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This study reports the results of laboratory investigations in pressurized high-temperature carbon-rich environments simulating operations in syngas production and root cause failure analysis and laboratory analysis simulations in refinery platformer operations. The results rank a variety of stainless steels and Ni alloys.
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Alloy 699 XA is a new alloy, which was developed for application in petrochemical industry under metal dusting conditions at high pressure. It contains 30% chromium and 2% aluminum.
Alloys are often found to suffer much greater metal-dusting attack under high-pressure conditions compared to ambient-pressure conditions. Ultimately, the resistance of a given alloy to metal dusting depends on the formation of an oxide scale that is impermeable to carbon which, in turn, depends on scale composition and structure. This paper reports the metal-dusting behavior of several Ni-based alloys having relatively high Cr contents (about 30 wt.%) and different controlled minor levels of Fe, Al, and/or Si. Testing was conducted under 20 bar total pressure of a high-carbon-activity gas at 600 °C (1112 °F). The exposed alloys were analyzed by SEM and TEM techniques to evaluate the oxide scales and evidence of carbon ingress. It was found that aluminum is beneficial to improve metal dusting resistance by reacting to form a continuous inner layer of alumina; whereas iron is detrimental to resistance. Mechanistic aspects of the role(s) played by minor elements in affecting metal-dusting resistance are considered.
VDM Alloy 699 XA (UNS N06699, EN Alloy number 2.4842) is a new alloy, which was developed for applications in the petrochemical industry under metal dusting conditions between 400°C and 800°C. Important properties of a new material are corrosion resistance, such as to metal dusting, oxidation resistance, and workability versus high temperature strength, which are essential for industrial applications. Currently, there are material solutions which demonstrate good metal dusting resistance, but may have issues with workability. In addition, there are also minimum requirements concerning creep resistance. It is therefore of fundamental interest, in the context of alloy design, to develop materials that has these important properties and satisfies the needs of industrial users.
Nickel-base N06235 alloy is a solid-solution strengthened Ni-Cr-Mo-Cu alloy that was developed to resist metal dusting corrosion attack in high temperature structural applications involving carbonaceous and other high temperature corrosive environments, particularly in syngas production and processing environments. Improved metal dusting resistance was achieved by significant additions of copper and high amounts chromium to inhibit carbon deposition, ingress, and coke formation as previously reported. The high temperature creep-rupture and tensile strength of the wrought alloy and its weldments were investigated in this paper. Weld samples produced by Gas Metal Arc Welding (GMAW) and Gas Tungsten Arc Welding (GTAW), exhibit tensile and creep-rupture strength similar to that of wrought alloy in the temperature range from 538 to 1093oC (1000 to 2000oF). In addition, the retained room and elevated temperature tensile properties of the wrought base metal after 4000-hour long-term aging at temperatures from 649 to 871°C (1200 to 1600oF) are reported.
Many industrial processes contain H2, CO, CO2, and H2O gas mixtures, such as syngas production and processing in hydrogen, ammonia, and methanol plants. These process environments have high carbon activity, i.e. ac > 1, and low oxygen partial pressure at their elevated operating temperatures, such as in the temperature range of 400-800 °C (752-1472 °F). The high carbon activity could result in a catastrophic material degradation, i.e. metal dusting. The resulting corrosion products consist of carbon or graphite and metal particles, along with possible carbides and oxides, and cause material disintegration.