Nitrous oxide metal oxides catalysts

A special case is the hydroxylation of benzene with nitrous oxide as oxidant, for which commercialization has been announced [55]. The reaction occurs on Fe-silicalite-1, in the gas phase, at temperatures close to 400 °C, producing molecular nitrogen as by-product. Other zeolites and supported metals and metal oxides are less satisfactory catalysts. Toluene, chlorobenzene, and fluorobenzene are similarly hydroxylated, yielding all three possible isomers. Phenol produces catechol and hydroquinone. 

The conventional selective reduction of NOx for car passengers still competes but the efficient SCR with ammonia on V205/Ti02 for stationary sources is not available for mobile sources due to the toxicity of vanadium and its lower intrinsic activity than that of noble metals, which may imply higher amount of active phase for compensation. As illustrated in Figure 10.9, such a solution does not seem relevant because a subsequent increase in vanadium enhances the formation of undesirable nitrous oxide at low temperature. Presently, various attempts for the replacement of vanadium did not succeed regarding the complete conversion of NO into N2 at low temperature. Suarez et al. [87] who investigated the reduction of NO with NH3 on CuO-supported monolithic catalysts... 

Copper metal surface area was determined by nitrous oxide decomposition. A sample of catalyst (0.2 g) was reduced by heating to 563 K under a flow of 10 % H2/N2 (50 cm min"1) at a heating rate of 3 deg.min 1. The catalyst was then held at this temperature for 1 h before the gas flow was switched to helium. After 0.5 h the catalyst was cooled in to 333 K and a flow of 5 %N20/He (50 cm3mirr ) passed over the sample for 0.25 h to surface oxidise the copper. At the end of this period the flow was switched to 10 % H2/N2 (50 entitlin 1) and the sample heated at a heating rate of 3 deg.min"1. The hydrogen up-take was quantified, from this a... 

Hydrogenation catalyst, Acid, Fuel Riesthuis, P. et al., J. Loss Prev. Process Ind., 1997, 10(10), 67 In the presence of precious metal hydrogenation catalyst, hydroxylamine salts may disproportionate and form dinitrogen monoxide. Such a mixture is present in a process whereby the hydroxyamine is formed by hydrogenation of nitrate. An explosion in the degassing line, after a period of abnormal operation, was attributed to nitrous oxide build-up. Fuel, in the form of hydrogen and methane diluent, was already present. 

The decomposition of nitrous oxide over various metal oxides has been widely investigated by many investigators (1-3). Dell, Stone and Tiley (4) have compared the reactivity of metal oxides and shown that in general p-type oxides were the best catalysts and n-type the worst, with insulators occupying an intermediate position. It has been generally accepted (5) that this correlation indicates that the electronic structure of the catalyst is an important factor in the mechanism of the decomposition of nitrous oxide over metal oxides catalysts. The reaction is usually written (4) as... 

Other reported syntheses include the Reimer-Tiemann reaction, in which carbon tetrachloride is condensed with phenol in the presence of potassium hydroxide. A mixture of the ortho- and para-isomers is obtained the para-isomer predominates. -Hydroxybenzoic acid can be synthesized from phenol, carbon monoxide, and an alkali carbonate (52). It can also be obtained by heating alkali salts of -cresol at high temperatures (260—270°C) over metallic oxides, eg, lead dioxide, manganese dioxide, iron oxide, or copper oxide, or with mixed alkali and a copper catalyst (53). Heating potassium salicylate at 240°C for 1—1.5 h results in a 70—80% yield of -hydroxybenzoic acid (54). When the dipotassium salt of salicylic acid is heated in an atmosphere of carbon dioxide, an almost complete conversion to -hydroxybenzoic acid results. They>-aminobenzoic acid can be converted to the diazo acid with nitrous acid followed by hydrolysis. Finally, the sulfo- and halogenobenzoic acids can be fused with alkali. 

