The iron oxides

This chapter is intended to offer a very brief introduction to the most important general features of iron oxides. It deals with the forms, ehemis-tiy, erystal structure, important properties and formation of these eom-pounds and their enviromental and industrial signifieance. For more information the reader is referred to the monograph The Iron Oxides by the same authors published in 1996 by Wiley-VCH. 

All iron oxides and hydroxides consist of Fe, O and/or OFl. They differ in composition, in the valence of Fe and, above all, in crystal structure. 

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DRI can be produced in pellet, lump, or briquette form. When produced in pellets or lumps, DRI retains the shape and form of the iron oxide material fed to the DR process. The removal of oxygen from the iron oxide during direct reduction leaves voids, giving the DRI a spongy appearance when viewed through a microscope. Thus, DRI in these forms tends to have lower apparent density, greater porosity, and more specific surface area than iron ore. In the hot briquetted form it is known as hot briquetted iron (HBI). Typical physical properties of DRI forms are shown in Table 1. 

In the EASTMET process iron oxide fines (minus 0.1 mm), pulverized coal, and binder are mixed together and pehetized. The green pehets are heated in a dryer to remove moisture and fed to a rotary hearth furnace, where the pehets are placed on a flat rotating surface (hearth) in an even layer one to two pehets deep. As the hearth rotates the pehets are heated to 1250—1350°C, and the iron oxide is reduced to metallic iron in 6 to 10 minutes. 

Synthetic mtile raw material is produced from ilmenite by reducing the iron oxides and leaching out the metallic iron with hydrochloric or sulfuric acids. In both processes, the objective is to increase the amount of Ti02 in the raw materials. 

Potassium bromate [7758-01-7] is much less soluble than the bromide and can mostly be removed by filtration the remaining bromate is reduced with iron. After filtration of the iron oxide, the KBr is crystallized. 

Some of the important parameters in the Bnchamp process are the physical state of the iron, the amount of water used, the amount and type of acid used, agitation efficiency, reaction temperature, and the use of various catalysts or additives. When these variables are properly controlled, the amine can be obtained in high yields while controlling the color and physical characteristics of the iron oxide pigment which is produced. 

Water. Based on the overall balanced equation for this reaction, a minimum of one mole of water per mole of nitro compound is required for the reduction to take place. In practice, however, 4 to 5 moles of water per mole of nitro compound are used to ensure that enough water is present to convert all of the iron to the intermediate ferrous and ferric hydroxides. In some cases, much larger amounts of water are used to dissolve the amino compound and help separate it from the iron oxide sludge after the reaction is complete. 

Several modifications to this process are possible (55). Instead of adding ferrous chloride directiy, it is more common to generate it by using iron and hydrochloric acid. The order in which the reactants are added can also be altered, and it is even possible to add all of the iron or aniline at the beginning of the reaction. There are also other ways to recover the aniline from the iron oxide sludge. 

The sulfur is thus removed from the gas stream and trapped in the sorbent as iron sulfide [1317-37-9]. Over time all of the iron oxide becomes sulfided and the adsorptive capacity of the sorbent becomes exhausted. The bed can be partially regenerated by oxidation, as follows ... 

Fig. 1. Iron oxide process where Kl represents the iron oxide sorbent bed ( ), the adsorption system and (-...

The zinc oxide [1314-13-2] process is similar to the iron oxide process. There is, however, one key distinction. The zinc sulfide [1314-98-3] ZnS,... 

Both processes also use up-graded ilmenite (slags). About 30% of the world s titanium feedstocks are suppHed by titanium slag producers in Canada, South Africa, and Norway. Slags are formed by the high temperature reduction of ilmenites in electric furnaces. Much of the iron oxide content is reduced to metallic iron and separated as a saleable by-product. Magnesium and other impurities may also be incorporated in the following equations. 

