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Department of Chemical and Environmental Engineering, National University of Singapore, 10 Kent Ridge Crescent,Singapore, 119260; E-Maih engp8896@nus.edu.sg

Key Words

Column liquid chromatography Heterogeneous packing Computational fluid dynamics

Summary

Based on the assumption of a radial parabolic porosity distribution across a chromatographic column and an ideal distribution and collection system for the column, a theoretical study of the effect of heterogeneous packing on the behavior of chromatographywas conducted using Computational Fluid Dynamics (CFD) simulation. This study examined the development of the velocity distribution in columns with different porosity variations and different diameters, visualized the effect of velocity distribution on concentration profiles inside the column and the elutecl pulses at the exit and finally the column efficiency Therefore, this study is helpful to enhance the understanding to the effect of packing quality on chromatography The final result suggests that packing heterogeneity in current widely used chromatographic columns might seriously impair the separation efficiency of the colu mns.

Introduction

In most chromatography theories, it is assumed that the packing is homogeneous, which results in a plug flow in the column. However, practically it is hard to achieve a homogeneous packing and a plug flow due to the complexity of packing materials and packing techniques. There have been a lot of findings that chromatographic columns are not radially homogeneous [1 8]. Baur et al. [3 4] and Farkas et al. [5] observed that in a slurrypacked column, the mobile phase velocity near the column wall was about 2 to 8% lower than that at center. The study of Original 0009-5893/00/02 679- 07 $ 03.00/0

Sarker et al. [9] illustrated the lack of homogeneity of the stress distribution during the dynamic axial compression. Guiochon and Farkas et al. [10] reviewed the effects of different packing methods. They found that different packing methods results in columns that have quite different mechanical properties. The packing close to the inner column wall is denser than but not as well organized as that at the center of the column. The effect of radial heterogeneity on the performance of HPLC appears to be more prominent in preparative scale columns than analytical scale columns. The large size of the column enhances the posChromatographia 21102, 56, December (No. 11/12)

sibility of large-scale fluctuations of the packing density and local velocity of the mobile phase, resulting in poor column efficiency and abnormal band profiles [11]. However, with the development of biochemical engineering and pharmaceutical industry, large scale HPLCs with high efficiency become more and more important. The understanding of the effect of heterogeneous packing is a key to the improvement of large scale HPLC. Using on-column fluorescence-detection, Farkas et al. found that at the exit of analytical HPLC columns, the mobile phase velocity profiles are nearly flat in the column center and falls rather rapidly towards the wall [12]; however, at the exit of an axial compression column (5 cm ID), the radial distributions of the velocity and the analyte concentration suggest a nearly parabolic distribution of the packing density [13]. The radial velocity distribution shown in Figure 4 in their work [13] is strongly curved and roughly parabolic. The velocity close to the column wall is 7% lower than that along its axis. Based on the cylindrical parabolic distribution of radial velocity, Yun and Guiochon [11], Miyabe and Guiochon[14] theoretically studied the effect of heterogeneity on the performance of HPLC. Both studies confirmed the degradation of separation performance when the ratio of the mobilephase velocities at the column center and at the wall differed by a few percent. The above studies of column heterogeneity were mainly based on the velocity distribution. However, a more direct observation should be based on the packing. Yun and Guiochon [15] visualized the het679

where "i" refers to coordinate r (the radial direction) or coordinate x (the axial direction), vi the superficial velocity, and c~ the permeability of porous medium, c~ is calculated by d 2 . c3 c~ 1 5 0 . (1 C) 2

(2)

Figure

erogeneity of columns using alternating layers of colorful packing materials. After packing they extruded the packing cake and cut it into halves to obtain the axial cross-section view. With different packing methods such as wet-dry packing and slurry packing, the colorful layers are all cylindrical parabolic and the difference is only of the extent of curvature. Lode et al.'s work [16] confirmed this result and excluded the suspicion that the extrusion might result in some disturbance of the shape of the colorful layer. Using a spin echo imaging method Lode et al. found a higher void fraction in the central region of the column. The measured column porosity vs. radial position is also roughly parabolic, as shown in Figurel 1 in their work [16]. Although there are a lot of experimental observations on radial distributions of porosity and velocity, the mechanism of how porosity distribution affects velocity distribution and how velocity distribution degrades the column efficiency is still to be revealed. Computational Fluid Dynamics (CFD) should be a promising tool for the understanding of the mechanism. Generally, CFD can provide detailed information on mass, momentum and energy distributions in flow geometry of interest (for example, chromatographic column in this study). It has long been known as an aid in the engineering of fluid flow systems. However, its potential was only realized by chemical engineers in the last decades evidenced by a number of systematical reviews on its application in chemical engineering by Colenbrander [17], Harris et al. [18], and Kuipers et al. [19]. The target of this work was to theoretically study the effect of packing heterogeneity on column efficiency using CFD simulation.

