling to alter their properties. For example, the amorphization of Zeolite A has been described by Kosanovic et al. [93] these authors observed a loss of crystallinity, a decrease of cation-exchange capacity, and an increase of solubility of A and Y zeolites which was caused by breaking of Si-O-Si and Si-O-Al bonds in the zeolite. 

The total exchange capacity (TEC) of a aluminosilicate zeolite is a function of the framework, that is, the Si/Al ratio. It is easy to get a numerical relation between the TEC in mequiv/g, C, and the number of A1 atoms per framework unit cell, NA1 [104] ... 

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