Rich cobalt catalysts

Most likely the cobalt catalyst is HCo(CO)2(L), which has a very electron rich metal centre and dissociation of CO does not occur under the reaction conditions. The first step is a reaction of the cobalt hydride with ethylene oxide forming a hydroxyethylcobalt species, which does not require dissociation of... 

However, a strong caustic solution is used to remove mercaptans from gas and liquid streams. In the Merox Process, for example, a caustic solvent containing a catalyst such as cobalt, which is capable of converting mercaptans (RSH) to caustic insoluble disulfides (RSSR), is used for streams rich in mercaptans after removal of H2S. Air is used to oxidize the mercaptans to disulfides. The caustic solution is then recycled for regeneration. The Merox process (Fig. 1-3) is mainly used for treatment of refinery gas streams. ... 

The NHCs have been used as ligands of different metal catalysts (i.e. copper, nickel, gold, cobalt, palladium, rhodium) in a wide range of cycloaddition reactions such as [4-1-2] (see Section 5.6), [3h-2], [2h-2h-2] and others. These NHC-metal catalysts have allowed reactions to occur at lower temperature and pressure. Furthermore, some NHC-TM catalysts even promote previously unknown reactions. One of the most popular reactions to generate 1,2,3-triazoles is the 1,3-dipolar Huisgen cycloaddition (reaction between azides and alkynes) [8]. Lately, this [3h-2] cycloaddition reaction has been aided by different [Cu(NHC)JX complexes [9]. The reactions between electron-rich, electron-poor and/or hindered alkynes 16 and azides 17 in the presence of low NHC-copper 18-20 loadings (in some cases even ppm amounts were used) afforded the 1,2,3-triazoles 21 regioselectively (Scheme 5.5 Table 5.2). 

CO Subsequently a migratory insertion will take place. Oxidative addition of H2 will be faster at the electron rich metal centre and thus the aldehyde will form. Hydrogenation takes place at ruthenium (added as Ru3(CO)i2) as indeed catalyst systems containing cobalt only are known to give 3-hydroxypropanal as the product. 

In the SCOT process, the sulfur compounds in the Claus tail gas are converted to hydrogen sulfide by heating and passing it through a cobalt-molybdenum catalyst with the addition of a reducing gas. The gas is then cooled and contacted with a solution of diisopropanolamine (DIPA) that removes all but trace amounts of hydrogen sulfide. The sulfide-rich diisopropanolamine is sent to a stripper, where hydrogen sulfide gas is removed and sent to the Claus plant. The diisopropanolamine is returned to the absorption column. 

Numerous studies have been published on catalyst material directly related to rich catalytic combustion for GTapplications [73]. However, most data are available on the catalytic partial oxidation of methane and light paraffins, which has been widely investigated as a novel route to H2 production for chemical and, mainly, energy-related applications (e.g. fuel cells). Two main types of catalysts have been studied and are reviewed below supported nickel, cobalt and iron catalysts and supported noble metal catalysts. 

Acetic acid has been generated directly from synthesis gas (CO/H2) in up to 95 wt % selectivity and 97% carbon efficiency using a Ru-Co-I/Bu4PBr "melt" catalyst combination. The critical roles of each of the ruthenium, cobalt and iodide catalyst components in achieving maximum selectivity to HOAc have been identified. Ci Oxygenate formation is observed only in the presence of ruthenium carbonyls [Ru(C0)3l3] is here the dominant species. Controlled quantities of iodide ensure that initially formed MeOH is rapidly converted to the more reactive methyl iodide. Subsequent cobalt-catalyzed carbonylation to acetic acid may be preparatively attractive (>80% selectivity) relative to competing syntheses where the [00(00)4] concentration is optimized that is, where the Co/Ru ratio is >1, the syngas feedstock is rich in 00 and the initial iodide/cobalt ratios are close to unity. 

The operation of an LC-Finer is best described by means of a process flow schematic (Figure 2). The LC-Finer reactor maintains the catalyst (typically American Cyanamid 1442B cobalt molybdenum 1/32 inch extrudate or Shell 324 nickel molybdenum 1/32 inch extrudate) in constant motion, suspended by the recirculation of copious volumes of liquid. This recirculation results in a 35-50% bed expansion and the reactor operates at a uniform temperature with essentially no pressure drop. In a commercial unit there is a recycle of hydrogen rich gas along with a distillate liquid stream which is combined with the fresh SRC. The PDU differs from the commercial unit design in that there is no recycle gas or liquid streams. The bed expansion is maintained with an external recirculation loop. It should be noted that the PDU fractionator separates the liquid product into a light oil (L.O.) and a heavy oil (H.O.). The combination of these two oil streams is designated as total liquid product (TLP). 

Cobalt complexes derived from Schiff bases 388 catalyzed the hydroxyacylation of electron-deficient alkenes (Fig. 90) [431, 432]. Thus, methyl acrylate 387 reacted with aliphatic aldehydes 386 in the presence of 5 mol% of the in situ generated catalyst, molecular oxygen, and acetic anhydride to 2-acyloxy-4-oxoesters 389 in 56-77% yield. When acetic anhydride was omitted, the yields of products were lower and mixtures of the free hydroxy compounds and acylated compounds resulting from Tishchenko reactions were obtained. Electron-rich alkenes did not undergo the transformation, since the addition of the acyl radical is much slower. The acylcobalt species inserts oxygen instead and acts as an epoxidation catalyst. 

Ruthenium compounds are widely used as catalysts for hydrogen transfer reactions. These systems can be readily adapted to the aerobic oxidation of alcohols by employing dioxygen, in combination with a hydrogen acceptor as a cocatalyst, in a multistep process. These systems demonstrate high activity. For example, Backvall and coworkers [146] used low-valent ruthenium complexes in combination with a benzoquinone and a cobalt-Schiffs base complex. Optimization of the electron-rich quinone, combined with the so-called Shvo Ru-cata-lyst, led to one of the fastest catalytic systems reported for the oxidation of secondary alcohols (Fig. 4.59). 

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