Particle size adsorption

Surface heterogeneity may merely be a reflection of different types of chemisorption and chemisorption sites, as in the examples of Figs. XVIII-9 and XVIII-10. The presence of various crystal planes, as in powders, leads to heterogeneous adsorption behavior the effect may vary with particle size, as in the case of O2 on Pd [107]. Heterogeneity may be deliberate many catalysts consist of combinations of active surfaces, such as bimetallic alloys. In this last case, the surface properties may be intermediate between those of the pure metals (but one component may be in surface excess as with any solution) or they may be distinctly different. In this last case, one speaks of various effects ensemble, dilution, ligand, and kinetic (see Ref. 108 for details). 

One of the most important uses of specific surface determination is for the estimation of the particles size of finely divided solids the inverse relationship between these two properties has already been dealt with at some length. The adsorption method is particularly relevant to powders having particle sizes below about 1 pm, where methods based on the optical microscope are inapplicable. If, as is usually the case, the powder has a raiige of particle sizes, the specific surface will lead to a mean particle size directly, whereas in any microscopic method, whether optical or electron-optical, a large number of particles, constituting a representative sample, would have to be examined and the mean size then calculated. 

It would be difficult to over-estimate the extent to which the BET method has contributed to the development of those branches of physical chemistry such as heterogeneous catalysis, adsorption or particle size estimation, which involve finely divided or porous solids in all of these fields the BET surface area is a household phrase. But it is perhaps the very breadth of its scope which has led to a somewhat uncritical application of the method as a kind of infallible yardstick, and to a lack of appreciation of the nature of its basic assumptions or of the circumstances under which it may, or may not, be expected to yield a reliable result. This is particularly true of those solids which contain very fine pores and give rise to Langmuir-type isotherms, for the BET procedure may then give quite erroneous values for the surface area. If the pores are rather larger—tens to hundreds of Angstroms in width—the pore size distribution may be calculated from the adsorption isotherm of a vapour with the aid of the Kelvin equation, and within recent years a number of detailed procedures for carrying out the calculation have been put forward but all too often the limitations on the validity of the results, and the difficulty of interpretation in terms of the actual solid, tend to be insufficiently stressed or even entirely overlooked. And in the time-honoured method for the estimation of surface area from measurements of adsorption from solution, the complications introduced by... 

An additional method for increasing particle size deserves mention. When a precipitate s particles are electrically neutral, they tend to coagulate into larger particles. Surface adsorption of excess lattice ions, however, provides the precipitate s particles with a net positive or negative surface charge. Electrostatic repulsion between the particles prevents them from coagulating into larger particles. 

A PVDF membrane filter has been shown to remove >10 particles of vims for vimses >50 nm independent of fluid type (8). Vimses smaller than 50 nm are not removed as efficientiy but are removed in a predictable manner which correlates to the vims particle size. The chemistry of the suspending fluid affects titer reduction for vimses <50 nm owing to other removal mechanisms, such as adsorption, coming into play. The effects of these other mechanisms can be minimized by using filtration conditions that minimize adsorption. 

Physical Properties. Physical properties of importance include particle size, density, volume fraction of intraparticle and extraparticle voids when packed into adsorbent beds, strength, attrition resistance, and dustiness. These properties can be varied intentionally to tailor adsorbents to specific apphcations (See Adsorption liquid separation Aluminum compounds, aluminum oxide (alumna) Carbon, activated carbon Ion exchange Molecular sieves and Silicon compounds, synthetic inorganic silicates). 

As manufactured, most resias have a Gaussian-Hke distributioa of particle size. Very few are as small as 0.3 mm or as large as 1.0 mm. Most are betweea 0.5—0.8 mm. A backwash before usiag aew resia is common practice to assure uniform flow during the adsorption and regeneration steps. The backwash eliminates air pockets that may have formed while filling the column and sorts the beads such that the smaller sizes are at the top of the bed and... 

Deterrnination of the specific surface area can be made by a variety of adsorption measurements or by air-permeability deterrninations. It is customary to calculate average particle size from the values of specific surface by making assumptions regarding particle size distribution and particle shape, ie, assume it is spherical. 

Several properties of the filler are important to the compounder (279). Properties that are frequentiy reported by fumed sihca manufacturers include the acidity of the filler, nitrogen adsorption, oil absorption, and particle size distribution (280,281). The adsorption techniques provide a measure of the surface area of the filler, whereas oil absorption is an indication of the stmcture of the filler (282). Measurement of the sdanol concentration is critical, and some techniques that are commonly used in the industry to estimate this parameter are the methyl red absorption and methanol wettabihty (273,274,277) tests. Other techniques include various spectroscopies, such as diffuse reflectance infrared spectroscopy (drift), inverse gas chromatography (igc), photoacoustic ir, nmr, Raman, and surface forces apparatus (277,283—290). 

