A portion of the wall of a reactor vessel used in burning impurities from carbon particles failed by localized melting. The vessel was made of Hastelloy X (Ni-22Cr-9Mo-18Fe). Considering the service environment, melting could have been caused either by excessive carburization (which would have lowered the melting point of the alloy markedly) or by overheating. A small specimen containing melted and unmelted metal was removed from the vessel wall and examined metallographically. It was observed that the interface between the melted zone and the unaffected base metal was composed of large grains and enlarged grain boundaries. An area a short distance away from the melted zone was fine grained and relatively free of massive carbides. This evidence supported the conclusion that the vessel failed by melting that resulted from heating to about 1230 to 1260 deg C (2250 to 2300 deg F), which exceeded normal operating temperatures, and carburization was not the principal cause of failure. No recommendations were made.

Welds in two CMo steel catalytic gas-oil desulfurizer reactors cracked under hydrogen pressure-temperature conditions that would not have been predicted by the June 1977 revision of the Nelson Curve for that material. Evidence of severe cracking was found in five weld-joint areas during examination of a naphtha desulfurizer by ultrasonic shear wave techniques. Defect indications were found in longitudinal and circumferential seam welds of the ASTM A204, grade A, steel sheet. The vessel was found to have a type 405 stainless steel liner for corrosion protection that was spot welded to the base metal and all vessel welds were found to be overlaid with type 309 stainless steel. Long longitudinal cracks in the weld metal, as well as transverse cracks were exposed after the weld overlay was ground off. A decarburized region on either side of the crack was revealed by metallurgical examination of a cross section of a longitudinal crack. It was concluded that the damage was caused by a form of hydrogen attack. Installation of a used Cr-Mo steel vessel with a type 347 stainless steel weld overlay was suggested as a corrective action.

A spherical carbon steel fixed-catalyst bed reactor, fabricated from French steel A42C-3S, approximately equivalent to ASTM A201 grade B, failed after 20 years of service while in a standby condition. The unit was found to contain primarily hydrogen at the time of failure. The vessel had a type 304 stainless steel shroud around the catalyst bed as protection against the overheating that was possible if the gas bypassed the bed through the refractory material. The failure was observed to have begun at the toe of the shroud-support ring weld. The ring was found to have a number of small cracks at the root of the weld. The cleavage mode of fracture was confirmed by SEM. The presence of extensive secondary cracking and twinning (Neumann bands) where the fracture followed the line of the shroud-support ring was revealed by metallography. It was revealed by refinery maintenance records that the ring had been removed for hydrotest and welded without any postweld heat treatment. The final cause of failure was concluded to be cracking that developed during the installation of the new shroud ring. Stress-relief heat treatments were recommended to be performed to reduce residual-stress levels after welding.

The failure of a reformer tube furnace manifold has been examined using metallography. It has been shown that the cause of failure was thermal fatigue; the damage was characterized by the presence of voids produced by creep mechanisms operating during the high temperature cycle under high local stress. The study indicates that standard metallographic procedures can be used to identify failure modes in high temperature petrochemical plants.

During a planned shut-down in 1990 it appeared that the bottom manifold parts made of wrought Incoloy 800H had undergone diametrical expansion of up to 2% due to creep. Further, cracking at the outer diam was found. It was decided to replace these parts. Microscopical investigations showed that the cracking could not be caused by creep. It was found that the cracking was confined to a 4-mm deep coarse-grained zone (ASTM 0-1) at the outer diameter. The cracking appeared to be caused by strain-induced intergranular oxidation. When the cracks reached the fine-grained material, the oxidation-cracks stopped. To determine the residual creep life of the sound (non-cracked) bottom manifold material, iso-stress creep tests were performed. It was found that tertiary creep started at 7% strain. The time-to-rupture was greater than 100,000 h. It was concluded that the bottom manifold (and thus the furnace) could be used safely during the foreseen production period.

Microstructural examinations on transverse cross sections of a steam reformer tube, showed the presence of large macrovoids elongated in the radial direction and emanating from the internal surface of the tube. The macrovoids were located at the interdendritic regions, and were partially filled by a Mn-Fe bearing chromium oxide film. The areas adjacent to the oxide film were chemically depleted in C, Cr and Mn and rich in Fe and Ni. Associated with this depletion were a large concentration of microvoids. It was suggested that the dissolution of carbides in areas surrounding the macrovoids and the concentration of stresses at their tips, caused extensive localized plastic deformation which led to the formation of microvoids and subsequently to the spalling of the oxide film. The non-protective character of the film induced a progressive deterioration of the grain boundaries properties. Grain boundary sliding and dislocation motion were enhanced, causing a local increase in the steady state strain rate and the premature failure of the tube.

