Ammonia stress

Final Purification. Oxygen containing compounds (CO, CO2, H2O) poison the ammonia synthesis catalyst and must be effectively removed or converted to inert species before entering the synthesis loop. Additionally, the presence of carbon dioxide in the synthesis gas can lead to the formation of ammonium carbamate, which can cause fouHng and stress-corrosion cracking in the compressor. Most plants use methanation to convert carbon oxides to methane. Cryogenic processes that are suitable for purification of synthesis gas have also been developed. 

Ammonia is corrosive to akoys of copper and zinc and these materials must not be used in ammonia service. Iron or steel should usuaky be the only metal in ammonia storage tanks, piping, and fittings. It is recommended that ammonia should contain at least 0.2% water to prevent steel stress corrosion. Mercury thermometers should be avoided. 

Stress corrosion is cracking that develops in sensitive aHoys under tensile stress which is either internally imposed or is a residual after forming, in environments such as the presence of amines and moist ammonia. The crack path can be either intercrystaHine or transcrystaHine, depending on aHoy and environment. Not aH aHoys are susceptible to stress corrosion (31). 

The relative susceptibHity of several commercial aHoys is presented in Table 8. The index used is a relative rating based on integrating performance in various environments. These environments include the harsh condition of exposure to moist ammonia, Hght-to-moderate industrial atmospheres, marine atmosphere, and an accelerated test in Mattsson s solution. The latter testing is described in ASTM G30 and G37 (35,36) and is intended to simulate industrial atmospheres. The index is linear. A rating of 1000 relates to the most susceptible and zero designates immunity to stress corrosion. 

Corrosion also occurs as a result of the conjoint action of physical processes and chemical or electrochemical reactions (1 3). The specific manifestation of corrosion is deterrnined by the physical processes involved. Environmentally induced cracking (EIC) is the failure of a metal in a corrosive environment and under a mechanical stress. The observed cracking and subsequent failure would not occur from either the mechanical stress or the corrosive environment alone. Specific chemical agents cause particular metals to undergo EIC, and mechanical failure occurs below the normal strength (5aeld stress) of the metal. Examples are the failure of brasses in ammonia environments and stainless steels in chloride or caustic environments. 

Virtuallv evety alloy system has its specific environment conditions which will prodiice stress-corrosion cracking, and the time of exposure required to produce failure will vary from minutes to years. Typical examples include cracking of cold-formed brass in ammonia environments, cracking of austenitic stainless steels in the presence of chlorides, cracking of Monel in hydrofluosihcic acid, and caustic embrittlement cracking of steel in caustic solutions. 

Brasses with up to 15 percent Zn are ductile but difficult to machine. Machinability improves with increasing zinc up to 36 percent Zn. Brasses with less than 20 percent Zn have corrosion resistance eqmvalent to that of copper but with better tensile strengths. Brasses with 20 to 40 percent Zn have lower corrosion resistance and are subject to dezincincation and stress-corrosion cracking, especially when ammonia is present. 

Finally, any living organism dies. Decomposition may generate ammonia at local concentrations high enough to produce stress-corrosion cracking of brass condenser tubes (Fig. 6.1). 

Figure 6.1 Stress-corrosion cracking of a brass condenser tube caused by ammonia from decomposing slime masses lodged on internal surfaces.

Figure 9.4 Both longitudinal and transverse stress-corrosion cracks on a brass heat exchanger tube that had been exposed to ammonia. Note the branching of the cracks.

The longitudinal orientation of these cracks reveals that hoop (circumferential) stresses caused by internal pressurization provided the necessary stresses. Ammonia was the specific corrodent involved. 

The confinement of the cracks to a specific area of the cooler suggests that condensate from atmospheric moisture initially formed in this area and dissolved a corrodent from the atmosphere such as ammonia, sulfur dioxide, or oxides of nitrogen. Since the previous cooler had been in service for 20 years, it is conjectured that the rapid failure of this exchanger was due principally to very high bending stresses, which may have been induced during construction of the cooler. 

Steam condensed in a thin film along the cold tube surface. This thin film of condensate then dissolved ammonia and oxygen present in the steam, which, in combination with stress, produced the observed cracking. 

In some materials and environments, cracks grow steadily under a constant stress intensity K which is much less than (Fig. 23.8). This is obviously dangerous a structure which is safe when built can become unsafe with time. Examples are brass in ammonia, mild steel in caustic soda, and some A1 and Ti alloys in salt water. 