Experimental Assumptions

The assumptions in the simulations were: The tracer was not retainable and thus no adsorption occurred. All processes occurring in the column were isothermal. So no energy balance was involved in the simulation. Physical parameters including density, viscosity and axial dispersion coefficient were independent of species concentration. The radial distribution of bed porosity was parabolic and the axial distribution was homogeneous. In practice, the systematic variations in the axial direction are quite possible but they are significantly less harmful than systematic radial fluctuations [12]. The distributions of physical properties, such as velocity and concentration were symmetric with the geometry. Therefore, the geometry used in the simulation represents a half of the column. The distribution and collection system at both ends of the column was ideal so that plug flow was achieved at the beginning of the column. This assumption excludes the effect of column ends on the performance of chromatography so that the effect of packing could be observed more clearly.

where c is porosity and dp the diameter of packing particles [20]. Based on the findings aforementioned [15 16], the radial distribution of porosity of the column studied in this work was assumed to be parabolic, defined by = a. +b (3)

where a and b are constant coefficients and R is the column radius. The average porosity over the crosssection of the column was defined by

R

f 27ere(r)dr

T= j 0 7rR2

(4)

and g was assumed to be 0.4. Substituting Eq. (3) into Eq. (4) yields a b ~ = 0.4 (5)

The porosity variation was defined as the percentage of the difference between the maximum and the minimum porosity over the average porosity: Porosity variation - cmax Cmi 100% n (At)max

100%

(6)

The maximum porosity locates at the column center where r is zero and the minimum porosity locates at the column wall where r equals the column radius R. Therefore

Cmax = b

(7) (8)

Cmi = a + b n

Theory

The CFD software FLUENT4.5 was used in the simulation. Generally, the flow pattern in a chromatographic column, which is usually packed with porous materials, is laminar flow. Laminar flow through porous medium is generally described by Darcy's law [20]

--

With a given porosity variation, a and b can be easily calculated by Eqs (5) (8). Then, by Eq. (3), the porosity at any radial position can be determined. The concentration balance used in FLUENT 4.5 for the species concentration is

Oc U Oc V Oc 02C 1 0

(9)

OX i

-vi

Oz

(1)

where u and v are the axial and radial superficial velocities, respectively. Original

680

Chromatographia 2002,

11/12)

Geometry

The geometry in the simulation is plotted in Figure 1. The shaded side represents the column wall and the dashed line at the bottom represents the axis of the column. With the assumption of an ideal distribution and collection system, the inlet and the outlet are just the beginning and the end of the column, respectively. Because FLUENT does not allow continuous distribution of porosity to be achieved, the piecewise distribution model was used. Therefore, in simulation the column was divided into N segments. In each segment the packing is homogeneous, but different segments have different porosities. The distribution of porosities follows the parabolic distribution defined by Eqs. (3), (4) and (6). The dimensions of the simulated columns in this study are 5 cm ID x 38 cm, 10 cm ID x 38 cm and 20 cm ID x 38cm. For columns with 5cm ID and 10 cm ID, segment number N (as shown in Figure 1) is 25; for column with 20 cm ID, N is 32. In FLUENT4.5, the geometry of simulation is divided into cells by structured grids and finite volume method is used for discretization [20]. Generally, an increase in grid density results in an increase in both calculation time and calculation accuracy. However, above a certain level of grid density there is a rapid increase in calculation time with little improvement in calculation accuracy. Based on preliminary investigation, a compromising grid density of 10 cells/cm was selected for the simulation.

After the momentum simulation reached a steady state, the dynamic simulation of component balance was switched on. A pulse input was applied as follows: at the inlet, the concentration was set as 1 for one second; after 1 second, the inlet concentration was changed to zero. At the end of the column, the eluted pulse of each segment was recorded and the average eluted pulse of the whole column was therefore obtained. The results were analyzed by the moments analysis method [21]: oo

p

Simulations with porosity variations 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 7.5%, 10.0%, 12.5% and 15% were carried out. The results and the corresponding discussion were elaborated in the following sections.

