Catalytic performance, comparison with

Table 1 Comparison of the catalytic performance achieved with different soUd acid catalysts. Tenperature 80°C, reaction time 2 h, initial formaldehyde/guaiacol ratio 18/1.

Catalytic Performance Comparison of Catalysts. There is a large number of studies comparing the catalytic behavior of different reforming catalysts with different feeds, both with pure hydrocarbons and naphtha cuts (76). Some of the results, summarized in Table 7, are the following ... 

From these results, the Institut Fran ais du Petrole (IFF) has developed a biphasic version of its established monophasic Dimersol process , which is offered for licensing under the name Difasol process [98]. The Difasol process uses slightly acidic chloroaluminate ionic liquids with small amounts of allcylaluminiums as the solvent for the catalytic nickel center. In comparison to the established Dimersol process , the new biphasic ionic liquid process drastically reduces the consumption of Ni-cata-lyst and allcylaluminiums. Additional advantages arise from the good performance obtained with highly diluted feedstodcs and the significantly improved dimer selectivity of the Difasol process (for more detailed information see Section 5.3). 

Characterization of catalytic phenomena at oxide surfaces includes (1) characterization of established catalyst surfaces to improve the catalytic performance, (2) characterization of new catalysts in comparison with conventional catalysts, (3) characterization of specific model surfaces such as single crystals and epitaxial flat surfaces to transfer the knowledge so obtained to catalytic systems or even to create a new type of catalyst, and (4) characterization of catalysis... 

The synthesis of Pd/ACF (0.42wt.% Pd) catalyst with monodispersed nanoparticles carried out at cuo = 3 is illustrated, as well as its catalytic performance in a liquid-phase hydrogenation of 1-hexyne in comparison with a traditional powdered Lindlar catalyst. 

Table 10.4. Comparison of the catalytic performances of various supported noble metal-based catalysts (reproduced with permission from Ref. [104])...

In the direct ammoxidation of propane over Fe-zeolite catalysts the product mixture consisted of propene, acrylonitrile (AN), acetonitrile (AcN), and carbon oxides. Traces of methane, ethane, ethene and HCN were also detected with selectivity not exceeding 3%. The catalytic performances of the investigated catalysts are summarized in the Table 1. It must be noted that catalytic activity of MTW and silicalite matrix without iron (Fe concentration is lower than 50 ppm) was negligible. The propane conversion was below 1.5 % and no nitriles were detected. It is clearly seen from the Table 1 that the activity and selectivity of catalysts are influenced not only by the content of iron, but also by the zeolite framework structure. Typically, the Fe-MTW zeolites exhibit higher selectivity to propene (even at higher propane conversion than in the case of Fe-silicalite) and substantially lower selectivity to nitriles (both acrylonitrile and acetonitrile). The Fe-silicalite catalyst exhibits acrylonitrile selectivity 31.5 %, whereas the Fe-MTW catalysts with Fe concentration 1400 and 18900 ppm exhibit, at similar propane conversion, the AN selectivity 19.2 and 15.2 %, respectively. On the other hand, Fe-MTW zeolites exhibit higher AN/AcN ratio in comparison with Fe-silicalite catalyst (see Table 1). Fe-MTW-11500 catalyst reveals rather rare behavior. The concentration of Fe ions in the sample is comparable to Fe-sil-12900 catalyst, as well as... 

Concerning the Fischer-Tropsch synthesis, carbon nanomaterials have already been successfully employed as catalyst support media on a laboratory scale. The main attention in literature has been paid so far to subjects such as the comparison of functionalization techniques,9-11 the influence of promoters on the catalytic performance,1 12 and the investigations of metal particle size effects7,8 as well as of metal-support interactions.14,15 However, research was focused on one nanomaterial type only in each of these studies. Yu et al.16 compared the performance of two different kinds of nanofibers (herringbones and platelets) in the Fischer-Tropsch synthesis. A direct comparison between nanotubes and nanofibers as catalyst support media has not yet been an issue of discussion in Fischer-Tropsch investigations. In addition, a comparison with commercially used FT catalysts has up to now not been published. 

The comparison of catalytic properties was made under identical reaction conditions, among three important candidate catalysts, namely, the Pt/y-Al203, Au/a-Fe203, and Cu Ce, x02 y systems [50], The catalytic tests were performed in the reactant feed containing CO, H2, C02, and HzO — the so-called reformate fuel. The effects of the presence of both C02 and H20 in the reactant feed on the catalytic performance (activity and selectivity) of these catalysts as well as their stability with time under reaction conditions have been studied. The composition of the prepared samples and their BET specific surface areas are presented in Table 7.6. The results obtained with the three catalysts in the presence of 15 vol% COz and of both 15 vol% COz and 10 vol% H20 in the reactant feed (with contact time wcat/v = 0.144 g sec/cm3 and X = 2.5) are shown in Figure 7.12. For comparison, the corresponding curves obtained under the same conditions but without water vapor in the feed are also shown in Figure 7.12. 

