Liquid supported catalysts

Many superacid-catalyzed reactions were found to be carried out advantageously not only using liquid superacids but also over solid superacids, including Nafion-H or certain zeolites. We extensively studied the catalytic activity of Nafion-H and related solid acid catalysts (including supported perfluorooctanesulfonic acid and its higher ho-... 

Findings with Bench-Scale Unit. We performed this type of process variable scan for several sets of catalyst-liquid pairs (e.g., Figure 2). In all cases, the data supported the proposed mechanism. Examination of the effect of temperature on the kinetic rate constant produced a typical Arrhenius plot (Figure 3). The activation energy calculated for all of the systems run in the bench-scale unit was 18,000-24,000 cal/g mole. 

As anticipated in the introduction, cross-linked polymers swell, to variable extent, when put in contact with liquids. Therefore, the working state of any cross-linked organic pol5uner under solid-liquid conditions, no matter if it is a catalyst, a support or a carrier for solid state S5mthesis, is the swollen state. In macroreticular CFPs swelling does not involve the whole polymeric mass it is... 

Recently, iodobenzoates anchored onto an ionic liquid support (6.4) were coupled to various aryl boronic acids (6.5) in aqueous media using Pd(OAc)2 as the catalyst at 80°C to give the coupled product 6.6 (Scheme 6.3). Compounds 6.6 were purified simply by washing the reaction mixture with ether, which removed the unreacted starting materials and the side product 6.7 without the need of chromatography. Compounds 6.6 were then cleaved from the ionic liquid support... 

The mercury penetration approach is based on the fact that liquid mercury has a very high surface tension and the observation that mercury does not wet most catalyst surfaces. This situation holds true for oxide catalysts and supported metal catalysts that make up by far the overwhelming majority of the porous commercial materials of interest. Since mercury does not wet such surfaces, the pressure required to force mercury into the pores will depend on the pore radius. This provides a basis for measuring pore size distributions through measurements of the... 

In SL-PC, a catalyst is supported on a solid matrix in the form of the film of a nonvolatile liquid phase adsorbed on the solid. The catalytic film can be, for example, a molten salt or a molten oxide (e.g., Deacon s catalyst (CUCI2/KCI) used to oxidize HCl with oxygen for the chlorination of ethylene in the synthesis of vinyl chloride. Figure 6.1 V2O5 for the oxidation of sulphurous to sulphuric anhydride). Alternately, it can be a liquid phase (e.g., ethylene glycol, PPh3, butyl benzyl phthalate, etc.) that contains a soluble catalytic species such as a metal complex. 

Research in this field started in the wake of the reports of SL-PC. Consisting of a catalyst-containing supported liquid layer for CF reactions in the gas phase, the concept was transferred to batch reactions, using a catalyst dissolved in a supported aqueous phase. This was first referred to as supported aqueous-phase catalysis (SAPC) by Davis in an article published in Nature in 1989. Later, the concept was extended, using a variety of names, but the essence has remained the same a supported catalyst-philic phase. 

In future research, it may be interesting to combine supported liquid phase (SLP) catalysts or supported aqueous phase (SAP) catalysts [61,62] with SCCO2 as a mobile phase. 

Keywords Carbonylation Homogeneous catalysis Hydroformylation Immobilisation Ionic liquids Supported catalysts... 

Interestingly, the dimeric Cr(salen) catalyst 64 supported on silica showed enhanced activity for ARO of 1,2-epoxyhexane and cyclohexene oxide in the presence of ionic liquids particularly with [BMIM][PF6] (64-IL) [86] (Table 6). A significant increase in the product selectivity was also observed with silica supported ionic liquid (64-SILP) for ARO of 1,2-epoxyhexane and cyclohexene oxide (ee, of 87% and 75% respectively) as eompared to silica supported catalyst minus the ionie liquid (Table 6, entries 5,6). However, after repeated recycling, the silica support material deteriorates due to the abrasive forees in the stirred reactor. As a result, silica material was non-recoverable, but the expensive dimeric Cr(salen) catalyst 64 and the ionic liquid was recovered quantitatively by Soxhlet extraction with acetone. SILP-catalyst system was also used in a eontinuous-flow reactor. 

Interest in ionic liquids, early on mostly in academia, centered around their remarkable properties as solvents and catalysts for supporting and enhancing reactions, many of which are often difficult to carry out using conventional process conditions. The perceived advantages of ionic liquids have been widely publicized, and enthusiasm has encouraged scientists to look upon these advantages sometimes with disproportionate favor. The main advantages that attract attention are as follows ... 

Microtrickle bed reactor. Key a, gas inlet b, liquid thermocouple d, jacket e, glass beads f, catalyst bed support i, gas outlet j, liquid outlet. 

The crude MNB is washed to remove residual acid and the impurities formed during the nitration reaction. The product is then distilled and residual benzene is recovered and recycled. Purified MNB is fed, together with hydrogen, into a liquid phase plug-flow hydrogenation reactor that contains a DuPont proprietary catalyst. The supported noble metal catalyst has a high selectivity and the MNB conversion per pass is 100%. 

The porosity of a catalyst or support can be determined simply by measuring the particle density and solid (skeletal) density or the particle and pore volumes. Particle density pp is defined as the mass of catalyst per unit volume of particle, whereas the solid density p, as the mass per unit volume of solid catalyst. The particle volume Vp is determined by the use of a liquid that does not penetrate in the interior pores of the particle. The measurement involves the determination by picnometry of the volume of liquid displaced by the porous sample. Mercury is usually used as the liquid it does not penetrate in pores smaller than 1.2/m at atmospheric pressure. The particle weight and volume give its density pp. The solid density can usually be found from tables in handbooks only in rare cases is an experimental determination required. The same devices as for the determination of the particle density can be used to measure the pore volume V, but instead of mercury a different liquid that more readily penetrates the pores is used, such as benzene. More accurate results are obtained if helium is used as a filling medium [10]. The porosity of the particle can be calculated as ... 

As in many other areas of catalysis in ionic liquids, the research of the past years in ionic liquid supported olefin metathesis has been dominated by demonstrating the general feasibility in this reaction medium. With the development of the task-specific complexes new prospects have been opened and the improved recyclability of these compounds relative to the common metathesis catalysts is impressive. Apart from more active and stable catalysts, the development of enantioselective catalysts and of continuous processes are likely to be the next goals. 

---