Engineering Failure Analysis 9 (2002) 553561 www.elsevier.

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Failure of reformer tube of an ammonia plant

S.K. Bhaumik*, R. Rangaraju, M.A. Parameswara, T.A. Bhaskaran, M.A. Venkataswamy, A.C. Raghuram, R.V. Krishnan
Failure Analysis Group, Materials Science Division, National Aerospace Laboratories, PO Box 1997, Bangalore 560 017, India Received 3 October 2001; accepted 13 October 2001

Abstract The present article describes the failure of a primary reformer tube in an ammonia plant. The failure took place at the stub end of the reformer tube where a SS 321 ange was joined to a HK 40 catalyst tube by welding. Detailed metallurgical examinations indicated that the failure was due to stress corrosion cracking. Both longitudinal and transverse cracks were observed at the region of fracture. The cracks originated at the interface of the weld and HAZ at the inner surface and progressed to the outside of the tube in the transverse (thickness) direction. Microstructural study revealed chromium carbides precipitation at the grain boundaries in the heat aected zones on either sides of the weld. The results clearly indicated that the steel had undergone sensitisation which subsequently led to failure of the reformer tube by stress corrosion cracking. # 2002 Published by Elsevier Science Ltd.
Keywords: Weld decay; Welded fabrications; Chemical-plant failures; Sensitisation; Stress corrosion cracking

1. Introduction The steam-gas reformer is a common but critical piece of equipment in ammonia and methanol plants, operating on feedstocks like natural gas or naptha. The steam reforming of hydrocarbon to CO, CO2 and H2 takes place under operating parameters of high temperatures and high pressures. During the process, various corrosive substances like uorine, hydrouorosilicic acid, SO2 and SO3 gas, NOx gas, acid mist etc. are formed. Because of the hot aggressive atmosphere, corrosion is the major problem contributing to the majority of failures in ammonia plants. Various forms of corrosion that are generally encountered are uniform corrosion, galvanic corrosion, intergranular corrosion, stress corrosion, cavitation, fretting corrosion, high temperature corrosion, hydrogen embrittlement, metal dusting etc. [1]. Although sucient care is taken in the selection of materials, fabrication and designing of the plant, failures can hardly be avoided because of various reasons. Reformers are the heart of the fertilizer industry and any failure in this section of the plant results in premature shutdown leading to huge losses in terms of damage to the equipment, production losses and safety hazard. This paper describes the analysis of failure of primary reformer tubes of an ammonia plant.
* Corresponding author. Fax: +91-80-5270098. E-mail address: subir@css.cmmacs.ernet.in (S.K. Bhaumik). 1350-6307/02/$ - see front matter # 2002 Published by Elsevier Science Ltd. PII: S1350-6307(01)00039-5

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2. Background 2.1. The process The primary reformer in an ammonia plant is used to crack naptha into its constituents such as carbon and hydrogen by heating the uid that passes through catalyst loaded tubes. In the present case, each reformer furnace in the plant had 224 reformer tubes130 mm dia. and 12.5 mm thick. The burners for heating are mounted on the roof of the furnace. There are 60 burners in the furnace. The feed for the individual tubes is sent through inlet pigtails and these pigtails are connected to inlet headers batch-wise. Similarly, the process gas from the catalyst tube is sent out through outlet pigtails which are further connected to outlet headers batch-wise. Naptha with 5 ppm sulphur is heated to a temperature of 380  C in a red heater, passed through Comox catalyst (cobalt and molybdenum) and then mixed with steam in the ratio 1:4.5 before entering the inlet header at a pressure of 30 kg cm2 and 380  C. 2.2. The failure In an incident, a number of catalyst tubes were found to have failed just below the inlet ange weld after about 2 years in service. The weld neck ange and the catalyst tube were made of SS 321 and HK40 (centrifugally cast) steels respectively. The nominal compositions of these steels are given in Table 1. One of the failed reformer tubes (ange end) along with an unfailed one was brought to the Laboratory for investigation to ascertain the cause of failure. The schematic of the catalyst tube and the location of cracking are shown in Fig. 1.

3. Observations 3.1. Visual and stereobinocular Visual observation revealed that the reformer tube had fractured circumferentially at the weld catalyst tube interface. The inner surface of the tube was found to be covered with black deposits. On dye penetrant inspection, a number of circumferential and longitudinal cracks were seen both outside and inside the tube (Figs. 2 and 3). The cracking was found to be extensive on either sides of the weld. The fracture surface was cleaned thoroughly in acetone and observed under a stereobinocular microscope. Gross fractographic features indicated that the fracture was brittle in nature.

