Mass transfer corrosion

The solubility of titanium is shown in Fig. 20-7. It has been shown [8] that titanium will reduce the mass-transfer corrosion of steels by liquid bismuth. 

The original hot carbonate process developed by the U.S. Bureau of Mines was found to be corrosive to carbon steel (55). Various additives have been used in order to improve the mass transfer rate as well as to inhibit corrosion. Vetrocoke, Carsol, Catacarb, Benfteld, and Lurgi processes are all activated carbonate processes. Improvements in additives and optimization of operation have made activated carbonate processes competitive with activated MDEA and nonaqueous solvent based systems. Typical energy requirements are given in Table 9. 

Selection of Equipment Packed columns usually are chosen for very corrosive materials, for liquids that foam badly, for either small-or large-diameter towers involving veiy low allowable pressure drops, and for small-scale operations requiring diameters of less than 0.6 m (2 ft). The type of packing is selected on the basis of resistance to corrosion, mechanical strength, capacity for handling the required flows, mass-transfer efficiency, and cost. Economic factors are discussed later in this sec tion. 

The choice of a bubble column or an agitated vessel depends primarily on the solubihty of the gas in the liquid, the corrosiveness of the liquid (often a gas compressor can be made of inexpensive material, whereas a mechanical agitator may have to be made of exotic, expensive materials), and the rate of chemical reac tion as compared with the mass-transfer rate. Bubble columns and agitated vessels are seldom used for gas absorption except in chemical reac tors. As a general rule. 

Engineering factors include (a) contaminant characteristics such as physical and chemical properties - concentration, particulate shape, size distribution, chemical reactivity, corrosivity, abrasiveness, and toxicity (b) gas stream characteristics such as volume flow rate, dust loading, temperature, pressure, humidity, composition, viscosity, density, reactivity, combustibility, corrosivity, and toxicity and (c) design and performance characteristics of the control system such as pressure drop, reliability, dependability, compliance with utility and maintenance requirements, and temperature limitations, as well as size, weight, and fractional efficiency curves for particulates and mass transfer or contaminant destruction capability for gases or vapors. 

Over the years the original Evans diagrams have been modified by various workers who have replaced the linear E-I curves by curves that provide a more fundamental representation of the electrode kinetics of the anodic and cathodic processes constituting a corrosion reaction (see Fig. 1.26). This has been possible partly by the application of electrochemical theory and partly by the development of newer experimental techniques. Thus the cathodic curve is plotted so that it shows whether activation-controlled charge transfer (equation 1.70) or mass transfer (equation 1.74) is rate determining. In addition, the potentiostat (see Section 20.2) has provided... 

Flow thins protective film to equilibrium thickness which is a function of both mass transfer rate and growth kinetics. Erosion corrosion rate is controlled by the dissolution rate of the protective film. 

It can be obtained from the available literature or measured experimentally. If the erosion corrosion rate (ECR) is directly proportional to the mass transfer rate ... 

However the expected simple linear relationship between mass transfer and erosion corrosion does not always hold for a variety of reasons which include ... 

If the film is removed above a certain mass transfer rate there will be a sudden increase in the erosion corrosion rate which will tend to rise to the rate the bare metal can dissolve. 

Corrosion involves both anodic and cathodic reactions and the localisation of these can lead to lack of conformity with mass transfer expectations... 

A number of workers have suggested that there are situations in which two processes in series control the erosion corrosion rate, for example diflfusion plus partial activation control, leading to a lower dependency on mass transfer than expected. 

Bignold has postulated that increasing flow increases both mass transfer and by lowering the free corrosion potential the oxide solubility. This would lead to a higher dependency on mass transfer than expected. 

Most mass transfer data is for smooth surfaces . It is well established that as a surface suffers erosion corrosion it will roughen and the mass transfer rate will increase. It has been suggested that when this occurs the roughness becomes more important than the original shape in controlling the mass transfer. 

Examples of some of these effects and the resulting mass transfer erosion corrosion behaviour are shown in Figure 1.92. 

Fig, 1.92 Possible relationships between erosion corrosion and mass transfer (after... 