There are several means by which boiler water can become highly concentrated. One of the most common is iron oxide deposition on radiant wall tubes. Iron oxide deposits are often quite porous and act as miniature boilers. Water is drawn into the iron oxide deposit. Heat appHed to the deposit from the tube wall generates steam, which passes out through the deposit. More water enters the deposit, taking the place of the steam. This cycle is repeated and the water beneath the deposit is concentrated to extremely high levels. It is possible to have 100,000 ppm of caustic beneath the deposit while the bulk water contains only about 5—10 ppm of caustic. 

The choice of selected raw materials is very wide, but they must provide calcium oxide (lime), iron oxide [1309-37-1/, siHca, and aluminum oxide (alumina). Examples of the calcereous (calcium oxide) sources are calcium carbonate minerals (aragonite [14791-73-2] calcite [13397-26-7] limestone [1317-65-3] or mad), seasheUs, or shale. Examples of argillaceous (siHca and alumina) sources are clays, fly ash, mad, shale, and sand. The iron oxide commonly comes from iron ore, clays, or mill scale. Some raw matedals supply more than one ingredient, and the mixture of raw matedals is a function of their chemical composition, as deterrnined by cost and availabiHty. 

Two or more soHd catalyst components can be mixed to produce a composite that functions as a supported catalyst. The ingredients may be mixed as wet or dry powders and pressed into tablets, roUed into spheres, or pelletized, and then activated. The promoted potassium ferrite catalysts used to dehydrogenate ethylbenzene in the manufacture of styrene or to dehydrogenate butanes in the manufacture of butenes are examples of catalysts manufactured by pelletization and calcination of physically mixed soHd components. In this case a potassium salt, iron oxide, and other ingredients are mixed, extmded, and calcined to produce the iron oxide-supported potassium ferrite catalyst. 

Graphitically corroded cast irons may induce galvanic corrosion of metals to which they are coupled due to the nobility of the iron oxide and graphite surface. For example, cast iron or cast steel replacement pump impellers may corrode rapidly due to the galvanic couple established with the graphitically corroded cast iron pump casing. In this or similar situations, the entire affected component should be replaced. If just one part is replaced, it should be with a material that will resist galvanic corrosion, such as austenitic cast iron. 

The lifetime of a conventional exhaust system on an average family car is only 2 years or so. This is hardly surprising - mild steel is the usual material and, as we have shown, it is not noted for its corrosion resistance. The interior of the system is not painted and begins to corrode immediately in the damp exhaust gases from the engine. The single coat of cheap cosmetic paint soon falls off the outside and rusting starts there, too, aided by the chloride ions from road salt, which help break down the iron oxide film. 

The Lo-Cat process can be used to sweeten or convert H2S to sulfur. It removes H2S only and will not remove CO2, COS, CS2, or mercaptans. Iron is held in dilute solution (high circulation rates) by the common chelating agent EDTA (ethylene diamine tetra acetic acid). The iron oxidizes the H2S to sulfur. The solution is circulated batchwise to an oxidizer for regeneration. 

Most commercial liquid ammonia contains up to several ppm of colloidal iron compounds, possibly the iron oxide catalyst commonly used in manufacturing ammonia. Reduction converts these compounds to colloidal iron which strongly catalyzes the reaction between alcohols and sodium and potassium. The reaction of lithium with alcohols is also catalyzed by iron but to a markedly lesser degree. The data in Table 1-4 illustrate the magnitude of these catalytic effects. The data of Table 1-5 emphasize how less than 1 ppm... 

Since Mn is both soluble in iron oxides and mobile to the same extent as Fe, the addition of Mn to steels has little effect on the overall scaling rate in air or oxygen. Jackson and Wallwork have shown that between 20% and 40% manganese must be added to steel before the iron oxides are replaced by manganese oxides. However, Mn supresses breakaway oxidation in CO/CO2 possibly by reducing the coalescence of pores in the oxide scale. 

Deep-bed condensate polishers are commonly used for nuclear reactor power plants. Due to the extreme operating conditions, the resin is sometimes taken out of service as frequently as every 3 weeks for ultrasonic cleaning. This process removes the iron oxides and other particulates filtered out by the resin media. 

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