Velocity Fields

Initially, with an assumption of an ideal distribution system for the column, a plug flow will be achieved at the inlet. After entering the heterogeneous medium, the flow will be redistributed to reach a new steady state. The fluid in Figure 2 flows from left to right. With parabolic porosity distribution, the porosity and the permeability in the column center are larger than those near the column wall; hence the fluid meets less resistance at the column center. This results in more fluid molecules forcing their way towards the column center while flowing downstream. This phenomenon continues until the mass distribution of the fluid adapts to the porosity distribution in the column. The development of velocity distributions in columns with different sizes and porosity variations was investigated. The radial distributions of velocity in columns (10 cm ID) with different porosity variations are plotted in Figures 3 (a) (c). It can be seen that the radial distribution of velocity is parabolic and its curvature increases along the axial direction. The rate 681

Parameters

In these simulations, the following parameters were assumed: fluid density p viscosity zl particle diameter dp inlet velocity vinlet 786kg/m 3 7.4 10 4 kg/(m.s) 50 pm 1.0 10 3m/s

Jo ctdt (10) f o ctdt The first moment represents the retention time. Retention time is the time which elapses between the injection and the elution of a solute. The First Moment: #

The porosity variation ranged from 0.5% to 15.0%. By Eqns (3) (8), the porosity in each segment was obtained. By Eq. (2) the permeability of each segment was calculated and applied in the momentum simulation.

f o c(t #)2dt f o cdt (11) The efficiency of a column is a statistical calculation of the standard deviation of the peak in unit time. It is measured in the number of theoretical units, NTU; or the Height Equivalent to a Theoretical Plate (HETP), which are defined as follows: #2 NTU = ~(12) L HETP - NTU (13)

where L is the length of the column. A higher N T U or a lower HETP indicates better column efficiency.

Original

Figure 3. Radial velocity distributions at different axial positions in column with 10 cm ID: (a) porosity variation of 0.5%; (b) porosity variation of 5%; (c) porosity variation of 10%.

Figure 4. The radial distributions of velocity at different axial positions in columns with porosity variation 5%: (a) column 5 cm ID; (b) column with 20 cm ID.

of increase of the curvature slows down gradually, and at last the radial distribution of velocity reaches a steady state. F o r convenience, in this work the distance from the beginning of the column to

where the radial distribution of velocity reaches the steady state is called the development length. Figure 3 illustrates that for the column with 10 cm ID, the development length is 0.0885 m no matter whatChromatographia 2002, 56, December (No. 11/12)

ever the porosity variation is. Therefore, the development length is independent of porosity variation. To further examine the development of the radial distribution of velocity, similar

682

Original

Figure 6. The change of velocity variation with porosity variation in columns of different sizes.

simulations were conducted with columns 5 cm and 20 cm in diameter. The simulated results are shown in Figures 4(a) and (b), respectively. By analyzing Figure 4 and Figure 3(b), it can be found that the development length depends on the column diameter. The development length is 0.0485m for column with 5cm ID, 0.0885m for column 10cm ID and 0.1585 m for column 20 cm ID. The correlation between the development length and column radius is roughly linear, as shown in Figure 5. After the radial distribution of velocity has reached the steady state, the difference between the maximum velocity (U~x) and the minimum velocity (Umin) at a certain axial position is fixed. Here we define the velocity variation as

The concentration profile in the column is affected by its packing condition. Figure 7 shows the simulation results of concentration profiles in columns under different conditions, namely, homogeneous packing and heterogeneous packing with different porosity variations ranged from 0.5% to 10%. Due to the axial dispersion in the column, in all cases, the concentration profile become wider and wider in the axial direction (Figure 7 (a) (d)). In a homogeneously packed column the concentration profile is a straight line (Figure 7 (a)). In contrast, except for the inlet, the concentration profile in a heterogeneously packed column appears to be parabolic, even at a porosity variation of 0.5% (Figure 7 (b) (d)). At the inlet of a heterogeneously packed column, as aforementioned, a plug flow pattern was assumed, which results in a straight concentration profile. The curvature of the concentration profiles is due to the fact that the tracer at the center always flows faster than that near the wall. For the same reason, in each heterogeneously packed column, the curvature of the concentration profiles increases along the axial direction (Figure 7 (b) (d)). Also, it can be observed that the curvature increases with increasing porosity variation (Figure 7 (b) (d)).

Velocity variation

where Uhom refers to the velocity in a homogeneous column with the same size as the studied heterogeneous column. Therefore it is equal to the velocity at the inlet. The velocity variation is different for columns with different porosity variations, which can be observed in Figure 3. To examine the correlation between velocity variation and porosity variation, more simulations were carried out. As shown in Figure 6, velocity variation is proportional to porosity variation. In this work, a small change in porosity variation would result in a roughly four times change in velocity variation. Figure 6 also illustrates that such correlation is independent of the column diameter.