When restarting an installation that is still moderately hot, diffieulty is often experieneed during the initial phase due to the use of saturated steam (from the auxiliary boiler), whieh is eooler than the superheated steam raised by ammonia eombustion. Consequently, a sturdy steam turbine must be ehosen, eapable of withstanding the thermal stresses imposed. 

Embrittlement embrittlement and for improperly heat treated steel, both of which give intergranular cracks. (Intercrystalline penetration by molten metals is also considered SCC). Other steels in caustic nitrates and some chloride solutions. Brass in aqueous ammonia and sulfur dioxide. physical environments. bases of small corrosion pits, and cracks form with vicious circle of additional corrosion and further crack propagation until failure occurs. Stresses may be dynamic, static, or residual. stress relieve susceptible materials. Consider the new superaustenitic stainless steels. 

Certain environments containing nitrate, cyanide, carbonate, amines, ammonia or strong caustic, due to the risk of stress corrosion cracking. Temperature is an important factor in assessment of each cracking environment ... 

Single-phase a-brasses are susceptible to stress-corrosion cracking in the presence of moist ammonia vapour or certain ammonium compounds Here the predominant metallurgical variable is alloy composition, and in... 

Nitrogen compounds These also arise from both natural and synthetic sources. Thus ammonia is formed in the atmosphere during electrical storms, but increases in the ammonium ion concentration in rainfall over Europe in recent years are attributed to increased use of artiflcial fertilisers. Ammonium compounds in solution may increase the wettability of a metaland the action of ammonia and its compounds in causing season cracking , a type of stress-corrosion cracking of cold-worked brass, is well documented. 

Neutral and alkaline solutions Copper-base materials are resistant to alkaline solutions " over a wide range of conditions but may be appreciably attacked by strong solutions, particularly if hot. Copper/nickel alloys usually give the best results in alkaline solutions. Copper and copper alloys should be avoided if ammonia is present, owing to the danger of both general corrosion and, if components are under stress, stress corrosion. 

Only certain specific environments appear to produce stress corrosion of copper alloys, notably ammonia or ammonium compounds or related compounds such as amines. Mercury or solutions of mercury salts (which cause deposition of mercury) or other molten metals will also cause cracking, but the mechanism is undoubtedly differentCracks produced by mercury are always intercrystalline, but ammonia may produce cracks that are transcrystalline or intercrystalline, or a mixture of both, according to circumstances. As an illustration of this, Edmundsfound that mercury would not produce cracking in a stressed single crystal of brass, but ammonia did. 

The behaviour of a wide range of a, a-0 and /3 brasses in various corrosive environments was studied by Voce and Bailey and the results summarised by Whitaker . Penetration by mercury and by molten solder was intercrystalline in all three types of brass. In moist ammoniacal atmospheres the penetration of unstressed brasses of all types was intercrystalline. Internal or applied stresses accelerated the intercrystalline penetration of a brasses and initiated some transcrystalline cracking, and also caused severe transcrystalline cracking of /3 alloys and transcrystalline cracking across the 0 regions in the two-phase brasses. Immersion in ammonia solution, however, caused intercrystalline cracking of stressed 0 brasses. 

Stress-corrosion cracking (Section 8.10) New metal/environment combinations which produce stress-corrosion cracking are continually being found. Combinations discovered in service in recent years include titanium in red fuming nitric acid carbon steel in liquid anhydrous ammonia and in... 

For carbon steels, however, a full stress-relief heat treatment (580-620°C) has proved effective against stress-corrosion cracking by nitrates, caustic solutions, anhydrous ammonia, cyanides and carbonate solutions containing arsenite. For nitrates, even a low-temperature anneal at 350°C is effective, while for carbonate solution containing arsenite the stress-relief conditions have to be closely controlled for it to be effective . 

Cracknell, A., Stress corrosion cracking of steel in ammonia an update of operating experience. In Proceedings of AlChE Symposium on Safety in Ammonia Plants and Related Facilities, Los Angeles, 1982 (1982)... 

Lunde, L., and Nyborg, R., Stress corrosion cracking of different steels in liquid and vaporous ammonia. In Proceedings of Corrosion 87, San Francisco, 1987, paper 174, NACE, Houston (1987)... 

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