Separation technique Ultrafiltration

Ultrafiltration of micellar solutions combines the high permeate flows commonly found in ultrafiltration systems with the possibility of removing molecules independent of their size, since micelles can specifically solubilize or bind low molecular weight components. Characteristics of this separation technique, known as micellar-enhanced ultrafiltration (MEUF), are that micelles bind specific compounds and subsequent ultrafiltration separates the surrounding aqueous phase from the micelles [70]. The pore size of the UF membrane must be chosen such, that the micelles are retained but the unbound components can pass the membrane freely. Alternatively, proteins such as BSA have been used in stead of micelles to obtain similar enan-tioselective aggregates [71]. 

Until this point, the sample preparation techniques under discussion have relied upon differences in polarity to separate the analyte and the sample matrix in contrast, ultraflltration and on-line dialysis rely upon differences in molecular size between the analyte and matrix components to effect a separation. In ultrafiltration, a centrifugal force is applied across a membrane filter which has a molecular weight cut-off intended to isolate the analyte from larger matrix components. Furusawa incorporated an ultrafiltration step into his separation of sulfadimethoxine from chicken tissue extracts. Some cleanup of the sample extract may be necessary prior to ultrafiltration, or the ultrafiltration membranes can become clogged and ineffective. Also, one must ensure that the choice of membrane filter for ultrafiltration is appropriate in terms of both the molecular weight cut-off and compatibility with the extraction solvent used. 

Molecules that vary significantly in their size can be separated by ultrafiltration or dialysis, while molecules that are only slightly different in size can often be separated by gel permeation chromatography. Ultracentrifugal techniques, while apparently separating on the basis of size, are strictly speaking more influenced by the mass and density of the molecule and to a lesser extent by its shape. 

For a detailed description of the separation processes that may take place at the sensing microzone, the foundation of which is closely related to non-chromatographic continuous separation techniques based on mass transfer across a gas-liquid (gas diffusion), liquid-liquid (dialysis, ultrafiltration) or liquid-solid interface (sorption), interested readers are referred to specialized monographs e.g. [3]). 

Figure 6.10 Effect of solute type and concentration on flux through the same type of ultrafiltration membrane operated under the same conditions [15]. Reproduced from M.C. Porter, Membrane Filtration, in Handbook of Separation Techniques for Chemical Engineers, P.A. Schweitzer (ed.), p. 2.39, Copyright 1979, with permission of McGraw-Hill, New York, NY...

Figure 6.24 Ultrafiltration flux in apple juice clarification as a function of the volumetric feed-to-residue concentration factor. Tubular polysulfone membranes at 55 °C [27]. Reprinted from R.G. Blanck and W. Eykamp, Fruit Juice Ultrafiltration, in Recent Advances in Separation Techniques-III, N.N. Li (ed.), AIChE Symposium Series Number 250, 82 (1986). Reproduced by permission of the American Institute of Chemical Engineers. Copyright 1986 AIChE. All rights reserved...

Now the major application of dialysis is the artificial kidney and, as described in Chapter 12, more than 100 million of these devices are used annually. Apart from this one important application, dialysis has essentially been abandoned as a separation technique, because it relies on diffusion, which is inherently unselec-tive and slow, to achieve a separation. Thus, most potential dialysis separations are better handled by ultrafiltration or electrodialysis, in both of which an outside force and more selective membranes provide better, faster separations. The only three exceptions—Donnan dialysis, diffusion dialysis and piezodialysis—are described in the following sections. 

Because the chapter is about DOM, detailed information about the role of colloids and the analytical techniques are given elsewhere (e.g., Buffle and Leppard, 1995 Kretzschmar et al., 1999 Frimmel et al., 2007). Different separation techniques, like ultrafiltration, size exclusion chromatography, and flow field-flow fractionation can be coupled with UV-vis absorption and ICP-MS to show the interaction of metals and colloids. Elements like Ni, Cu, Cr, and Co are associated mainly with smaller-size DOM fractions whereas Al, Fe, lanthanides, Sn, and Th are associated with larger-size DOM fractions (Bolea et al., 2006). The laser-induced breakdown detection (LIBD) is a new, sensitive method for the quantification of aquatic colloids of lower-range nanometer size in very low concentration, which cannot be... 

