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Tallarek - Et - Al-2002-Phenomenological Approach - Marburg Germany PDF
Tallarek - Et - Al-2002-Phenomenological Approach - Marburg Germany PDF
Tallarek - Et - Al-2002-Phenomenological Approach - Marburg Germany PDF
Due to the complex, often sponge-like structure of monolithic adsorbents it is difficult to define appropriate constituent units
that characterize the hydrodynamics of the material, or to determine relevant shape and size distribution factors comparable to
those for spherical particles in (particulate) fixed beds. Based on a phenomenological analysis of the friction factor (Reynolds
number relation and the longitudinal dispersivity ± Peclet number dependence for random sphere packings) we derive
characteristic lengths (i.e., equivalent particle dimensions) for a monolith with regard to its hydraulic permeability and
dispersion originating in stagnant zones. Equivalence to the hydrodynamic behavior in ªreferenceº sphere packings is
established by dimensionless scaling of the respective data for the monolithic structure. This phenomenological approach, which
is simply based on liquid flow and stagnation in a porous medium, can successfully relate hydrodynamic properties of the
monolith to that of particulate beds.
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where DP/L is pressure drop over length L of the bed (in the
macroscopic flow direction), r is the density of the liquid, and
qi and wi are parameters for particle shape and size
distribution. Eq. (1) may be much simplified when the
deviation from a uniform spherical shape and differences in
particle size distribution, surface roughness, interparticle
porosity (einter) and bed structure for different sphere
packings may be considered insignificant. Eq. (1) then reduces
to a simple unique relation between friction factor F and Re
[16,17].
Figure 2. Morphology of the silica-based monolith. a) SEM picture showing the
macroporous interskeleton pore space with dmacro = 1.9 lm, and b) the ±
mesoporous skeleton, dmeso = 25 nm. c) Discrete bimodal pore size distribution. 1) List of symbols at the end of the paper.
Table 1. Characteristic dimensions and parameters of the porous media. dcol is the column diameter and L denotes the bed length. etotal, einter and eintra are the total,
interparticle (interskeleton) and intraparticle (intraskeleton) porosities of the porous medium, respectively [12]. Aspec is the specific and Arel the volume-weighted
surface area.
Fixed bed L [mm] dcol [mm] dp [lm] etotal einter eintra Aspec [m2 g±1] Arel [m2 cm±3] Lflow [lm] Lstag [lm]
Spheres (nonporous) 53 4.6 3.0 0.36 0.36 ± 0.6 0.7 3.0 ±
Spheres (porous) 55 2.0 6.4 0.75 0.37 0.60 76 65 6.4 3.2
Monolithic structure 100 4.6 ± 0.92 0.72 0.70 147 39 9.5 1.0
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Fig. 3 demonstrates, as then expected, a superposition of which, in contrast to Eq. (1), includes features of both the
these data for different sphere packings having similar einter, qi convection-dominated interparticle and diffusion-limited
and wi. The linear dependence of F on Re represents the intraparticle pore space. Eq. (2) can also be simplified for
validity of Darcy's law. An equivalent permeability length packed beds with comparable einter, qi, wi and structure,
(Lflow) for the monolithic structure, i.e., a particle diameter dp resulting in a relationship between the dispersivity D and Pe
for a fictitious bed (with similar einter, qi, wi, and structure as almost as simple as that between F and Re. The remaining
the other two sphere packings) is obtained by dimensionless difficulty in Eq. (2) is associated with an evaluation of the
scaling of the pressure drop ± flow rate dependence for analyte diffusivity in stagnant zones (Dstag), as in general it
monoliths to the F ± Re relation characterizing particulate depends on the morphology of the intraparticle pore space.
beds (Fig. 3). It is achieved by adjusting dp which gives Lflow = However, when Dstag is similar the dispersion data for
9.5 lm in the present case. The fact that the data for porous different particulate beds and monoliths are expected to
and nonporous sphere packings coincide by means of their collapse on a unique curve by means of the characteristic
mean dp shows that the intraparticle pore network of these dimension Lstag. This is demonstrated by the data in Tab. 2 and
porous particles does not contribute measurably to macro- Fig. 4 which show Dstag is very similar for the porous particles
scopic flow. The actual macro-to-mesopore diameter ratio in and monolith used in this work. For completely porous
the sphere packing (and monolith) is of the order of 100, thus, spheres Lstag = rp is easily measured (cf. Fig. 1), and has been
hydraulic permeability of the intraparticle (and intraskeleton) used to calculate Pe in Fig. 4.