Schwab and co-workers (5-7) found a parallel between the electron concentration of different phases of certain alloys and the activation energies observed for the decomposition of formic acid into H2 and CO2, with these alloys as catalysts. Suhrmann and Sachtler (8,9,58) found a relation between the work function of gold and platinum and the energy of activation necessary for the decomposition of nitrous oxide on these metals. C. Wagner (10) found a relation between the electrical conductivity of semiconducting oxide catalysts and their activity in the decomposition of N2O. 

According to this work the catalytic decomposition of nitrous oxide molecules proceeds in the following way a N2O molecule adsorbed by the catalyst binds metal electrons, and thus the bond between the 0 atom and N2 in the molecule is loosened, and N2 is thermally dissociated from O at sufficiently high temperature. The 0 atom is held to the surface through the influence of the metal electrons. It can combine with a neighboring... 

Studies in this field are just beginning, and the number of publications hardly exceeds a dozen. The most interesting results were obtained by the research groups of Yamada [160-162], Neumann [163,164] and Kozhevnikov [165, 166], Using various type catalysts (Ru porphyrene complexes, polyoxometalates, supported metals), the authors conducted selective oxidations of various types. These include epoxidation of alkenes, oxidation of alcohols, oxidation of alkylaromatics, oxidation and aromatiza-tion of dihydroanthracenes, and some other reactions. The experiments were typically conducted at 373—423 K under 1.0 MPa pressure of nitrous oxide. 

Porphyrins are often employed in sensors on account of their ability to act as cation hosts and, with a suitable metal ion coordinated, as redox catalysts. Electropolymerised poly(metalloporphyrin)s have been used as potentiometric anion-selective electrodes [131] and as amperometric electrocatalytic sensors for many species including phenols [132], nitrous oxide [133] and oxygen [134]. Panasyuk et al. [135] have electropolymerised [nickel-(protoporphyrin IX)dimethylester] (Fig. 18.10) on glassy carbon in the presence of nitrobenzene in an attempt to prepare a nitrobenzene-selective amperometric sensor. Following extraction of the nitrobenzene the electrode was exposed to different species and cyclic voltammetric measurements made. A response was observed at the reduction potential of nitrobenzene (the polyporphyrin film acts only to accumulate the analyte and not in a catalytic fashion). Selectivity for nitrobenzene compared with w-nitroaniline and o-nitroto-luene was enhanced compared with an untreated electrode, while a glassy carbon-... 

Ammonia oxidation can also form nitrous oxide (N2O) in small amoimts. The desired NO producing reaction [Eq. (1)] is extremely fast as the contact time is about 1 msec and is limited by gas-solid mass transfer. For this reason, both the gas linear velocity and flow uniformity are critical issues. The yield to NO is an increasing function of temperature and a slightly decreasing function of total pressure. The NO yield is 98% at atmospheric pressure and 50°C, while it is 96%i at 8 atm and 900°C. The loss of precious metal catalyst is an important consideration at higher temperatures. 

The various processes for the catalytic reaction are similar. The factor that makes the difference is the choice of catalyst, which in turn affects the temperature regime needed to trigger the decomposition of nitrous oxide. In the literature, numerous works illustrate the several classes of catalysts appropriate for this reaction [9a, k] noble metals (Pt, Au), pure or mixed metal oxides (spinels, perovskite-types, oxides from hydrotalcites), supported systems (metal or metal oxides on alumina, silica, zirconia) and zeolites. 

ZSM5 type zeolites were used as catalysts for the one-step synthesis of phenol hy benzene partial oxidation with nitrous oxide. Isomorphous substitution of Al ions by other trivalent metal ions revealed a high catalytic performance of the H-Ga-ZSM5 in a wide temperature range. Systematic variation of the partial pressures of the reactants led to satisfactory preliminary kinetic models. Deactivation could be reduced by postsynthetic catalyst silylation which is believed to block the strongest acid sites responsible for coke formation. 

This part of the research was undertaken in order to prove whether or not N2O was an intermediate in the reaction of NOx reduction and to demonstrate a possible effect of zinc in the surprising low production of N2O. Indeed, it is well known than under TWC conditions one of the by-product when using noble metal type catalysts is nitrous oxide [3]. 

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