Anode protection

Riggs O L and Locke C E 1981 Anodic Protection Theory and Practice in the Prevention of Corrosion (New York Plenum)... 

Anodic passivation and its appHcation to sulfuric acid equipment such as stainless steel acid coolers and carbon steel storage tanks has been weU studied (102—104). More recently, sheU and tube coolers made from Sandvik SX or Saramet have been installed in several acid plants. These materials do not requHe anodic protection. 

Plate and frame coolers using HasteUoy C-276 plates have been used successfuUy. Anodically protected plate coolers are available as weU as plate coolers with plates welded together to minimize gasketing. Another promising development is the introduction of plate coolers made of HasteUoy D205 (105). This aUoy has considerably better corrosion resistance to concentrated sulfuric acid at higher temperatures than does C-276. Because of the close clearance between plates, cooling water for plate coolers must be relatively clean. 

Anodic Inhibitors. Passivating or anodic inhibitors produce a large positive shift in the corrosion potential of a metal. There are two classes of anodic inhibitors which are used for metals and alloys where the anodic shift in potential promotes passivation, ie, anodic protection. The fkst class includes oxidking anions that can passivate a metal in the absence of oxygen. Chromate is a classical example of an oxidking anodic inhibitor for the passivation of steels. 

Anodic Protection This electrochemical method relies on an external potential control system (potentiostat) to maintain the metal or alloy in a noncorroding (passive) condition. Practical applications include acid coolers in sulfuric acid plants and storage tanks for sulfuric acid. 

Anodic Protection On the reverse anodic scan there will be a low current region (LCB) in the passive range. The passive potential range of the LCB is generally much narrower than the passive region seen on a forward slow scan. In anodic protection (AP) work the midpoint of the LCB potential is the preferred design range. This factor was verified for sulfuric acid in our laboratory and field studies. 

Note that zinc anodes are often used to protect steel and other relatively noble metals cathodically. In this case, the fasteners were acting as unintentional sacrificial anodes, protecting the stainless steel. Simple solutions to the problem would be to insulate the fasteners from the stainless steel electrically or to use stainless steel fasteners. 

These three passive systems are important in the technique of anodic protection (see Chapter 21). The kinetics of the cathodic partial reaction and therefore curves of type I, II or III depend on the material and the particular medium. Case III can be achieved by alloying additions of cathodically acting elements such as Pt, Pd, Ag, and Cu. In principle, this is a case of galvanic anodic protection by cathodic constituents of the microstructure [50]. 

Fatigue life can be slightly lengthened by anodic protection or by passivation. In acids even passive stainless CrNi steels suffer corrosion fatigue [104]. Resistance can occur if the passive film itself has a fatigue strength (e.g., in neutral waters [105]). 

There are limits to the use of anodic protection in the following cases ... 

In this section a survey is given of the critical protection potentials as well as the critical potential ranges for a possible application of electrochemical protection. The compilation is divided into four groups for both cathodic and anodic protection with and without a limitation of the protection range to more negative or more positive potentials respectively. 

Number Tank Volume (m ) Surface area (m ) No. of anodes Protection current (A) Voltage (V) Soil resistivity (Q m) [after Eq. (3-44)]... 

For partial protection of the stem, 33% of the anodes used for complete protection should be installed instead of the usual 25%. Of these, 25% serve as actual protection for the stem and 8% as shielding for the stem area against the remainder of the current-consuming body of the ship. These anodes are known as gathering anodes and are fixed in front of the anodes protecting the stem. 

Test potential Cu-C S04(V) Medium at the anode Protection current density (mA m ) Anode 1 Anode 2 ... 

Measures a and c in Section 2.2 are directly relevant for internal electrochemical protection. In the previous chapter examples of the application of not only cathodic protection but also anodic protection were dealt with in this connection see the basic explanation in Sections 2.2 and 2.3 and particularly in Section 2.3.1.2. 

Besides the use of anodic polarization with impressed current to achieve passivation, raising the cathodic partial current density by special alloying elements and the use of oxidizing inhibitors (and/or passivators) to assist the formation of passive films can be included in the anodic protection method [1-3]. 

Anodic Protection of Chemical Plant 21.4.1 Special Features of Anodic Protection... 

The fundamentals of this method of protection are dealt with in Section 2.3 and illustrated in Fig. 2-15. Corrosion protection for the stable-passive state is unnecessary because the material is sufficiently corrosion resistant for free corrosion conditions. If activation occurs due to a temporary disturbance, the material immediately returns to the stable passive state. This does not apply to the metastable passive state. In this case anodic protection is necessary to impose the return to the passive state. Anodic protection is also effective in the unstable passive state of the material but it must be permanently switched on, in contrast to the metastable passive state. 

Three types of anodic protection can be distinguished (1) impressed current, (2) formation of local cathodes on the material surface and (3) application of passivating inhibitors. For impressed current methods, the protection potential ranges must be determined by experiment (see information in Section 2.3). Anodic protection with impressed current has many applications. It fails if there is restricted current access (e.g., in wet gas spaces) with a lack of electrolyte and/or in the... 

