Other spinel formation reactions

Armijo [1198] has discussed a number of features of the kinetics and mechanisms of spinel formation. Under suitable conditions, the rates of some high temperature spinel syntheses can be studied gravimetrically [1199]. Holt [1180] has been concerned with the role of oxygen diffusion in CoA1204 formation. 

Parker et al. [1158], considering observations for the reaction NiO + Fe203 = NiFe204 

Laqua et al. [1292] have made a detailed kinetic study of the interaction between CoO and 3-Ga203. In this reaction of the second kind (i.e. each reactant has been presaturated with the other), growth of the spinel product layer is parabolic and E = 300 kJ mole-1. 

The autocatalytic behaviour found [1203] for chromite formation, through the reactions of Cr203 with various oxides (CdO, CuO, MgO, NiO, and ZnO) in air, was attributed to the intermediate production of the chromate which later decomposed to MCr204. Haber [1204] concluded that during the reaction 

Further investigations of spinel formation reactions are to be found in the literature [1], but the above representative selection illustrates a number of typical features of these rate processes. Following migration of cations from one constituent onto the surfaces of the other, the process is limited by the rate of diffusion across a barrier layer. While obedience to a particular kinetic expression is sometimes reported, the data available are not always sufficiently precise to enable the fit found to be positively 

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A review is given of studies of reactions in ionic solid systems and of the implications of these studies for industrial applications. Work on the kinetics of solid-state reaction systems is discussed, as are studies of reaction mechanisms and of the effects of process variables on product characteristics. As examples of the significance of these studies for industry the formation of ferrites and of other spinels by reaction in the solid state, the use of catalytic processes employing such solid catalysts as zeolites, and the development of batteries and fuel cells using solid-state electrolytes are described. 

Reaction 3 also occurs on cooling since the concentration of SO is very low at roaster temperatures of 950°C and approaches zero at 1000°C. Another important reaction that occurs during roasting is the formation of zinc ferrite, Zn0-Fe2 03 above 650°C (see Ferrites). Zinc ores contain 5—12% iron. Zinc ferrite forms soHd solutions with other spinels, such as Fe0-Fe203, and therefore the zinc—iron compositions formed are of indefinite stoichiometry. Ferritic zinc is difficult to solubilize in hydrometaHurgical leaching but several recovery processes are discussed below. 

In principle, reaction schemes similar to that given in the preceding paragraph may be developed for other comparable rate processes, for example spinel formation. However, Stone [27] has pointed out that, where the barrier phase is not an efficient ionic conductor, the overall reaction may be controlled by the movement of a single cation and anion. In addition, there is the probability that lattice imperfections (internal surfaces, cracks, leakage paths [1172], etc.) may provide the most efficient route to product formation.]... 

Spinel formation is usually treated under some tacit assumptions which do not always hold. For example, it is tacitly assumed that the oxygen potential of the surrounding gas atmosphere prevails throughout the reaction product during reaction. In other words, it is assumed that d,u0 = 0. Although this inference reduces the number of variables by one and simplifies the formal treatment, the subsequent analysis will show that the assumption is normally not adequate. 

Figure 6-6. Fluxes and interlace reactions for different boundary conditions during spinel formation AO + BjOj = AB204. a) Oxygen excluded from phase boundaries, b) Oxygen has access to both boundaries. c) Only oxygen (of different potential) is available at the boundaries. d) Oxygen (of different potential) and one reactant (AO) is available at the boundaries, e) AO (but no oxygen) is available at one boundary both B203 and oxygen are available at the other boundary.

The results of catalytic partial oxidation of methanol over the spinel catalysts derived from CoAl- and CoAISn-LDH are presented in Table 2. A methanol conversion of 30 to 50 mol % was obtained over catalyst derived from CoAI-LDH. The products obtained were H2, H20, CO and C02. Other products such as formaldehyde, methyl formate or dimethyl ether was not observed under the present experimental conditions. The selectivity of H20 was very high (= 40 to 60 %), probably because of the involvement of the complete oxidation of methanol over these catalysts. It is interesting to note from the Table that the methanol conversion rate and the selectivity of CO2 increased over the catalyst derived from the Sn-containing analogue. The observation that only traces of CO is produced in the Sn-containing catalyst, is attractive for the development of catalyst for POM reaction to produce H2 for fuel cell applications. The only inconvenience is the higher selectivity of H2O by complete oxidation, probably because of the higher Co content in the sample. 

Abbattista et al. (26) found that phosphorus addition prevents crystallization of the y-alumina phase and the transformation from y- to a-alumina in the system AI2O3 —AIPO4 (Fig. 23). More precisely, Morterra et al. (77) reported that phosphates do not affect the phase transition from low-temperature spinel alumina (y-alumina) to high-temperature spinel aluminas 8 and 6 phases) but delay the transition of 8 and 9 to a-alumina (corundum). Stanislaus et al 46) also reported that phosphorus significantly improves the thermal stabihty of the y-alumina phase in P/Al catalysts. However, the same authors found that the positive effect of phosphorus seems to be canceled in the presence of molybdenum due to the formation of aluminum molybdate. Thermal treatments of MoP/Al catalysts at temperatures >700°C result in a considerable reduction of SSA and mechanical strength. The presence of phosphorus does not prevent the reaction between the molybdenum oxo-species and alumina since the interaction between molybdates and phosphates is weak. The presence of nickel does not obviously affect the positive effect of phosphorus in terms of thermal stability 46). On the other hand, Hopkins and Meyers 78) reported that the thermal stability of commercial CoMo/Al and NiMo/Al catalysts is improved by the addition of phosphorus. 

In the oceanic setting, spinel Iherzolite xenoliths from Pali (Hawaii) have olivine 5 0 values of 5.09-5.12 per mil, typical of olivines from other oceanic and continental mantle rocks (Ducea et al., 2002). In contrast, olivines from plagioclase peridotites are enriched by 0.5 per mil. This is interpreted to be due to the formation of plagioclase by reaction with or crystallization from melts intruding the Pacific lithospheric mantle. 

Catalyst deactivation and resistance to coking are two important issues of the methane reforming reaction with CO2 over Ni based catalysts because of their potential industrial application. Chen and Wren (9) and Bhattacharya and Chang (10) have recently proposed that the nickel aluminate spinel produced by interaction between nickel and alumina has a positive effect on the suppression of carbon deposition in CO2 reforming of methane. On the other hand, the formation of various types of nickel silicate species between the nickel and the support, attributed to the strong metal-support interaction, has been reported in Ni-silica catalysts (11,12). From these conclusions, it seems interesting to study the influence of Ni-silica interaction on carbon deposition. 

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