mesopore space is some 104 times lower than that of the As with the permeability data (Fig. 3), the next step consists
interparticle (and interskeleton) macroporous network, and of dimensionless scaling, this time of the monoliths dispersion
the assumption that the former constitutes a stagnant zone data to those obtained with the fixed bed of porous spheres,
seems to be justified. giving Lstag = 1.0 lm (Fig. 4). The equivalence in this case
states that dispersion in the monolith associated with liquid
holdup in the intraskeleton pore space resembles the
contribution from stagnant zones (characterized by the same
Dstag) in a bed of spherical particles with porous layer of
thickness Lstag. It is important to note that, if liquid holdup
exists in a monolith and dominates dispersion, nonporous
spheres are not appropriate for evaluating an equivalence
based on this particular (nonmechanical) contribution.
Figure 3. Friction factor vs. Reynolds number for the liquid in beds of
(non)porous spheres, with dp as Lflow in Re (Fig. 1). Dimensionless scaling for
the monolith gives Lflow = 9.5 lm. Re = 0.1 corresponds to a pressure drop DP
over the monolith (L = 100 mm) of about 15 MPa.
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Table 2. Physical properties of the analytes. RG is the radius of gyration and Dstag denotes the effective diffusion coefficient of analyte molecules in the (intraparticle
or intraskeleton) stagnant zone. Dstag = eintraKpDm/sintra where sintra = eintra + 1.5 (1 ± eintra) is the tortuosity factor [18] and Kp characterizes hindered pore diffusion
depending on the molecule size [19].
cally-structured pore network into distinct particle dimen- Dstag [m2 s±1] effective diffusion coefficient in
sions of what is most conventionally understood by a stagnant zone, Dstag = eintraKpDm/sintra
ªrandom-closeº sphere packing. The actual ratio of equivalent usf [m s±1] superficial mobile phase velocity,
lengths, R hp = Lflow/Lstag, may be used as a parameter usf = Fv/Acol
characterizing the hydrodynamic performance (hp) of a uav [m s±1] average analyte velocity through the
monolith. While this material provides relatively large flow- bed, uav = usf/etotal
through pores (Lflow = 9.5 lm), it only needs a comparatively Fv [ml min±1] volumetric flow rate
short diffusion length (Lstag = 1.0 lm) to combine the high Re [±] Reynolds number
permeability with a large surface area. With regard to R hp, the Pe [±] Peclet number
monolithic column resembles a fixed bed of (solid core-porous dp [m] mean diameter of spherical particles
shell) spheres with dp = Lflow and a porous layer of thickness Kp [±] hindrance factor concerning pore-level
Lstag (cf. Fig. 1). Thus, the volume-weighted surface area for a diffusion
monolith can much larger than for a bed of core-shell spheres F [±] friction factor
with the same R hp, and may be the origin of the superior L stag [m] characteristic length for liquid holdup
performance displayed by the monolith in many applications. in porous medium
Vice versa, completely porous particles provide a higher Lflow [m] characteristic length for hydraulic
surface area than the core-shell particles, which is still of the permeability
same order as that of the monolith, but in this case R hp = 2 qi [±] parameter(s) of particle size
(while R hp » 10 for the monolith). Thus, due to the high distribution
porosity (etotal > 0.9) and its unique, rigid structure that can R hp [±] hydrodynamic performance factor,
withstand high pressure, this type of monolith offers sub- R hp = Lflow/Lstag
stantial adsorption capacity (see Aspec and Arel in Table 1) for Vcol [m3] column volume
fast and efficient liquid phase separations. Vinter [m3] interparticle (interskeleton) pore
volume
Vintra [m3] intraparticle (intraskeleton) pore
volume
Acknowledgements Vsolid [m3] volume of particle (skeleton) solid
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