As an aside, we should mention that the same principles apply to the formation of bimetallic clusters on a support. In the case of Pt-Re on AI2O3 it has been shown that hydroxylation of the surface favors the ability of Re ions to migrate toward the Pt nuclei and thus the formation of alloy particles, whereas fixing the Re ions onto a dehydroxylated alumina surface creates mainly separated Re particles. As catalytic activity and selectivity of the bimetallic particles differ vastly from those of a physical mixture of monometallic particles, the catalytic performance of the reduced catalyst depends significantly on the protocol used during its formation. The bimetallic Pt-Re catalysts have been identified by comparison with preparations in which gaseous Re carbonyl was decomposed on conventionally prepared Pt/Al203 catalysts. ... 

The reactions with nG-105 dendrimers show a different trend. Enhanced catalytic performance was observed with increasing dendrimer generation (77.3% yield, 97.2% selectivity, 15.5% ee for Gl 85% yield, 98% selectivity, 37% ee for G4). This comparison indicates that the introduction of an alkyl spacer not only facilitates the access of reactant to the catalytic active sites but also prevents the formation of frozen-in conformations and thus different chiral active sites. However, when the fifth-generation dendrimer is reached, the multiple interactions between end groups become more pronounced, which leads to a decrease in the catalyst performance (68% yield, 95.3% selectivity, 17.6% ee). 

Three syntheses of 1,2-dicyanocyclobutene (2) have been previously described. The first, involving dehydration of cyclobutene-1,2-dicarboxamide does not specify the yield.9 The second procedure involves a concomitant chlorination and catalytic dehydrochlorination of 1,2-dicyanocyclobutane in the gas phase, yielding 1,2-dicyanocyclobutene (2) in a mixture of several other products.10 The third method consists of dechlorination of 1,2-dichloro-1,2-dicyanocyclobutane using metals, such as zinc copper couple,11 Raney nickel,11 and, especially, Raney cobalt.2 In comparison with this last-mentioned synthesis, the overall yield of the present procedure is 5-10% higher. Furthermore, the reaction is performed in less time and utilizes considerably cheaper reagents. 

The catalytic hydration of olefins can also be performed in a three-phase system solid catalyst, liquid water (with the alcohol formed dissolved in it) and gaseous olefin [258,279,280]. The olefin conversion is raised, in comparison with the vapour phase processes, by the increase in solubility of the product alcohol in the excess of water [258]. For these systems with liquid and vapour phases simultaneously present, the equilibrium composition of both phases can be estimated together with vapour-liquid equilibrium data [281]. For the three-phase systems, ion exchangers, especially, have proved to be very efficient catalysts [260,280]. With higher olefins (2-methylpropene), the reaction was also performed in a two-phase liquid system with an ion exchanger as catalyst [282]. It is evident that the kinetic characteristics differ according to the arrangement (phase conditions), i.e. whether the vapour system, liquid vapour system or two-phase liquid system is used. However, most kinetic and mechanistic studies of olefin hydration were carried out in vapour phase systems. 

The comparison of the catalytic performances of metals and their alloys is sometimes hampered by the different degree of deactivation by carbonaceous residues (107, 67). Therefore, it seems appropriate to start with a discussion of the exchange reactions of the hydrogen isotopes protium and deuterium on platinum and Pt-Au films (31). A comparison of this reaction on platinum and its alloy shows that of the two reaction paths possible on platinum in the temperature region studied, one remains unchanged on the alloy but the other, which prevails on platinum except at very low temperatures, seems... 

Figure 24.9 A comparison of catalytic performances of iso-butane dehydrogenation on vanadium and on vanadium carbide catalysts. The reaction was carried out in a circulating batch reactor. The initial partial pressure of isobutane was 13.3 kPa Torr, which was mixed with He for a total pressure of 100 kPa.

Figure 1 summarizes the main differences and objectives between the major preparation strategies. A collection of the major individual reaction steps for the synthesis of unsupported catalysts can be found in Table 1. One fundamental insight from this rather schematic comparison is that differences in the reaction kinetics of the synthesis of a given material will lead to different mesoscopic and macroscopic structures which considerably affect the catalytic performance. It is necessary to control these analytically difficult-to-describc parameters with much the same precision as the atomic arrangement or the local electronic structure. Whereas these latter parameters influence the nature of the active site, it is the mcso/macrostructure which controls the distribution and abundance of active sites on a given material. It is necessary in certain cases to apply the costly method of fusion as there is no other way to... 

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