Two steam-methane reformer furnaces were subjected to short-time heat excursions because of a power outage, which resulted in creep bulging in the Incoloy 800 outlet pigtails, requiring complete replacement. Each furnace had three cells, consisting of 112 vertical tubes per cell, each filled with a nickel catalyst. The tubes were centrifugally cast from ASTM A297, grade HK-40 (Fe-25Cr-20Ni-0.40C), heat-resistant alloy. The tube was concluded after metallurgical inspection to have failed from creep rupture (i.e., stress rupture). A project for detecting midwall creep fissuring was instigated as a result of the failure. It was concluded after laboratory radiography and macroexamination that if the fissure were large enough to show on a radiograph, either with or without the catalyst, the tube could be expected to fail within one year. The set up for in-service radiograph examination was described. The tubes of the furnace were radiographed during shut down and twenty-four tubes in the first furnace and 53 in the second furnace showed significant fissuring. Although, radiography was concluded to be a practical technique to provide advance information, it was limited to detecting fissures caused by third-stage creep in tubes because of the cost involved in removing the catalysts.

One of the coils in the radiant section of a primary reformer furnace used in an ammonia plant was found leaking. The bottom of one of seven outlet headers (made of ASME SA-452, grade TP316H, stainless steel) was revealed during examination to be ruptured. It was revealed by metallurgical examination that it had failed as a result of intergranular fissuring and oxidation (creep rupture). The ruptured area revealed that the header had failed by conventional long-time creep rupture as a result of exposure to operating temperatures probably between 900 and 955 deg C. Three samples from different sections (ruptured area, slightly bulged but nonruptured area and visually sound metal) were inspected. The presence of pinhead-size intergranular fissures throughout the cross sections of the latter two samples was observed. An ultrasonic attenuation method was employed to investigate the remaining headers. All headers were revealed by ultrasonic readings to be in an advanced stage of creep rupture and no areas were found to be fissured to a degree that they needed immediate replacement. As a conclusion, the furnace was deemed serviceable and it was established that in the absence of local hot spots, the headers would survive for a reasonable period of time.

An HK-40 alloy tubing weld in a reformer furnace of a petrochemical plant failed by leaking after a shorter time than that predicted by design specifications. Leaking occurred because of cracks that passed through the thickness of the weldment. Analysis of the cracked tubing indicated that the sulfur and phosphorus contents of the weld metal were higher than specified, the thickness was narrower at the weld, and the mechanical resistance of the weld metal was lower than specified. Cracking initiated at the weld root by coalescence of creep cavities. Propagation and expansion was aided by internal carburization. Quality control of welding procedures and filler metal was recommended.

During 5.7 years of service, dye penetrant inspection of Inconel 800H pigtail connections regularly showed cracks at weld toes. Weld repairs were not able to prevent reoccurrence but often aggravated the condition. Samples containing small, but detectable, reducer-to-pigtail cracks showed intergranular cracks originating at weld toes and filled with oxidation product, which precluded determination of the cracking mechanism. All weldments exhibited high degrees of secondary precipitates, with original fabrication welds exhibiting higher apparent levels than repair welds. SEM/EDS analysis showed base metal grain boundary precipitates to be primarily chromium carbides, but some titanium carbides were also observed. Failure was believed to result from the synergism of thermally driven tube distortion, which resulted in over-stress, and from the intergranular oxidation products and intergranular carbides which contributed to cracking. It was recommended that stresses be reduced and /or that materials and components be changed. Refinements in welding procedures and implementation of preweld/postweld heat treatments were recommended also.

A low-carbon steel (St35.8) tube in a phthalic anhydride reactor system failed. Visual and stereomicroscopic examination of fracture surfaces revealed heavy oxide/deposits on the outer surface of the tube, tube wall thinning in the area of the fracture, and discolorations and oxides/deposits on the inner surface. Cross sections from the fracture surface were metallographically examined, and the deposits were analyzed. It was determined that the tube had thinned from the inner surface because of a localized overheating condition (probably resulting from a runaway chemical reaction within the tube) and then fractured, which allowed molten salt to flow into the tube.