Techniques can be classified into two main categories those that detect total metal concentrations and those that detect some operationally defined fraction of the total. Methods which detect total concentrations such as inductively coupled plasma spectrometry, neutron activation analysis, atomic absorption spectrometry and atomic emission spectrometry have no inherent speciation capabilities and must be combined with some other separation technique(s) to allow different species to be detected (approach A in Fig. 8.2). Such separation methods normally fractionate a sample on the basis of size, e.g. filtration/ultrafiltration, gel filtration, or a combination of size and charge, e.g. dialysis, ion exchange and solvent extraction (De Vitre et al., 1987 Badey, 1989b Berggren, 1989 1990 Buffle et al., 1992). In all instances the complexes studied must be relatively inert so that their concentrations are not appreciably modified during the fractionation procedure. 

Membrane separation techniques, which are used mainly in industrial processes, include dialysis, electrodialysis, reverse osmosis, ultrafiltration,... 

The word flow implies fluid moving through (or across) a rigid framework or conduit (a container, tube, or packed bed) and not being carried with it as in the case of mechanical transfer. Flow is an integral part of many separation techniques, including chromatography, field-flow fractionation, ultrafiltration, and elutriation. The flow process is not itself selective, but it enables one to multiply by many times the benefits of separations attempted without flow. This point is explained in Chapter 7. 

Commonly encountered separation techniques include ultrafiltration, dialysis, precipitation and sedimentation. 

The majority of reports have used electrospray ionization mass spectroscopy (ESI-MS) as an analytical detection method because of its sensitivity and the soft namre of its ionization procedure, which generally only leads to the detection of the molecular ions of the positive library members. Many separation techniques have been coupled to ESI-MS, including affinity chromatography (49), size exclusion chromatography (50, 51), gel filtration (52), affinity capillary electrophoresis (53-58), capillary isoelectric focusing (59), immunoaffinity ultrafiltration (60), and immunoaffinity extraction (61). ESI-MS has also been used alone (62) to screen a small carbohydrate library. Other examples reported alternative analytical techniques such as MALDI MS, either alone (63, 64) or in conjunction with size exclusion methods (65), or HPLC coupled with immunoaffinity deletion (66). 

Nanofiltration is a rapidly advancing membrane separation technique for concentration/separation of important fine chemicals as well as treatment of effluents in pharmaceutical industry due to its unique charge-based repulsion property [5]. Nanofiltration, also termed as loose reverse osmosis, is capable of solving a wide variety of separation problems associated with bulk drug industry. It is a pressure-driven membrane process and indicates a specific domain of membrane technology that hes between ultrafiltration and reverse osmosis [6]. The process uses a membrane that selectively restricts flow of solutes while permitting flow of the solvent. It is closely related to reverse osmosis and is called loose RO as the pores in NF are more open than those in RO and compounds with molecular weight 150-300 Da are rejected. NF is a kinetic process and not equilibrium driven [7]. 

Hollow-fiber ultrafiltration can be a very usefiil tool in obtaining size-fractionated samples for chemical and physical analyses of humic and fulvic acids in surface and groundwaters. The technique is very reproducible because it is strictly a physical separation, it minimizes the potential artifacts associated with the more classical chemical separation techniques. The separation method assumes a spherical structure for the cutoffs and therefore is an empirical approach. Nevertheless, hollow fibers can be used much as 0.45 im filters are used to separate particulate versus dissolved material with a great deal of success. 

Most problems with this procedure have involved tracer impurities and the separation of bound and free labeled fractions. Several separation techniques have been used, including equilibrium dialysis, membrane ultrafiltration, and steady-state gel filtration. Their deficiencies include a requirement for a large sample volume, the need for complicated correction of sample volume changes that occur during the separation, and difficulties of collecting and measuring radioactivity in numerous fractions of each sample. Equilibrium dialysis has been used most often in the past, but serious errors often arise from the sample dilution required by this method. Symmetrical dialysis of undiluted samples is reported to be less susceptible to tracer contamination and dilution effects. Ultrafiltration also appears to overcome these problems and to obviate errors caused by dilution. 

Enrichment More sophisticated separation techniques such as solvent extraction, precipitation, adsorption, and ultrafiltration (UF) are commonly used to concentrate and partially purify the product. The purity of the product usually reaches 10-80% (w/v) at the end of these steps. 

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