Cooling water, corrosion

Sulfate reducers. The best-known form of microbiologically influenced corrosion involves sulfate-reducing bacteria.- Without question, sulfate reducers cause most localized industrial cooling water corrosion associated with bacteria. Desulfovibrio, Desulfomonas, and Desulfotomacu-lum are three genera of sulfate-reducing bacteria. 

Organic toxic pollutants and chromium are present in the raw wastewater and normally consist of raw materials, impurities, and metals used as cooling water corrosion inhibitors. 

Corn-Bat [Betz Industrial] Alkaline cooling water corrosion and scale in-hibitots. 

One early approach for cooling water corrosion inhibition was the use of inorganic polyphosphates. These complex molecularly dehydrated phosphates came into widespread industrial use beginning in the 1930 s. 

Maruthi, B. N. Mayanna, S. M. Substituted and unsubstituted sahcylaldehyde semicarbazones as cooling water corrosion inhibitors. Indian J. Ghent. Technol. 1994,1, 275-278. 

J3]Degnan, T. F. and Fynsk, A. W., Improved Techniques for Cooling Water Corrosion Control, presented at Cooling Water Symposium, 21st NACE Conference, St. Louis, MO, 15-19 March 1965. 

In addition to NACE Standard RP-62-72, for more details of the economics of corrosion control in recirculating cooling systems see Economic Data on Chemical Treatment of Gulf Coast Cooling Waters, Corrosion, 11, 61-62 (1965) Nov., reported by the NACE Recirculating Cooling Water Sub-Committee. 

Cooling water systems are dosed with corrosion inhibitors, polymers to prevent solid deposition, and biocides to prevent the growth of microorganisms. 

Water as coolant in a nuclear reactor is rendered radioactive by neutron irradiation of corrosion products of materials used in reactor constmction. Key nucHdes and the half-Hves in addition to cobalt-60 are nickel-63 [13981 -37-8] (100 yr), niobium-94 [14681-63-1] (2.4 x 10 yr), and nickel-59 [14336-70-0] (7.6 x lO" yr). Occasionally small leaks in fuel rods allow fission products to enter the cooling water. Cleanup of the water results in LLW. Another source of waste is the residue from appHcations of radionucHdes in medical diagnosis, treatment, research, and industry. Many of these radionucHdes are produced in nuclear reactors, especially in Canada. 

Not only may the cooling-tower plume be a source of fog, which in some weather conditions can ice roadways, but the plume also carries salts from the cooling water itself. These salts may come from salinity in the water, or may be added by the cooling-tower operator to prevent corrosion and biological attack in the column. 

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. 

The best way to prevent crevice corrosion is to prevent crevices. From a cooling water standpoint, this requires the prevention of deposits on the metal surface. Deposits may be formed by suspended soHds (eg, silt, siUca) or by precipitating species, such as calcium salts. 

Scaling is not always related to temperature. Calcium carbonate and calcium sulfate scaling occur on unheated surfaces when their solubiUties are exceeded in the bulk water. Metallic surfaces are ideal sites for crystal nucleation because of their rough surfaces and the low velocities adjacent to the surface. Corrosion cells on the metal surface produce areas of high pH, which promote the precipitation of many cooling water salts. Once formed, scale deposits initiate additional nucleation, and crystal growth proceeds at an accelerated rate. 

Foulants enter a cooling system with makeup water, airborne contamination, process leaks, and corrosion. Most potential foulants enter with makeup water as particulate matter, such as clay, sdt, and iron oxides. Insoluble aluminum and iron hydroxides enter a system from makeup water pretreatment operations. Some well waters contain high levels of soluble ferrous iron that is later oxidized to ferric iron by dissolved oxygen in the recirculating cooling water. Because it is insoluble, the ferric iron precipitates. The steel corrosion process is also a source of ferrous iron and, consequendy, contributes to fouling. 

Continuous chlorination of a cooling water system often seems most pmdent for microbial slime control. However, it is economically difficult to maintain a continuous free residual in some systems, especially those with process leaks. In some high demand systems it is often impossible to achieve a free residual, and a combined residual must be accepted. In addition, high chlorine feed rates, with or without high residuals, can increase system metal corrosion and tower wood decay. Supplementing with nonoxidizing antimicrobials is preferable to high chlorination rates. 

Hydrogenations can be carried out in batch reactors, in continuous slurry reactors, or in fixed-bed reactors. The material of constmetion is usually 316 L stainless steel because of its better corrosion resistance to fatty acids. The hydrogenation reaction is exothermic and provisions must be made for the effective removal or control of the heat a reduction of one IV per g of C g fatty acid releases 7.1 J (1.7 cal), which raises the temperature 1.58°C. This heat of hydrogenation is used to raise the temperature of the fatty acid to the desired reaction temperature and is maintained with cooling water to control the reaction. 

