Case study of the failure of supercritical water oxidation reactor tubing during the treatment of 2,4 DNP with ammonium sulphate

摘要

During the process of Supercritical Water Oxidation (SCWO) organic chemical streams are oxidized at high temperature and pressure, typically in excess of 647 K and 22.1 MPa. Due to high operating temperatures and pressures severely corrosive environments often ensue and eventually lead to SCWO reactor tube failures. This case study looked at one such failure of Alloy 625 (61Ni-21.5Cr-9Mo) tubing which occurred at the UBC/NORAM SCWO pilot plant while treating a feed of waste water containing 2.4 wt percent 2,4 dinitrophenolate, 2 percent ammonium sulphate and 6 percent excess ammonia. Although the feed pH was approximately 9 and therefore not expected to be corrosive, in fact the tube failed when exposed to this feed (with oxygen) for a period of about 1 hour at 650-655 K. Through the examination of the ensuing thermodynamic system as well as SEM and Optical Microscope analysis of the ruptured portions of tubing, it was found that the addition of ammonium sulphate to the treated media caused rapid failure due to de-alloying. Findings show that the high sub-critical temperature and high density of the feed water at failure points, as well as the corrosion morphology are consistent with attack by ammonia. The formation of a stable soluble nickel-ammine phase is suspected.