Stainless steels in a corrosive environment like ammonium carbamate owe their corrosion resistance to the presence of a protective oxide

layer on the surface. As long as this layer is intact, the metal corrodes only at a very low rate. Passive corrosion rates in liquid phases are generally between 0.01 and 0.1mm/year. In gas phases where mixtures of ammonia, carbon dioxide and water vapour can condense to form carbamate solutions passive corrosion rates can increase to 0.2mm/year. Active corrosion rates in carbamate solutions can be as high as 50mm/year. Stainless steels exposed to carbamate-containing solutions in urea synthesis section can be kept in a passivated state by adding a given amount of oxygen. If the oxygen content drops below this limit, acive corrosion starts after some time. Adding oxygen and maintaining a sufficiently high oxygen content in the various process streams are prerequisites to preventing corrosion of the equipment and pipelines. From the point of view of corrosion prevention, condensation of NH3-CO2-H2O gas mixtures to carbamate solutions warrants extra attention. Despite the presence of oxygen, a more corrosive condensate is initially formed on condensation. Passivation is believed to take place via a metal ion redox system, which is missing in freshly formed condensate. This accounts for the severe corrosion sometimes observed in cold spots in the channels of HP equipment and gas lines fabricated from urea grade 316L. Such corrosion can be prevented by adequate insulation and tracing. When condensation forms part of the process, as in the HP carbamate condenser, special technological measures must be taken. One such measure is adding an oxygen-rich liquid phase containing a metal ion redox system into the condenser, with liquid-gas distribution devices preventing dry spots on surfaces where condensation takes place. The risk of condensation corrosion can also be diminished by choosing a more corrosionresistant material of onstruction. The higher alloyed austenitic stainless steeltype X2CrNiMoN 25 22 2 is less susceptible to condensation corrosion than urea grade 316L. Type X2CrNiMoN 22 5 3 duplex stainless steel has proved to be more corrosion-resistant in condensing environments too. Another benefit of duplex stainless steels is their higher strength. Duplex high-pressure piping can be much thinner than austeniticstainless steel piping. During a turnaround in October 1996, after being on-stream for about 28 years, the strip gas line from the HP stripper (d) to the HP carbamate condenser (e) had to be replaced due to condensation corrosion. The urea grade 316L line, measuring 219 X 22.2mm and 70 m long had a corrosion allowance of about 6mm. For duplex stainless steel a corrosion allowance of 4mm will do, so leading to 219 X 14mm pipe. Replacement by type X2CrNiMoN 22 5 3 duplex (seamless hot extruded) pipe gave a cost saving of about 10%. Another advantage of duplex is its high resistance to chloride stress corrosion cracking. This can be particularly relevant for plants in coastal areas. Such piping in austenitic stainless steel needs to be suitably painted to minimise the risk of SCC. Duplex stainless steel piping need not be painted. Stress corrosion cracking in HP carbamate condenser The ammonia and carbon dioxide leaving the stripper are condensed in the HP carbamate condenser (e) at synthesis pressure. The heat released in the formation of ammonium carbamate is used for the production of 4.5 bar steam. Any chlorides entering the shell side of the HP carbamate condenser are likely to initiate stress corrosion cracking of the austenitic stainless steel tubes, starting from the outside surface of the tubes. Numerous cases of stress corrosion cracking are on record. Cracking has been observed in both urea grade 316L and

X2CrNiMoN 25 22 2 tubes. An example of stress corrosion cracking a urea grade AISI 316L HP carbamate condenser tube is shown in figure 2. The location of the cracks is indicated in figure 3 for expanded-and-welded tubes and for welded tubes. Stamicarbon does not allow the tubes to be expanded in the tubesheet because this would render the leak detection system in operative tube joints. In most cases cracking merely occurred in or near the top tubesheet. The locations have been found to depend on theorigin of the chloride contamination. The following causes of SCC in HP carbamate condensers have been identified:

Chloride contamination of water used for hydrostatic testing, cleaning or flushing. Transport and storage in a chloride-containing (maritime) atmosphere (infiltration as a result of breathing due to cyclic temperature changes). Chloride contamination of boiler feed water (e.g. leakage of vent condenser in steam condensate tank). The steam and condensate system in the urea process is shown in figure 4. SCC in HP carbamate condensers can be avoided by changing the corrosive environment (inhibition) or by using a material that is more resistant to chloride SCC: The chloride content of water used for hydrostatic testing, flushing or cleaning should be less than 1 ppm. As an additional precaution it is advised to inhibit the water with 2% TSP (trisodium phosphate). During transport and storage in a chloride-containing atmosphere the equipment should be inerted with nitrogen (0.3-0.5 bar gauge). The chloride content of the blow-down should be less than 0.2 ppm. The oxygen content should be zero; this will be the case when the blow-down contains excess oxygen scavenger (0.1-0.5 ppm). If chloride contamination cannot be avoided, continuous inhibition with TSP should be considered. Application of a more SCC-resistant material like type X2CrNiMoN 22 5 3 duplex