Organophosphonates are similar to polyphosphates in chelation properties, but they are stable to hydrolysis and replace the phosphates where persistence in aqueous solution is necessary. They are used as scale and corrosion inhibitors (52) where they function via the threshold effect, a mechanism requiring far less than the stoichiometric amounts for chelation of the detrimental ions present. Threshold inhibition in cooling water treatment is the largest market for organophosphonates, but there is a wide variety of other uses (50). 

The three major forms of concentration cell corrosion are crevice corrosion, tuberculation, and underdeposit attack. Each form of corrosion is common in cooling systems. Many corrosion-related problems in the cooling water environment are caused by these three forms of wastage. The next three chapters—Chap. 2, Crevice Corrosion, Chap. 3, Tuberculation, and Chap. 4, Underdeposit Corrosion — will discuss cooling water system corrosion problems. 

As the name implies, crevice corrosion occurs between two surfaces in close proximity, such as a crack. Table 2.1 gives a partial listing of common crevice corrosion sites in cooling water systems. 

A test water box was installed during a 2-week trial to monitor corrosion and fouling in a utility cooling water system. A baffle plate from the test box was removed after the test. Small, hollow incipient tubercles dotted surfaces (Fig. 3.28). Small amounts of carbonate were present atop and around each tubercle. Each tubercle capped a small depression no deeper than 0.005 in. (0.013 cm) (Fig. 3.29). This indicated local average corrosion rates were as high as 130 mihy (3.3 mm/y). 

Cooling water was used to cool hot aluminum. Calcium carbonate spotting had occurred at alkaline pH. After reducing pH, the staining problem disappeared, but corrosion increased substantially. 

Attack always occurs beneath a deposit. Cooling water system deposits are ubiquitous. Deposits can be generated internally as precipitates, laid down as transported corrosion products, or brought into the system from external sources. Hence, underdeposit corrosion can be found in virtually any cooling water system at any location. Especially troubled... 

Almost all cooling water system deposits are waterborne. It would be impossible to list each deposit specifically, but general categorization is possible. Deposits are precipitates, transported particulate, biological materials, and a variety of contaminants such as grease, oil, process chemicals, and silt. Associated corrosion is fundamentally related to whether deposits are innately aggressive or simply serve as an occluding medium beneath which concentration cells develop. An American... 

Calcium carbonate makes up the largest amount of deposit in many cooling water systems (Fig. 4.16) and can be easily detected by effervescence when exposed to acid. Deposits are usually heavily stratified, reflecting changes in water chemistry, heat transfer, and flow. Corrosion may be slight beneath heavy accumulations of fairly pure calcium carbonate, as such layers can inhibit some forms of corrosion. When nearly pure, calcium carbonate is white. However, calcium carbonates are often intermixed with silt, metal oxides, and precipitates, leading to severe underdeposit attack. 

Petroleum greases and oils can be excellent corrosion inhibitors on a variety of alloys. The hydrophobic layer produced by oil or grease can prevent water from contacting surfaces and can, therefore, almost eliminate corrosion. Unfortunately, the addition of oil and grease cannot be recommended as a corrosion-reduction measure in cooling water systems for three basic reasons. 

Substituting one alloy for another may be the only viable solution to a specific corrosion problem. However, caution should be exercised this is especially true in a cooling water environment containing deposits. Concentration cell corrosion is insidious. Corrosion-resistant materials in oxidizing environments such as stainless steels can be severely pitted when surfaces are shielded by deposits. Each deposit is unique, and nature can be perverse. Thus, replacement materials ideally should be tested in the specific service environment before substitution is accepted. 

Cracking was caused by stress-corrosion cracking (see Chap. 9, Stress-Corrosion Cracking ) involving hydrogen sulfide and/or moist sulfur dioxide. The sulfur entered the cooling water stream through process leaks, which were repaired. 

When a clean steel coupon is placed in oxygenated water, a rust layer will form quickly. Corrosion rates are initially high and decrease rapidly while the rust layer is forming. Once the oxide forms, rusting slows and the accumulated oxide retards diffusion. Thus, Reaction 5.2 slows. Eventually, nearly steady-state corrosion is achieved (Fig. 5.2). Hence, a minimum exposure period, empirically determined by the following equation, must be satisfied to obtain consistent corrosion-rate data for coupons exposed in cooling water systems (Figs. 5.2 and 5.3) ... 

Figure 5.2 Schematic of carbon steel corrosion rate versus exposure time in a typical oxygenated cooling water. Note how the average corrosion rate decreases with time and converges to CR at t (the minimum exposure time to get reproducible results).

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