The two steps in the removal of a particle from the Hquid phase by the filter medium are the transport of the suspended particle to the surface of the medium and interaction with the surface to form a bond strong enough to withstand the hydraulic stresses imposed on it by the passage of water over the surface. The transport step is influenced by such physical factors as concentration of the suspension, medium particle size, medium particle-size distribution, temperature, flow rate, and flow time. These parameters have been considered in various empirical relationships that help predict filter performance based on physical factors only (8,9). Attention has also been placed on the interaction between the particles and the filter surface. The mechanisms postulated are based on adsorption (qv) or specific chemical interactions (10). 

Important physical properties of catalysts include the particle size and shape, surface area, pore volume, pore size distribution, and strength to resist cmshing and abrasion. Measurements of catalyst physical properties (43) are routine and often automated. Pores with diameters <2.0 nm are called micropores those with diameters between 2.0 and 5.0 nm are called mesopores and those with diameters >5.0 nm are called macropores. Pore volumes and pore size distributions are measured by mercury penetration and by N2 adsorption. Mercury is forced into the pores under pressure entry into a pore is opposed by surface tension. For example, a pressure of about 71 MPa (700 atm) is required to fill a pore with a diameter of 10 nm. The amount of uptake as a function of pressure determines the pore size distribution of the larger pores (44). In complementary experiments, the sizes of the smallest pores (those 1 to 20 nm in diameter) are deterrnined by measurements characterizing desorption of N2 from the catalyst. The basis for the measurement is the capillary condensation that occurs in small pores at pressures less than the vapor pressure of the adsorbed nitrogen. The smaller the diameter of the pore, the greater the lowering of the vapor pressure of the Hquid in it. 

Surface Area and Permeability or Porosity. Gas or solute adsorption is typicaUy used to evaluate surface area (74,75), and mercury porosimetry is used, ia coajuactioa with at least oae other particle-size analysis, eg, electron microscopy, to assess permeabUity (76). Experimental techniques and theoretical models have been developed to elucidate the nature and quantity of pores (74,77). These iaclude the kinetic approach to gas adsorptioa of Bmaauer, Emmett, and TeUer (78), known as the BET method and which is based on Langmuir s adsorption model (79), the potential theory of Polanyi (25,80) for gas adsorption, the experimental aspects of solute adsorption (25,81), and the principles of mercury porosimetry, based on the Young-Duprn expression (24,25). 

Settling and rainout are important mechanisms of contaminant transfer from the atmospheric media to both surface soils and surface waters. Rates of contaminant transfer caused by these mechanisms are difficult to assess qualitatively however, they increase with increasing soil adsorption coefficients, solubility (for particulate contaminants or those adsorbed to particles), particle size, and precipitation frequency. 

Physical adsorption—surface areas of any stable solids, e.g., oxides used as catalyst supports and carbon black Chemisorption—measurements of particle sizes of metal powders, and of supported metals in catalysts... 

In particular, emphasis will be placed on the use of chemisorption to measure the metal dispersion, metal area, or particle size of catalytically active metals supported on nonreducible oxides such as the refractory oxides, silica, alumina, silica-alumina, and zeolites. In contrast to physical adsorption, there are no complete books devoted to this aspect of catalyst characterization however, there is a chapter in Anderson that discusses the subject. 

Each application for carbon treatment must be cognizant of the characteristics of the contaminant to be removed and designed with the proper carbon type in order to attain optimum results. Basically, there are two forms of activated carbon powdered and granular. The former are particles that are less than U.S. Sieve Series No. 50, while the latter are larger. The adsorption rate is influenced by carbon particle size, but not the adsorptive capacity which is related to the total surface area. —... 

Ultrafiltration utilizes membrane filters with small pore sizes ranging from O.OlS t to in order to collect small particles, to separate small particle sizes, or to obtain particle-free solutions for a variety of applications. Membrane filters are characterized by a smallness and uniformity of pore size difficult to achieve with cellulosic filters. They are further characterized by thinness, strength, flexibility, low absorption and adsorption, and a flat surface texture. These properties are useful for a variety of analytical procedures. In the analytical laboratory, ultrafiltration is especially useful for gravimetric analysis, optical microscopy, and X-ray fluorescence studies. 

Adsorption efficiency can be optimized by using finer particle size products which will improve the diffusion rate to the surface of the activated carbon. However, there is a tradeoff in using finer particles with pressure drop and, hence energy use. Note that during start-up of an activated carbon filter bed, a bed expansion of 25 to 35 % is recommended in order to remove soluble matter and to stratify particles in order to ensure that the MTZ is maintained when future backwashing is performed. 

New templated polymer support materials have been developed for use as re versed-phase packing materials. Pore size and particle size have not usually been precisely controlled by conventional suspension polymerization. A templated polymerization is used to obtain controllable pore size and particle-size distribution. In this technique, hydrophilic monomers and divinylbenzene are formulated and filled into pores in templated silica material, at room temperature. After polymerization, the templated silica material is removed by base hydrolysis. The surface of the polymer may be modified in various ways to obtain the desired functionality. The particles are useful in chromatography, adsorption, and ion exchange and as polymeric supports of catalysts (39,40). 

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