Table 1 Nominal composition (wt.%) of SS 321 and HK 40 stainless steel Element C Mn Si Cr Ni P S Ti Fe SS 321 0.08 2.00 1.00 17.019.0 9.012.0 0.045 0.03 5% C (min) Balance HK 40 0.350.45 1.75 (max) 23.027.0 19.022.0 Balance

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Fig. 1. Schematic showing the location of cracking in the reformer tube.

Both the longitudinal and the circumferential cracks originated at the inside surface and at the heat aected zone (HAZ) of the parent materials. It was found that circumferential cracks originated at the interfaces of the weld layer and HAZ at the inner surface of the tube and progressed outward in the transverse (thickness) direction. Many of the longitudinal cracks extended to both sides of the weld (Fig. 3). 3.2. Scanning electron microscopy (SEM) A specimen containing the fracture surface was cut from the failed tube, cleaned by repeated acetate replica stripping followed by ultrasonic cleaning in acetone and observed in a SEM. The fracture surface exhibited mixed mode of transgranular and intergranular cracking being predominantly intergranular (Fig. 4). A large number of secondary cracks were also observed along the grain boundaries. The gross fractographic features were indicative of brittle type of failure.

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Fig. 2. Photograph of the ange portion of the failed reformer tube showing longitudinal and transverse cracks on the outside surface.

Fig. 3. Photograph of the ange portion of the failed reformer tube showing longitudinal and transverse cracks on the inside surface.

3.3. Metallography A sample piece was cut from the HAZ, mounted, metallographically prepared and observed in an optical microscope and SEM in both unetched and etched conditions. For purposes of comparison, similar studies were also carried out on a sample piece removed well away from the cracked region. The sample away from the cracked region, which conforms to the parent material of the ange, showed a microstructure of twinned grains (Fig. 5). This type of microstructure is typical of 321 stainless steel. The microstructure showed no abnormalities. In the region of cracking (HAZ), however, considerable cracking and crack branching were observed on the polished specimen (Fig. 6). Extensive carbide precipitation was seen along the grain boundaries (Fig. 7)

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Fig. 4. SEM fractograph showing intergranular/transgranular cleavage on the fracture surface of the failed reformer tube.

Fig. 5. Optical micrograph showing twinned grains in the parent material of SS 321 ange.

with the carbide present as a continuous lm in some regions. Compositional analysis carried out by EDX indicated these carbides to be rich in chromium. The carbide precipitation was seen predominantly in the region adjacent to the weld. Extensive intergranular cracking was also seen in this region (Fig. 8). These cracks were found to have propagated in both longitudinal and transverse directions of the tube. Away from this region, the extent of precipitation fell drastically. 3.4. Compositional analysis Semiquantitative EDX analysis of the ange material showed that the material conforms to SS 321. Analysis on the fracture surface revealed the presence of chlorine and sulphur in some regions, as well as

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Fig. 6. SEM micrograph showing extensive crack branching in the HAZ.

depletion of chromium. Deposits from the inner surface of the reformer tube showed presence of oxygen, potassium and sulphur (Table 2). 3.5. Hardness measurements Microhardness measurements were carried out at a load of 500 g on polished specimens across the weld from the longitudinal sections of both failed and unfailed tubes. No signicant variation in hardness values was observed. 3.6. Weld fabrication The welding of the ange and the catalyst tube was done in four passes, the rst pass being carried out with Inconel alloy and the subsequent passes with HK 40 alloy. However, in the failed reformer tube, it is seen that the Inconel alloy layer has been removed completely during post weld machining exposing the HK 40 alloy layer to the inside surface. However, in the unfailed tube, the weld was found to have all four layers with the rst layer being the Inconel alloy.

4. Analysis of results Fractographic features showing intergranular/transgranular fracture and microscopic features showing extensive branching cracks are typical of stress corrosion cracking. The presence of chromium carbide along the grain boundaries both as discrete particles and as a continuous lm is indicative of sensitisation of the stainless steel. Sensitisation of stainless steel can occur both from welding and service conditions. Since sensitisation is seen only in the region of HAZs, it can, therefore, be concluded that the problem lies with the welding. A specic concern in the welding of corrosion resistant stainless steel castings is the production of a sensitised structure. Sensitisation occurs in stainless steel alloys when chromium rich phasesM23C6 carbides, sigma (s), chi (w), and laves phasesprecipitate during exposure to temperatures between 400 and

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Fig. 7. Optical micrograph showing extensive carbide precipitation along the grain boundaries in the HAZ of the ange material.

Fig. 8. Optical micrograph showing extensive intergranular cracking in the HAZ.

