Phase breakthrough

Acidic micro- and mesoporous materials, and in particular USY type zeolites, are widely used in petroleum refinery and petrochemical industry. Dealumination treatment of Y type zeolites referred to as ultrastabilisation is carried out to tune acidity, porosity and stability of these materials [1]. Dealumination by high temperature treatment in presence of steam creates a secondary mesoporous network inside individual zeolite crystals. In view of catalytic applications, it is essential to characterize those mesopores and to distinguish mesopores connected to the external surface of the zeolite crystal from mesopores present as cavities accessible via micropores only [2]. Externally accessible mesopores increase catalytic effectiveness by lifting diffusion limitation and facilitating desorption of reaction products [3], The aim of this paper is to characterize those mesopores by means of catalytic test reaction and liquid phase breakthrough experiments. 

Liquid-phase breakthrough experiments were also developed in order to characterize mesopores. The principle of the methodology relied on the analysis of the diffusion and adsorption of molecular probes with various molecular dimensions and adsorption strength. The relative proportion of occluded and accessible mesopores in the studied dealuminated Y zeolite could then be estimated. To allow this estimation, it is necessary to use molecular probes that can or cannot penetrate into the microporosity of the Y zeolite (see Figure 2). 

Combination of usual characterization techniques (N2 and Hg adsorption, TEM), catalytic test and liquid-phase breakthrough technique is a useful methodology to give complete information on micro- and mesoporous solids. 

Membrane reactors can be considered passive or active according to whether the membrane plays the role of a simple physical barrier that retains the free enzyme molecules solubilized in the aqueous phase, or it acts as an immobilization matrix binding physically or chemically the enzyme molecules. Polymer- and ceramic-based micro- and ultrafiltration membranes are used, and particular attention has to be paid to the chemical compatibility between the solvent and the polymeric membranes. Careful, fine control of the transmembrane pressure during operation is also required in order to avoid phase breakthrough, a task that may sometimes prove difficult to perform, particularly when surface active materials are present or formed during biotransformahon. Sihcone-based dense-phase membranes have also been evaluated in whole-cell processes [55, 56], but... 

As a result of tlie construction of the membrane module, the interface area for mass transfer per volume is very high compared to extraction towers and is not influenced by flow volumes. The flow volumes are only restricted by the phase breakthrough into the other phase caused by the pressure loss along the contactor. HTU values are lower compared to other extraction units therefore the membrane contactor has higher extraction efficiency. HTU values increase with higher loading of the membrane module. To reach a higher theoretical plate munber, comparable to extraction towers, more module units have to be set in series. 

Porous membrane modules were therefore effectively used in bioreactors as an alternative to direct two-liquid contact systems, as long as phase breakthrough was avoided. This required a careful control of the transmembrane pressure, particularly if surface-active material was produced during bioconversions [126,184, 187]. Fouling problems also developed in membrane-assisted multi-phase separation systems. This was observed by Conrad and Lee in the recovery of an aqueous bioconversion product from a broth containing 20% soybean oil by using ceramic membranes fouling was caused mainly by soluble proteins and surfactants [188]. 

Non-Micellar Mobile Phases. Figure 4.2A shows the low concentration part of the adsorption isotherm. From an experimental point of view, the breakthrough volume of mobile phase can be very large. The 1.9 pmol/m SDS amount adsorbed on the ODS phase with a 0.001 M SDS mobile phase corresponds to 0.0002 moles of SDS because the ODS surface area is 105 m /g (Table 4.1). This amount of SDS is contained in 200 mL of mobile phase (=breakthrough volume). It means the duration of the experiment at this point is at least 4 hours at 1 mL/min. 

The solution to this model for a deep bed indicates an increase in velocity of the fluid-phase concentration wave during breakthrough. This is most dramatic for the rectangular isotherm—the instant the bed becomes saturated, the fluid-phase profile Jumps in velocity from that of the adsorption transition to that of the fluid, and a near shocklike breakthrough curve is obseived [Coppola and LeVan, Chem. Eng. Sci.,36, 967(1981)]. 

