Pore size aluminas

Preliminary experiments on such a strategy of coupled separation and photodegradation were carried out on a simplified experimental device schematically represented in Figure 25.15a. It consists of two tanks separated by a 1.8 pm pore size alumina microfiltration symmetric membrane with grains coated with an anatase layer. The feed tank contained methylene blue (MB) and the reception tank was initially filled with pure water. Under continuous UV irradiation, MB is completely destroyed as it arrives in the reception tank (Figure 25.15b). The quantity of destroyed MB per surface area unit is equal to 1.0 X 10 mol.s. m . 

Thin-film MIP composite membranes (cf. Scheme lb), imprinted for theophyUin and caffein, had been prepared by Hong et al. [99], using photo-copolymerization of a MAA/EDMA mixture on top of an asymmetric 20 nm pore size alumina membrane. Additional gas permeation studies suggested that the membranes were defect ( pinhole ) free. 

The sol—gel technique has been used mosdy to prepare alumina membranes. Figure 18 shows a cross section of a composite alumina membrane made by sHp coating successive sols with different particle sizes onto a porous ceramic support. SiUca or titanium membranes could also be made by the same principles. Unsupported titanium dioxide membranes with pore sizes of 5 nm or less have been made by the sol—gel process (57). 

Fig. 18. Cross-sectional scanning electron micrograph of a three-layered alumina membrane/support (pore sizes 0.2, 0.8, and 12 p.m, respectively).

The large majority of activated alumina products are derived from activation of aluminum hydroxide, rehydrated alumina, or pseudoboehmite gel. Other commerical methods to produce specialty activated aluminas are roasting of aluminum chloride [7446-70-0], AIQ calcination of precursors such as ammonium alum [7784-25-0], AlH2NOgS2. Processing is tailored to optimize one or more of the product properties such as surface area, purity, pore size distribution, particle size, shape, or strength. 

Rehydration Bonded Alumina. Rehydration bonded aluminas are agglomerates of activated alumina, which derive their strength from the rehydration bonding mechanism. Because more processing steps are involved in the manufacture, they are generally more expensive than activated aluminum hydroxides. On the other hand, rehydration bonded aluminas can be produced in a wider range of particle shape, surface area, and pore size distribution. 

Membranes. Membranes comprised of activated alumina films less than 20 )J.m thick have been reported (46). These films are initially deposited via sol—gel technology (qv) from pseudoboehmite sols and are subsequently calcined to produce controlled pore sizes in the 2 to 10-nm range. Inorganic membrane systems based on this type of film and supported on soHd porous substrates have been introduced commercially. They are said to have better mechanical and thermal stabiUty than organic membranes (47). The activated alumina film comprises only a miniscule part of the total system (see Mel rane technology). 

Transition aluminas are good catalyst supports because they are inexpensive and have good physical properties. They are mechanically stable, stable at relatively high temperatures even under hydrothermal conditions, ie, in the presence of steam, and easily formed in processes such as extmsion into shapes that have good physical strength such as cylinders. Transition aluminas can be prepared with a wide range of surface areas, pore volumes, and pore size distributions. 

Because of the industrial magnitude of these processes, many catalysts have been examined with variations in metal distribution, pore size, and alkalinity. In most synthetic work where catalyst life and small variations in yield are not of great importance, most palladium-on-carbon or -on-alumina powder catalysts will be found satisfactory for conversion of phenols to cyclohexanones. Palladium has a relatively low tendency to reduce aliphatic ketones, and a sharp decrease in the rate of absorption occurs at about 2 mol of consumed hydrogen. Nickel may also be used but overhydrogenation is more apt to occur. 

Once the membrane was successfully produced, it was analysed for characterisation and scanning. The sol-gel technique was successfully used to obtain a crack-free unsupported membrane, which was expected to have pore size of 1-2 nm. The development of the crack-free membrane may not have the same strength without strong, solid support. The next stage of this work was to characterise the fabricated membrane. Hie objectives of this study were to develop a zirconia-coated 7-alumina membrane with inorganic porous support by the sol-gel method and to characterise the surface morphology of the membrane and ceramic support. 

The advantage of sol-gel technology is the ability to produce a highly pure y-alumina and zirconia membrane at medium temperatures, about 700 °C, with a uniform pore size distribution in a thin film. However, the membrane is sensitive to heat treatment, resulting in cracking on the film layer. A successful crack-free product was produced, but it needed special care and time for suitable heat curing. Only y-alumina membrane have the disadvantage of poor chemical and thermal stability. 