Table 2 Semiquantitative EDX analysis of reformer deposit Element O Al Si S K Wt.% 29.0 0.5 0.8 0.2 0.3 Element V Cr Mn Ni Fe Wt.% 0.3 9.2 1.4 1.7 Balance

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900  C. The precipitation of these constituents can result in local depletion of chromium in the matrix, lowering the corrosion resistance to a point where corrosion induced failure of the casting can result. Precipitation of carbides at grain boundaries can occur in both the HAZ and fusion zone [2]. The problem is further aggravated when welding dissimilar alloys like wrought stainless steel of low carbon content (approximately 0.08% C in SS 321) with cast heat resistant stainless steel of medium carbon content (approximately 0.4% C in HK 40), as in the present case. In such a case, the carbon from the medium carbon steel diuses into the low carbon steel resulting in the precipitation of chromium carbide at the grain boundaries. In cases where sensitisation results from welding heat, as has happened in the present case, solution annealing following the welding dissolves the precipitates and restores the immunity of the material to corrosion attack. However, in many cases this cannot be done because of the distortion problems or the size of the component. In these cases, suitable control of weld parameters such as the heat input, using ller metal electrodes with low carbon (such as the SS 321 grades) helps to prevent sensitisation. Stabilising the steel grades with additions of Nb (up to 1%) is also a good solution. In the present case, the welding was done in four passes, the rst pass being carried out with Inconel alloy and the subsequent passes with HK 40 alloy. This was adopted basically to prevent the sensitisation of the steel on the inner surface of the tube which is exposed to hot aggressive process gases and vulnerable for corrosion attack. However, due to inadvertent machining, the Inconel alloy layer has been removed exposing the HK 40 alloy in the weld to hot corrosive gases providing an easy path for the stress corrosion cracking. The presence of an extensive network of intergranular cracks on the inner surface of the reformer tube shows that it is subjected to corrosive attack subsequent to sensitisation. The presence of intergranular/ transgranular cracks and traces of chlorine on the fracture surface suggest that both chloride and caustic stress corrosion cracking could be the mechanisms for the failure. Small traces of chloride and alkali present in the steam entering the reformer tube are considered the possible source of corrodent.

5. Failure mechanisms From the above analysis, it is apparent that the reformer tube has failed by stress corrosion cracking. During welding, the steel in the HAZ has undergone sensitisation and this has subsequently led to stress corrosion cracking. The sensitisation of steel has taken place due to (a) improper welding such as the use of improper ller metal electrodes while joining dissimilar stainless steels of low and medium carbon contents, and (b) removal of the protective Inconel alloy layer in the weld exposing the HK 40 steel layer to hot corrosive gases. The source of corrodent could be the traces of chloride and alkali present in the steam. In normal operation, this concentration of corrodents in the process gases should not pose a great deal of problem as far as the corrosion of SS 321 and HK 40 steels are concerned. However, in the circumstances of sensitisation of steels, these are sucient enough for corrosion attack leading to stress corrosion failure.

6. Conclusions (a) Sensitisation of the reformer tube has taken place in the HAZ on either sides of the weld. (b) Subsequently, corrosion and cracking of the sensitised tube have been caused by the chlorides and alkalies present in the steam. The crack has initiated on the inner surface of the tube and progressed towards the outer surface. (c) The problem of stress corrosion cracking was further aggravated in the failed tube due to the removal of the protective Inconel alloy layer during post weld machining which resulted in the exposure of HK 40 alloy to hot corrosive process gases.

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7. Recommendations (a) When welding dissimilar alloys like wrought stainless steel of low carbon content (SS 321) and cast heat resistant stainless steel (HK 40), extra precautions should be taken to prevent sensitisation. Using ller metal electrodes with low carbon content (such as the 321 grades) and stabilising the steel grades with additions of Nb (up to 1%) will help preventing sensitisation during welding. (b) Another fact that is responsible for sensitisation, particularly in multi-pass welds, is heat input because of low thermal conductivity of stainless steels. For this reason, while welding stainless steels, it is advisable to cool the steel after every pass to below 100  C, before the next pass is applied.

Acknowledgements The authors thank Mr. C.R Kannan and Ms. Kalavathi for NDT and Scanning Electron Microscopic support. The authors are thankful to the Director, NAL, for permission to publish this work.

References
[1] Metals handbook. Corrosion in petroleum rening and petrochemicals operations, vol. 13. Corrosion. 9th ed. American Society for Metals, 1987. p. 126298. [2] Metals handbook. Corrosion failures, vol. 10: Failure analysis and accident prevention. 8th ed. American Society for Metals, 1975. p. 168205.