Eluted Pulses

The simulated results of a column with 10 cm ID were used to analyze the eluted pulses. The porosity variation changed from 0.5% to 15%. For each case, the segment eluted pulses and the average eluted Chromatographia 2002, 56, December (No. 11/12)

pulse were recorded at the outlet. These pulses were analyzed by moments analysis method described in the section "Simulation procedures and the analysis method". The segment eluted pulses of two cases with porosity variations of 0.5% and 5% are plotted in Figure 8 (a) and (b), respectively. It can be observed that the segment eluted pulses are separated farther and farther from each other with the increase in porosity variation. With porosity variation of 0.5%, the peaks are very close to each other, which means tracers in all segments are eluted out of the column roughly at the same time. While the porosity variation increases to 5%, the tracer in segment 1 near the column axis is eluted out first. The tracer in segment 25 begins to leave the column after most tracer in segment 1 has been eluted out. The effect of porosity variation on retention time difference between segments is shown in Figure 9. Similarly, retention time difference between segments increases with porosity variation. With a given porosity variation, the retention time of the segments near the axis is shorter than those near the wall. However, for a given segment, the variation of its retention time with the increase in porosity variation depends on its radial position. Retention time increases for segments near the wall but decreases for segments near the center. Such changes of segment retention times are controlled by the velocity distribution. The larger the porosity variation, the larger the velocity at the column center and the smaller the velocity near the wall, as shown in Figure 3 (a) (c). This results in an enlargement in the range of segment retention time distribution. It is also observed that from the axis to the wall, the segment eluted pulse peak de-

Original

683

Figure 7. The concentration profiles in column (10 cm ID). (a) Homogeneouslypacked column, time 1s, 40s, 80s, 120s, 150s. (b) Porosity variation 0.5%, time ls, 40s, 80s, 120s, 150s. (c) Porosity variation 5.0%, time ls, 40s, 80s, 120s. (d) Porosity variation 10%, ls, 40s, 80s, 150s.

Figure 8. Segmenteluted pulses (a) porosity variation of 0.5%; (b) porosity variation of 5%. creases (Figure 8). The difference in peak heights is enlarged by the increase in porosity variation. The aforementioned enlarged difference between segment eluted pulses at larger porosity variations results in an enlarged deviation of average eluted pulse from that of the homogeneous column. As shown in Figure 10, when the porosity variation is 0.5%, which deviates slightly from homogeneity, the average eluted pulse is almost identical to that of the homogeneous column. With the increase in porosity variation, the average eluted pulse peak becomes shorter and wider, denoting a larger deviation from the homogeneous case. When porosity variation reaches 5.0%, the average eluted pulse peak is no longer symmetric and appears to be flat-topped, indicating poor column performance.

Column Efficiency

In this work, relative HETP refers to the ratio of HETP of the column studied under certain conditions to that of a homogeneous column with the same size. The change in relative HETP with porosity variations is illustrated in Figurel 1. It is observable that the relative HETP is independent of the column diameter but positively correlated to porosity variation. According to the statement in Farkas and coworkers' work [5], the velocity variation from the center to the wall is 2 - 8%. By the correlation between velocity variation and porosity variation demonstrated in this work, as shown in Figure 6, it could be deduced that the related porosity variation could be in the range of 0.5 - 2.0%. Hence, by the correlation between relative HETP and porosity variation demonstrated in Figure 11, the increase in the relative HETP should be in the range of 5.0 ~ 60.0%! It then can be concluded that the negative effect of heterogeneous packChromatographia 2002, 56, December (No. 11/12)

ing is not negligible and the improvement of packing quality is very important for further improvement of chromatographic technology. This provides an additional explanation why some chromatographic columns failed to perform as effectively as before scaled up. Since the change of the relative column efficiency with respect to porosity variation is independent of the column diameter, the poor separation performance of some large-scale chromatographic columns may be due to an enlarged heterogeneity and/or the poor distribution and collection system, both of which result from the enlarged complexity and difficulty in controlling it on a large scale.