Anodic Protection with Impressed Current 21.4.2.1 Preparatory Investigations... 

A particular problem arises in the anodic protection of the gas space because the anodic protection does not act here and there is a danger of active corrosion. Thus these endangered areas have to be taken account of in the design of chemical... 

Anodic protection against acids has been used in a number of processes in the chemical industry, as well as during storage and transport. It is also successful in geometrically complicated containers and tubings [12], Carbon steel can be protected from nitric and sulfuric acids. In the latter case, temperature and concentration set application limits [17]. At temperatures of up to 120°C, efficient protection can only be achieved with concentrations over 90% [ 18]. At concentrations between 67 and 90%, anodic protection can be used at up to 140°C with CrNi steels [19]. 

In sulfuric acid production involving heat recovery and recovery of waste sulfuric acid, acids of various concentrations at high temperatures can be dealt with. Corrosion damage has been observed, for example, in sulfuric acid coolers, which seriously impairs the availability of such installations. The use of anodic protection can prevent such damage. 

Anodic protection allows the use of materials under unfavorable conditions if they are also passivatable in sulfuric acid. CrNi steels [material Nos. 1.4541 (AISI 321) and 1.4571 (AISI 316 Ti)] can be used in handling sulfuric acid of 93 to 99% at temperatures up to 160°C. This enables a temperature of 120 to 160°C to be reached, which is very suitable for heat recovery. 

Anodic protection today allows safe and efficient protection of air coolers and banks of tubes in sulfuric acid plants. In 1966 the air cooler in a sulfuric acid plant in Germany was anodically protected. Since then more than 10,000 m of cooling surfaces in air- and water-cooled sulfuric acid plants worldwide have been protected. The dc output supply of the potentiostats amounts to >25 kW, corresponding to an energy requirement of 2.5 W per m of protected surface. As an example. Fig. 21-9 shows two parallel-connected sulfuric acid smooth tube exchangers in a production plant in Spain. 

Fig. 21-10 Diagram for the internal anodic protection of a sulfonation plant.

Economic heat recovery could be achieved in certain cases by the further development of anodic protection at higher temperatures. High temperatures allow the production of steam and lead to a considerable increase in efficiency [20]. 

Anodic protection is particularly suitable for stainless steels in acids. Protection potential ranges are given in Section 2.4. Besides sulfuric acid, other media such as phosphoric acid can be considered [13,21-24]. These materials are usually stable-passive in nitric acid. On the other hand, they are not passivatable in hydrochloric acid. Titanium is also a suitable material for anodic protection due to its good passivatability. 

Carbon steels can be anodically protected in certain salt solutions. This involves mainly products of the fertilizer industry such as NH3, NH4NO3 and urea. Anodic protection is effective up to 90°C [26]. Corrosion in the gas space is suppressed by control of pH and maintenance of a surplus of NH3. 

Stress corrosion can arise in plain carbon and low-alloy steels if critical conditions of temperature, concentration and potential in hot alkali solutions are present (see Section 2.3.3). The critical potential range for stress corrosion is shown in Fig. 2-18. This potential range corresponds to the active/passive transition. Theoretically, anodic protection as well as cathodic protection would be possible (see Section 2.4) however, in the active condition, noticeable negligible dissolution of the steel occurs due to the formation of FeO ions. Therefore, the anodic protection method was chosen for protecting a water electrolysis plant operating with caustic potash solution against stress corrosion [30]. The protection current was provided by the electrolytic cells of the plant. 

Six caustic soda evaporators were anodically protected against stress corrosion in the aluminum industry in Germany in 1965 [27]. Each evaporator had an internal surface area of 2400 m. The transformer-rectifier had a capacity of 300 AJ 5 V and was operated intermittently for many years. Automatic switching on of the protection current only took place in case of need when the drop in potential reached... 

The external heating boxes for the caustic soda evaporator with forced circulation must be anodically protected separately. Ring-shaped impressed current electrodes of carbon steel are mounted and insulated on supporting brackets (see Fig, 21-12). 

The safety, availability and capacity of production plants are predetermined by the quality of the materials and the corrosion protection measures in the essential areas both are major considerations in the initial planning. Even today, damage to equipment and tanks is often assumed to be unavoidable and the damaged components are routinely replaced. By carrying out damage analysis, which points the way to knowledge of prevention of damage, the availability and life of plants can be increased considerably. This particularly applies to the use of anodic protection. 

In recent years, a number of protective installations have come into operation, especially where new installations must be maintained, or where older and already damaged installations have to be saved and operating costs have to be lowered. Worldwide, equipment, tanks and evaporators in the aluminum industry and industries using caustic alkalis with a capacity of 60,000 m and a surface area of 47,000 m are being anodically protected. Equipment for electrochemical protection has been installed with a total rating of 125 kW and 12 kA. 

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