Under certain conditions, it will be impossible for the metal and the melt to come to equilibrium and continuous corrosion will occur (case 2) this is often the case when metals are in contact with molten salts in practice. There are two main possibilities first, the redox potential of the melt may be prevented from falling, either because it is in contact with an external oxidising environment (such as an air atmosphere) or because the conditions cause the products of its reduction to be continually removed (e.g. distillation of metallic sodium and condensation on to a colder part of the system) second, the electrode potential of the metal may be prevented from rising (for instance, if the corrosion product of the metal is volatile). In addition, equilibrium may not be possible when there is a temperature gradient in the system or when alloys are involved, but these cases will be considered in detail later. Rates of corrosion under conditions where equilibrium cannot be reached are controlled by diffusion and interphase mass transfer of oxidising species and/or corrosion products geometry of the system will be a determining factor. 

Mass-transfer deposits can lead to blockages in non-isothermal circulating systems, cis in the case of liquid-metal corrosion. In fused salts, the effect can be reduced by keeping contamination of the melt by metal ions to a minimum e.g. by eliminating oxidising impurities or by maintaining reducing conditions over the melt . 

Sodium, potassium and sodium-potassium alloys Liquid sodium, potassium or alloys of these elements have little effect on niobium at temperatures up to 1 000°but oxygen contamination of sodium causes an increase in corrosionSodium does not alloy with niobium . In mass transfer tests, niobium exposed to sodium at 600°C exhibited a corrosion rate of approximately 1 mgcm d . However, in hot trapped sodium at 550°C no change of any kind was observed after 1 070 h . 

Fig. 10.5 Polarisation diagram representing corrosion and cathodic protection when the cathodic process is under mass transfer control. The values of fcorr and /cor, are lower than when there is no mass transfer restriction, i.e. when the cathodic kinetics follow the dotted line...

Mass transfer This phenomenon manifests itself as the physical transport of a metal from one portion of the system to another, and may occur when there is an alloy compositional difference or a temperature gradient between parts of the unit joined by the flowing liquid phase. An exceedingly small solubility of the metal component or corrosion product in the molten metal or salt appears sufficient to permit mass transfer to proceed at a fairly rapid pace. 

In general, it is fair to state that one of the major difficulties in interpreting, and consequently in establishing definitive tests of, corrosion phenomena in fused metal or salt environments is the large influence of very small, and therefore not easily controlled, variations in solubility, impurity concentration, temperature gradient, etc. . For example, the solubility of iron in liquid mercury is of the order of 5 x 10 at 649°C, and static tests show iron and steel to be practically unaltered by exposure to mercury. Nevertheless, in mercury boiler service, severe operating difficulties were encountered owing to the mass transfer of iron from the hot to the cold portions of the unit. Another minute variation was found substantially to alleviate the problem the presence of 10 ppm of titanium in the mercury reduced the rate of attack to an inappreciable value at 650°C as little as 1 ppm of titanium was similarly effective at 454°C . 

The parameter p (= 7(5 ) in gas-liquid sy.stems plays the same role as V/Aex in catalytic reactions. This parameter amounts to 10-40 for a gas and liquid in film contact, and increases to lO -lO" for gas bubbles dispersed in a liquid. If the Hatta number (see section 5.4.3) is low (below I) this indicates a slow reaction, and high values of p (e.g. bubble columns) should be chosen. For instantaneous reactions Ha > 100, enhancement factor E = 10-50) a low p should be selected with a high degree of gas-phase turbulence. The sulphonation of aromatics with gaseous SO3 is an instantaneous reaction and is controlled by gas-phase mass transfer. In commercial thin-film sulphonators, the liquid reactant flows down as a thin film (low p) in contact with a highly turbulent gas stream (high ka). A thin-film reactor was chosen instead of a liquid droplet system due to the desire to remove heat generated in the liquid phase as a result of the exothermic reaction. Similar considerations are valid for liquid-liquid systems. Sometimes, practical considerations prevail over the decisions dictated from a transport-reaction analysis. Corrosive liquids should always be in the dispersed phase to reduce contact with the reactor walls. Hazardous liquids are usually dispensed to reduce their hold-up, i.e. their inventory inside the reactor. 

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