Conclusions

The focus of this work was the effect of heterogeneous packing on the performance of chromatographic columns. This work is based on the assumptions of raOriginal

684

dially parabolic porosity distribution and an ideal distribution and collection system at both ends of the column. With parabolic porosity distributions, the radial distribution of velocity changes from a plug flow pattern at the inlet to a parabolic shaped flow pattern anywhere else. The curvature of the parabolic velocity distribution gradually increases along the column length until a steady state is reached. The development length is independent of porosity variation but positively correlated to the column diameter. In contrast, the change in velocity variation is independent of the column diameter but depends on the porosity variation. The parabolic velocity distribution results in parabolic concentration profiles inside the column. The curvature of the concentration profile steadily increases along the length of the column because the tracer molecules near the column center always run faster than those near the column wall. Simultaneously, the width of the tracer profiles increases due to axial dispersion. Segment performance differences increase with porosity variation, which corresponds to more curved concentration profiles within the column and shorter and wider eluted peaks recorded at the column exit, indicating lower column efficiency. The relative HETP increases with porosity variation, however, it is independent of the column diameter. Based on experimentally observed velocity variations across columns by former researchers, the increase in HETP of a heterogeneous column ranges 5% to 60%, suggesting improvement in the packing technique is needed for current widely used preparative chromatographic columns. Heterogeneous packing is one of the important factors causing poor performance of chromatographic columns. In practice, the inlet or outlet pipe connecting to a real chromatographic column (especially a preparative column) has a much smaller diameter than the column, which indicates that a plug flow at the beginning of a chromatographic column is actually impossible. Thereby, the distribution and collection system also affects the flow field in a chromatographic column, and hence the column efficiency, to a great extent. Further work is in progress to elucidate the effect of the distribution and collection system on both homogeneous and heterogeneous columns.

Figure 9. The variation of segment retention time with porosity variation under parabolic porosity

distribution.

Figure 10. The average eluted pulses with different porosity variations.

Original Chromatographia 2002, 56, December (No. 11/12)

68 5

References

[1] Knox, J.H.; Laird, G.R.; Raven, P.A.J. Chromatogr. 1976, 122, 129 145. [2] Eon, C.H.J. Chromatogr. 1978, 149, 29 42. [3] Baur, J.E.; Kristensen, E.W.; Wightman, R.M. Anal. Chem. 1988, 60, 2334 2338. [4] Baur, J.E.; Wightman, R.M.J. Chromatogr. 1989,482, 65 73. [5] Farkas, T.; Chambers, J.Q.; Guiochon, G. J. Chromatogr. A 1994, 679, 231 245. [6] Fernandez, E.J.; Grotegut, C.A.; Braun, G.W.; Kirshner, K.J.; Staudaher, J.R.; Dickson, M.L.; Fernandez, V.L. Phys. Fluids 1995, 7, 468 477. [7] Bayer, E.; Mfiller, W.; Ilg, M.; Albert, K. Angew. Chem. int. Ed. 1989, 28, 1029 1032.

[8] Tallarek, U.; Baumeister, E.; Albert, K.; Bayer, E.; Guiochon, G. J. Chromatogr. A 1995, 696, 1 18. [9] Sarker, M.; Katti, A.M.; Guiochon, G. J. Chromatogr. A 1996, 719, 275 289. [10] Guiochon, G.; Farkas, T.; Hong, G.-S.; Koh, J.-H.; Sarker, M.; Stanley, B.J.; Yun, T. J. Chromatogr. A 1997, 762, 83 88. [11] Yun, T.; Guiochon, G. J. Chromatogr. A 1996, 734, 97 103. [12] Farkas, T.; Sepaniak, M.J.; Guiochon, G. J. Chromagr. A 1996, 740, 169 181. [13] Farkas, T.; Sepaniak, M.J.; Guiochon, G. A1ChEJ. 1997,43, 1964 1974. [14] Miyabe, K.; Guiochon, G. Z Chromatogr. A 1999,830, 263 274. [15] Yun, T.; Guichon, G. Z Chromatogr. A 1997, 760, 17 34.

[16] Lode, F.G.; Rosenfeld, A.; Yuan, Q.S.; Root, T.W.; Lightfoot, E.N.J. Chromatogr. A 1998, 796, 3 14. [17] Colenbrander, G.W. Appl. Sci. Res. 1991, 48,211 245. [18] Harris, C.K.; Roekaerts, D.; Rosendal, F.J.J.; Buitendijk, F.G.J.; Daskopoulos, Ph.; Vreenegoor, A.J.N; Wang, H. Chem. Eng. Sci. 1996,51, 1569 1594. [19] Kuipers, J.A.M.; van Swaaij, W.P.M. Rev. Chem. Eng. 1997, 13, 1 118. [20] User's Guide of FLUENT 4.5, FLUENT Inc. 1992. [21] Ruthven, D.M. Principles of Adsorption and Adsorption processes. John Wiley & Sons, Inc., New York, 1984. Received: Ju126, 2002 Accepted: Sep 4, 2002

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