The consideration that many zeolite types exist, each with many tunable properties (e.g., pore size and alumina content), leads not only to a wealth of options but also to a high level of complexity. Owing to this complexity and limited understanding of zeolite formation and permeation behavior, a lot of experimental effort is required in this field, slowing down developments toward successful application. 

To overcome the limitations of natural zeolites a whole range of synthetic zeolites have been manufactured since the 1950s. These have tailored pore sizes and tuned acidities, as well as often incorporating other metal species. The basic synthesis involves mixing a source of silica, usually sodium silicate or colloidal Si02, with a source of alumina, often sodium aluminate, and a base such as sodium hydroxide. The mixture is heated at temperatures up to 200 °C under autogenous pressure for a period of a few days to a few weeks to allow crystallization of the zeolite. 

Silica is the support of choice for catalysts used in processes operated at relatively low temperatures (below about 300 °C), such as hydrogenations, polymerizations or some oxidations. Its properties, such as pore size, particle size and surface area are easy to adjust to meet the specific requirements of particular applications. Compared with alumina, silica possesses lower thermal stability, and its propensity to form volatile hydroxides in steam at elevated temperatures also limits its applicability as a support. Most silica supports are made by one of two different preparation routes sol-gel precipitation to produce silica xerogels and flame hydrolysis to give so-called fumed silica. 

While our discussion will mainly focus on sifica, other oxide materials can also be used, and they need to be characterized with the same rigorous approach. For example, in the case of meso- and microporous materials such as zeolites, SBA-15, or MCM materials, the pore size, pore distribution, surface composition, and the inner and outer surface areas need to be measured since they can affect the grafting step (and the chemistry thereafter) [5-7]. Some oxides such as alumina or silica-alumina contain Lewis acid centres/sites, which can also participate in the reactivity of the support and the grafted species. These sites need to be characterized and quantified this is typically carried out by using molecular probes (Lewis bases) such as pyridine [8,9],... 

Fig. 3.23 shows pore volume distributions of some commercially important porous materials. Note that zeolites and activated carbon consist predominantly of micropores, whereas alumina and silica have pores mainly in the me.sopore range. Zeolites and active carbons have a sharp peak in pore size distribution, but in the case of the activated carbon also larger pores are present. The wide-pore silica is prepared specially to facilitate internal mass-transfer. 

Pore. size and surface area distribution. Pore sizes and pore volume distributions may be calculated from the relative pressures at which pores are filled (in the adsorption mode) or emptied (in the desorption mode). Fig. 3.45 shows the pore size distribution of a commercial y-alumina. The distribution is very broad both meso- and macropores are present. In practice this is usually a desired situation a texture consisting of a network of large pores (main roads) and small pores (side roads) is ideal. 

Fig. 3.45. Pore size distribution of a commercial y-alumina calculated using the Kelvin equation.

Manufacturer Product Type of Alumina Pore size (nm) Particle Size Distribution (pm)... 

Another potential vertical medium is not a continuous thin film, but rather an assembly of metal particles deposited in well defined pores in an alumina film on Al [109-117]. The shape anisotropy of the particles gives the desired vertical anisotropy. In producing such structures, the proper conditions for the anodization of the Al disk and for the subsequent control of pore size are as important as the conditions of metal deposition. The structures of such disks are discussed in detail below. 

Vertical media with very high coercivities can be produced by plating into alumina pores [112], Some of these media are too hard to be easily written with present heads. Tailoring of the pore size can be used to obtain structures with the desired Hc [115, 116], however. Recording characteristics of disks have been determined [112-114, 116] such media show excellent promise as vertical recording media. In addition, structures with electrodeposited Fe in the pores were tested in life-tests at elevated temperatures and humidity and in corrosive atmospheres. They were found to perform satisfactorily. 

This value is considerably higher than the experimental value (0.17) obtained from rate measurements on different size particles, but several factors may be invoked to explain the inconsistency. There will be a distribution of both pore radii and pore lengths present in the actual catalyst rather than uniquely specified values. Alumina catalysts often have a bimodal pore-size distribution. Our estimate of an apparent first-order rate constant using the method outlined above will be somewhat in error. The catalyst surface may not be equally active throughout if selective deactivation has taken place and the peripheral region is less active than the catalyst core. Other sources of error are the... 

---