stainless steel. For existing carbamate condensers the remedies were focused on changing the environment but for new equipment the use of duplex stainless steel was considered. We had gained ample experience with such steels in terms of SCC resistance. In a naphtha cracking plant of DSM two process steam generators, with U-bundles in type X2CrNiMoN 22 5 3 duplex stainless steel, have been in service since 1988. Conditions on the shell side are even more severe than in carbamate condensers. Steam is generated from chloride-containing process condensate (average chloride content 10 ppm with pH varying from 4-12) at a temperature of 180C. The carbon steel tubesheet is overlay welded with AISI 309L (X2CrNi 24 12). The duplex stainless steel tubes were automatically welded (GTAW) with 309S/309Mo welding consumable. The tubes were lightly expanded within the tubesheet over a length of 25mm. The thickness of the tubesheet is 193mm. A light hydraulic expansion cannot prevent crevices between the tubes and the tubesheet. The horizontal bundle is not fully immersed, accumulation of corrosive components like chlorides is likely to occur in the wet/dry zone. Until now, after about nine years on stream, no corrosion has been observed in these steam generators. In numerous other applications we found that duplex stainless steels offer good SCC-resistance at pH values above about 4. At lower pH values the advantage of duplex stainless steels over austenitic stainless steel diminishes. This has been confirmed in stress corrosion cracking experiments by means of Constant Extension Rate Testing (CERT) (ref. 1, 3). Duplex stainless steel test coupons have been exposed in the HP synthesis section of the DSM urea plant since the mid-seventies. The average corrosion rate of X2CrNiMoN 22 5 3 proved to be as follows:

top of reactor: 0.04mm/year top of stripper: 0.08mm/year top of HP carbamate condenser: 0.03mm/year

The corrosion rates of duplex stainless steel in the urea reactor and in the HP carbamate condenser are comparable with those of X2CrNiMoN 25 22 2. The measured corrosion rate of duplex in the stripper is slightly higher than that of type X2CrNiMoN 25 22 2 steel. Based on these results and experience with chloride-containing environments, we wondered if the chloride stress corrosion cracking problems in the HP carbamate condenser could be resolved by using duplex stainless steel instead of urea grade 316L or X2CrNiMoN 25 22 2. In order to assess the corrosion resistance of duplex stainless steel, we installed three tubes of X2CrNiMoN 22 5 3 in the HP carbamate condenser of the DSM urea plant for a period of 1.5 years. After this period, a maximum decrease in wall thickness of 0.05mm was found. Corrosion was slightly intergranular and had propagated via the ferrite/austenite grain boundaries (figure 5). In October 1993, the first HP carbamate condenser and HP scrubber with duplex stainless steel tubes and tube sheets overlay welded with duplex stainless steel were installed in a urea plant. In September 1996, after 3 years on stream, the HP heat exchangers were checked by visual inspection and eddy current measurements of the tubes. This inspection revealed no signs of corrosion, neither of the overlay welding and tube-totubesheet joints, nor of the tubes. A HP carbamate condenser with duplexstainless steel tubes and overlay weldedtubesheets is only slightly more expensive than the same unit in urea grade AISI 316L and about 5% cheaper than one in X2CrNiMoN 25 22 2. Three other HP heat exchangers with duplex stainless steel tubes and overlay welded tubesheets are now under construction. Corrosion of HP stripper tubes In the stripper the unconverted carbamate is decomposed and the ammonia and carbon dioxide are stripped off. Stripping is effected by countercurrent contact between the urea solution and carbon dioxide at synthesis pressure. The stripper is the falling film type. Liquid dividers with gas tubes are positioned on the protruding tube ends with the joints being sealed with PTFE bushes. Process conditions are severest in the stripper, especially at the top of the tubes, due to the relatively low oxygen partial pressure and high tubewall temperature. In the Stamicarbon urea stripping plants the stripper tubes are fabricated from X2CrNiMoN 25 22 2. The corrosion rate of this material in these conditions is 0.05mm/year, which is quite low. If a liquid divider with PTFE bush is not properly seated a higher corrosion rate may occur due to flooding in the tube. Figure 6 shows part of a seriously corroded stripper tube due to flooding. Given the performance of duplex stainless steels in oxygen-containing and oxygen-free carbamate solutions we feel sure that a duplex high in chromium and nitrogen and low in nickel will give good performance even in these extreme conditions.