Particle pore diameter

Ghrist, B.F., Stadalius, M.A., Snyder, L.R. (1987). Predicting bandwidth in the high-performance liquid chromatographic separation of large biomolecules. I. Size-exclusion studies and the role of solute stokes diameter versus particle pore diameter. J. Chromatogr. 387,1-19. 

Adsorption allows the selective collection and concentration onto solid surfaces of specific dissolved molecules from the broth. Adsorption can be non-specific, for those mechanisms based on polar, van der Waals and ionic interactions, or highly selective for affinity binding based on biochemical means (1,8) Commercially available adsorbants are generally granular porous particles to provide extensive surface area, with void volumes approaching 30-50% of the whole particle. Pore diameters are usually less than 0.01 mm. 

Adsorbent Pore diameter, nm Particle density, g/cm Specific area, mVg Apphcations... 

Other immobilization methods are based on chemical and physical binding to soHd supports, eg, polysaccharides, polymers, glass, and other chemically and physically stable materials, which are usually modified with functional groups such as amine, carboxy, epoxy, phenyl, or alkane to enable covalent coupling to amino acid side chains on the enzyme surface. These supports may be macroporous, with pore diameters in the range 30—300 nm, to facihtate accommodation of enzyme within a support particle. Ionic and nonionic adsorption to macroporous supports is a gentle, simple, and often efficient method. Use of powdered enzyme, or enzyme precipitated on inert supports, may be adequate for use in nonaqueous media. Entrapment in polysaccharide/polymer gels is used for both cells and isolated enzymes. 

Material and uses Shape"of particles Size range, U.S. standard mesh f Internal porosity, % Bulk dry density, kg/L Average pore diameter, nm Surface area, kmVkg Sorptive capacity, kg/kg (dry)... 

Two other deposition mechanisms, in addition to the six listed, may be in operation under particular circumstances. Some dust particles may be collected on filters by sieving when the pore diameter is less than the particle diameter. Except in small membrane filters, the sieving mechanism is probably limited to surface-type filters, in which a layer of collected dust is itself the principal filter medium. 

When the catalyst is expensive, the inaccessible internal surface is a liabihty, and in every case it makes for a larger reactor size. A more or less uniform pore diameter is desirable, but this is practically reahz-able only with molecular sieves. Those pellets that are extrudates of compacted masses of smaller particles have bimodal pore size distributions, between the particles and inside them. Micropores have diameters of 10 to 100 A, macropores of 1,000 to 10,000 A. The macropores provide rapid mass transfer into the interstices that lead to the micropores where the reaction takes place. 

Freeing a solution from extremely small particles [e.g. for optical rotatory dispersion (ORD) or circular dichroism (CD) measurements] requires filters with very small pore size. Commercially available (Millipore, Gelman, Nucleopore) filters other than cellulose or glass include nylon, Teflon, and polyvinyl chloride, and the pore diameter may be as small as 0.01 micron (see Table 6). Special containers are used to hold the filters, through which the solution is pressed by applying pressure, e.g. from a syringe. Some of these filters can be used to clear strong sulfuric acid solutions. 

Figure 6. Range of common particle sizes (diameter) over range of UF pore size.

SynChropak GPC supports were introduced in 1978 as the first commercial columns for high-performance liquid chromatography of proteins. SynChropak GPC columns were based on research developed by Fred Regnier and coworkers in 1976 (1,2). The first columns were only available in 10-yu,m particles with a 100-A pore diameter, but as silica technology advanced, the range of available pore diameters increased and 5-yu,m particle diameters became available. SynChropak GPC and CATSEC occasionally were prepared on larger particles on a custom basis, but generally these products have been intended for analytical applications. 

SynChropak size exclusion supports are composed of spherical uniformly porous silica that has been derivatized with a suitable layer. SynChropak GPC supports are available in six pore diameters ranging from 50 to 4000 A and particle diameters from 5 to 10 /zm. SynChropak CATSEC supports are available in four pore diameters. Table 10.1 details the physical characteristics of the product lines. 

The HdC calibration curves of different particle sizes, as shown in Fig. 22.12 (30), are similar to the calibration curves of different pore size columns the separation ranges of MW due to hydrodynamic chromatography depend on particle size. The larger the particle size, the higher the MW ranges. Stegeman et al. (30) proposed that a smooth calibration curve may be achieved by proper ratio of the particle diameter to the pore diameter. 

FIGURE 22.12 Theoretical HdC/SEC calibration graphs for different particle diameters. Pore diameter = 10 nm particle diameters dotted line, S /xm dashed line, 3 /xm solid line, I /xm. (Reprinted from J. Chromatogr., 550, 728, Copyright 1991, with permission from Elsevier Science.)... 

Figure 20 A typical scanning electron micrograph of the macroporous uniform poly(styrene-divinylbenzene) late> particles. Magnification 1200 x, (particle size = 16.0/rm average pore diameter = 200 nm).

