Temperature sulphides

D. Farrell and L. Roberts. A study of high temperature sulphidation under actual process conditions. 

Cie2] Cieslak, J., Dubiel, S.M., Zmek, Z., High-Temperature Sulphidation of Fe-Cr Alloys , Hyperfine Interact, 112(1-4), 179-182 (1998) (Experimental, Interface Phenomena, Phase Relations, 4)... 

Fig. 13. High-temperature sulphidation of Incoloy 800H with and without ceria coating applied over a preoxidized substrate (Fransen et al. 1984).

For a more detailed review of the influence of reactive elements, including the rare earths, on the resistance to high-temperature sulphidation, see Stott et al. (1989). 

Mrowec S, W drychowska M, High temperature sulphidation of iron-chromium aluminum alloys , BuUetin de i Acaddmie Polonaise des Sciences, Sdrie des Sciences Chimiques, 1977 25(11) 877-883. 

PPha, pyridine) organic groups (olefines, aromatic derivatives) and also form other derivatives, e.g. halides, hydrides, sulphides, metal cluster compounds Compounds containing clusters of metal atoms linked together by covalent (or co-ordinate) bands, metaldehyde, (C2H40) ( = 4 or 6). A solid crystalline substance, sublimes without melting at I12 1I5" C stable when pure it is readily formed when elhanal is left in the presence of a catalyst at low temperatures, but has unpredictable stability and will revert to the monomer, ft is used for slug control and as a fuel. 

The last equation explains the funetion of the limestone. An older process, in which the ore was partially roasted, the air shut off and the temperature raised so that excess sulphide reacted with the oxide produced to give lead, is now obsolete. 

There aie a number of major indusuial problems in the operation of the steam reforming of metlrane. These include the formation of carbon on the surface of the catalyst, the sulphidation of the catalyst by the H2S impurity in commercial natural gas, and die decline of catalytic activity due to Ostwald ripening of the supported catalyst particles by migration of catalyst atoms from the smaller to tire larger particles, as the temperamre is increased. A consideration of tire thermodynamics of the principal reaction alone would suggest that the reaction shifts more favourably to the completion of the reaction as the temperature is increased. 

The reaction of metals with gas mixtures such as CO/CO2 and SO2/O2 can lead to products in which the reaction of the oxygen potential in the gas mixture to form tire metal oxides is accompanied by the formation of carbon solutions or carbides in tire hrst case, and sulphide or sulphates in the second mixture. Since the most importairt aspects of this subject relate to tire performairce of materials in high temperature service, tire reactions are refeiTed to as hot corrosion reactions. These reactions frequendy result in the formation of a liquid as an intermediate phase, but are included here because dre solid products are usually rate-determining in dre coiTosion reactions. 

Molten sulphides are almost invariably semiconductors, and so their conductivities are typically larger than Arose of the average molten electrolyte. For example, the specific conductairce of molten AgaS can be described, as a function of temperature by the equation... 

Lead The production of lead from lead sulphide minerals, principally galena, PbS, is considerably more complicated than the production of zinc because tire roasting of the sulphide to prepare the oxide for reduction produces PbO which is a relatively volatile oxide, and therefore the temperature of roasting is limited. The products of roasting also contain unoxidized galena as well as die oxide, some lead basic sulphate, and impurities such as zinc, iron, arsenic and antimony. 

In the blast furnace reduction slag-making materials are also added together with a small amount of iron, the function of which is to reduce any sulphide which remains, to the product of the roasting operation to produce a sinter. The sinter is then reduced with coke in a vertical shaft blast furnace in which air is blown tluough tuyeres at the bottom of tire shaft. The temperature in the heartlr where metal is produced must be controlled to avoid the vaporization of any zinc oxide in the sinter. The products of tlris process are normally quite complex, and can be separated into four phases. Typical compositions of these are shown in Table 13.1. 

The production of copper from sulphide minerals is accomplished with a preliminary partial roast of die sulphides before reaction widr air in the liquid state, known as mattes, to form copper metal (conversion). The principal sources of copper are minerals such as chalcopyrite, CuFeSa and bornite CuaFeSa, and hence the conversion process must accomplish the preferential oxidation of non, in the form of FeO, before the copper metal appears. As mentioned before, tire FeO-SiOa liquid system is practically Raoultian, and so it is relatively easy to calculate the amount of iron oxidation which can be canned out to form this liquid slag as a function of the FeO/SiOa ratio before copper oxidation occurs. The liquid slag has a maximum mole fraction of FeO at the matte blowing temperatures of about 0.3, at solid silica saturation. 

The presence of the either linkages is sufficient to allow the material to be melt processed, whilst the polymer retains many of the desirable characteristics of polyimides. As a consequence the material has gained rapid acceptance as a high-temperature engineering thermoplastics material competitive with the poly-sulphones, poly(phenylene sulphides) and polyketones. They exhibit the following key characteristics ... 

As with the polysulphones, the deactivated aromatic nature of the polymer leads to a high degree of oxidative stability, with an indicated UL Temperature Index in excess of 250°C for PEEKK. The only other melt-processable polymers in the same league are poly(phenylene sulphides) and certain liquid crystal polyesters (see Chapter 25). 

It has already been shown (e.g. Chapters 20 and 21) that the insertion of a p-phenylene into the main chain of a linear polymer increased the chain stiffness and raised the heat distortion temperature. In many instances it also improved the resistance to thermal degradation. One of the first polymers to exploit this concept commercially was poly(ethylene terephthalate) but it was developed more with the polycarbonates, polysulphone, poly(phenylene sulphides) and aromatic polyketones. 

Over the years polymers have been produced suitable for use at progressively higher temperatures. Where this is a requirement, it is usual first to decide whether a rubbery or a rigid material is required. If the former, this has been dealt with by the author elsewhere." If the latter, it is usually convenient to look in turn at polycarbonates, PPO-based materials, polyphenylene sulphides, polysul-phones, polyketones such as PEEK and PEK, polyamide-imides, poly-phthalamides, fluoropolymers, liquid crystal polymers and polyimides. 

Hydrogen sulphide oeeurs naturally, e.g. in natural gas and petroleum, voleanie gases, and from deeaying organie matter. It may be present near oil wells and where petroleum is proeessed. Commereially it is obtained as a by-produet from many ehemieal reaetions ineluding off-gas in the produetion of some synthetie polymers (e.g. rayon, nylon) from petroleum produets, and by the aetion of dilute mineral aeids on metal sulphides. Physieal properties are summarized in Table 9.14 and effeets of temperature on vapour pressure are shown in Figure 9.5. 

Figure 9.5 Hydrogen sulphide vapour pressure vs temperature...

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