Fig. 6. Breakthrough curves for aqueous acetone (10 mg 1" in feed) flowing through exnutshell granular active carbon, GAC, and PAN-based active carbon fibers, ACF, in a continuous flow reactor (see Fig. 5) at 10 ml min" and 293 K [64]. C/Cq is the outlet concentration relative to the feed concentration. Reprinted from Ind. Eng. Chem. Res., Volume 34, Lin, S. H. and Hsu, F. M., Liquid phase adsorption of organic compounds by granular activated carbon and activated carbon fibers, pp. 2110-2116, Copyright 1995, with permission from the American Chemical Society.

Attempts by Kao and others to enhance transparency by chemically removing impurities from glass met with little success the level of purity required was indeed comparable with that needed in silicon for integrated circuits. In the event, the required purification was achieved in the same way in which semiconductor-grade silicon is now manufactured, by going through the gas phase (silicon tetrachloride), which can be separated from the halides of impurity species because of dilTerences in vapour pressures. This breakthrough was achieved by R.D. Maurer and his... 

A single-column system for liquid-phase carhon adsorption is used in situations where the following conditions prevail laboratory testing has indieated that the breakthrough curve will be steep the extended lifetime of the earbon at normal operating conditions results in minor replacement or regeneration eosts the eapital... 

An alternative way of eliminating water in the RPLC eluent is to introduce an SPE trapping column after the LC column (88, 99). After a post-column addition of water (to prevent breakthrough of the less retained compounds), the fraction that elutes from the RPLC column is trapped on to a short-column which is usually packed with polymeric sorbent. This system can use mobile phases containing salts, buffers or ion-pair reagents which can not be introduced directly into the GC unit. This system has been successfully applied, for example, to the analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples (99). 

A breakthrough curve with the nonretained compound was carried out to estimate the axial dispersion in the SMB column. A Peclet number of Pe = 000 was found by comparing experimental and simulated results from a model which includes axial dispersion in the interparticle fluid phase, accumulation in both interparticle and intraparticle fluid phases, and assuming that the average pore concentration is equal to the bulk fluid concentration this assumption is justified by the fact that the ratio of time constant for pore diffusion and space time in the column is of the order of 10. ... 

An important breakthrough in that respect was the use of soHd-phase organic synthesis (SPOS) where the attachment of the substrate to an insoluble support allowed for easy workup (filtration) and for rapid generation of products via split-mix procedures [1,2]. An important subsequent development consisted of the immobihzation of reagents, scavengers and catalysts. This technique, coined polymer-assisted solution phase chemistry (PASP), allowed solution phase synthesis of compoimds, yet still enjoying the bene-... 

The semiconducting properties of the compounds of the SbSI type (see Table XXVIII) were predicted by Mooser and Pearson in 1958 228). They were first confirmed for SbSI, for which photoconductivity was found in 1960 243). The breakthrough was the observation of fer-roelectricity in this material 117) and other SbSI type compounds 244 see Table XXIX), in addition to phase transitions 184), nonlinear optical behavior 156), piezoelectric behavior 44), and electromechanical 183) and other properties. These photoconductors exhibit abnormally large temperature-coefficients for their band gaps they are strongly piezoelectric. Some are ferroelectric (see Table XXIX). They have anomalous electrooptic and optomechanical properties, namely, elongation or contraction under illumination. As already mentioned, these fields cannot be treated in any detail in this review for those interested in ferroelectricity, review articles 224, 352) are mentioned. The heat capacity of SbSI has been measured from - 180 to -l- 40°C and, from these data, the excess entropy of the ferro-paraelectric transition... 

Although MIL-47, and especially MIL-53(A1), had been found on many occasions to dynamically respond to adsorption of particular compounds, referred to as breathing [35] in the literature, in these liquid phase conditions, only minor changes of the lattice parameters have been observed. A study of xylene separations in vapor phase on MIL-5 3(A1) shows that breathing profoundly influences the shape of the obtained breakthrough profiles as a function of adsorbate concentration [97]. 

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