A research group in Lehigh University has extensively studied the synthesis and characterization of uniform macroporous styrene-divinylbenzene copolymer particles [125,126]. In their studies, uniform porous polymer particles were prepared via seeded emulsion polymerization in which linear polymer (polystyrene seed) or a mixture of linear polymer and solvent were used as inert diluents [125]. The average pore diameter was on the order of 1000 A with pore volumes up to... 

The catalyst should be reduced and sulfided during the initial stages of operation before use. Other catalyst systems used in HDS are NiO/MoOs and NiOAVOs. Because mass transfer has a significant influence on the reaction rates, catalyst performance is significantly affected by the particle size and pore diameter. 

The pores of tire separating membrane are to be most uniformly distributed and of minimum size to avoid deposition of metallic particles and thus electronic bridging. One distinguishes between macroporous and microporous separators, the latter having to show pore diameters below I micron (/urn ), i.e., below one-thousandth of a millimeter. Thus the risk of metal particle deposition and subsequent shorting is quite low, since active materials in storage batteries usually have particle diameters of several microns. 

Microporous insulation materials consist mainly of highly dispersed silica with a particle size of only 5-30 nm. The highly dispersed silica powder is pressed to plates, which receive heat treatment up to 800 °C, after which the plates are self-supporting and possess a micropore structure with pore diameter of 0.1pm. The addition of opacifiers to the highly dispersed silica starting material reduces the loss of heat by radiation. The dates for such insulation boards are shown in Table 18. 

Some authors have suggested the use of fluorene polymers for this kind of chromatography. Fluorinated polymers have attracted attention due to their unique adsorption properties. Polytetrafluoroethylene (PTFE) is antiadhesive, thus adsorption of hydrophobic as well as hydrophilic molecules is low. Such adsorbents possess extremely low adsorption activity and nonspecific sorption towards many compounds [109 111]. Fluorene polymers as sorbents were first suggested by Hjerten [112] in 1978 and were tested by desalting and concentration of tRN A [113]. Recently Williams et al. [114] presented a new fluorocarbon sorbent (Poly F Column, Du Pont, USA) for reversed-phase HPLC of peptides and proteins. The sorbent has 20 pm in diameter particles (pore size 30 nm, specific surface area 5 m2/g) and withstands pressure of eluent up to 135 bar. There is no limitation of pH range, however, low specific area and capacity (1.1 mg tRNA/g) and relatively low limits of working pressure do not allow the use of this sorbent for preparative chromatography. 

The column used in the separation depicted in figure 1 was 25 cm long and 6.2 mm in diameter packed with silica gel having a mean pore diameter of 100 A and a particle diameter of 5 jum. Thus, the column would have an HETP of approximately 0.001 cm (twice the particle diameter). Consequently, a column 25 cm long would have an 25... 

Example 10.6 A commercial process for the dehydrogenation of ethylbenzene uses 3-mm spherical catalyst particles. The rate constant is 15s , and the diffusivity of ethylbenzene in steam is 4x 10 m /s under reaction conditions. Assume that the pore diameter is large enough that this bulk diffusivity applies. Determine a likely lower bound for the isothermal effectiveness factor. 

The value for is conservatively interpreted as the particle diameter. This is a perfectly feasible size for use in a laboratory reactor. Due to pressure-drop limitations, it is too small for a full-scale packed bed. However, even smaller catalyst particles, dp 50 yum, are used in fluidized-bed reactors. For such small particles we can assume rj=l, even for the 3-nm pore diameters found in some cracking catalysts. 

The mechanical incorporation of active nanoparticles into the silica pore structure is very promising for the general synthesis of supported catalysts, although particles larger than the support s pore diameter cannot be incorporated into the mesopore structure. To overcome this limitation, pre-defined Pt particles were mixed with silica precursors, and the mesoporous silica structures were grown by a hydrothermal method. This process is referred to as nanoparticle encapsulation (NE) (Scheme 2) [16] because the resulting silica encapsulates metal nanoparticles inside the pore structure. 

Over An deposited on 3-D mesoporous Ti-Si02 with pore diameter of 9nm, one of the best results was obtained. At an SV of 4000 h/mL/g-cat., propylene conversion above 8%, PO selectivity of 91% giving a steady STY of 80 g PO/h/kg-cat. [84]. The surfaces of 3-D mesoporous Ti-Si02 were trimethylsilylated for rendering hydro-phobicity, which enables higher temperature operation of reaction [86]. As a solid phase promoter, alkaline or alkaline earth metal chlorides are efficient, however, chloride anions markedly enhance the coagulation of An particles in a short period [87]. Finally, Ba(N03)2 was selected as the best promoter which might kill the steady acid sites as BaO (after calcination) on the catalyst surfaces [84,88]. 

However, production engineers have been reluctant to use particle bridging because of the possibility of particle transport into the formation, resulting in formation damage and/or costly and often ineffective stimulation treatments. A particle bridging fluid has been developed that quickly and effectively controls fluid loss in a wide range of permeabilities and pore diameters [916]. 

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