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INTRODUCTION
The leakage of waste heat boiler located at secondary reformer downstream can cause a serious threat to sustainable plant operation. The leakage an cause BFW to enter the HTSC reactor flooding it and causing a thermal shock which can drastically decrease or even end the performance of the catalyst. In a worst case scenario catalyst replacement may also be required along with WHB tube rectification
INTRODUCTION
Terra industries faced two significant WHB failures at different manufacturing sites, both M.W. Kellogg design. Both events were similar in severity in that the HTS reactor was completely flooded, one of which had boiler water spraying out of the hot vent (sometimes referred to as high mute vent). These events led to a severe catalyst bed temperature decrease of 300 F (149 C) in 2 minutes. In addition to the thermal shock, both cases experienced a very long drain time to remove the water from the HTS reactor, thus exposing the catalyst bed to a hot water soak for approximately 12 hours. Despite the severity of these events, They made a successful recovery with only repair of the waste heat boiler
SEQUENCE OF EVENTS
On July 22, the plant was in start up mode. The feed gas was established to the primary reformer at 3:15 p.m. and the air was established to the secondary reformer at 4:20 p.m. By 5:15 p.m., it was apparent there was a significant leak in one of the 101-C waste heat boilers exchangers. Temperatures indicated it was in the 101-CA. The catalyst bed was at approximately 650F (343.3C) (when it was flooded with boiler feed water). The air was taken out of the secondary reformer at 5:28 pm and the feed gas was out of the primary reformer at 5:40 pm.
As the table shows, the HTS charge returned to service near start of run conditions and performed well during the entire life of the charge, significantly adding value to Terras operations by eliminating a shutdown and the expenses of a catalyst replacement.
PRECAUTIONS TAKEN
The was catalyst was replaced 4 months earlier so it was of main concern during this period. At the point in which the process gas was removed, the low point bleeds on the WHB (101-C) were opened along with the HTS inlet low point bleed, and HTS outlet bleeds. All of the low point locations were draining copious amounts of water. Water was also being emitted from the front-end mute vent. A stream of water continued to drain from these bleeds until approximately 7:00 a.m. At this time, the nitrogen to the front end for purge purposes was stopped in order to verify that water had ceased draining from the 101-C leak.
PRECAUTIONS TAKEN
In an attempt to improve chances of salvaging the HTS catalyst, the nitrogen purge was re established through the warm reforming section and allowed to continue through the HTS and out the 103-C and 104-C bleeds. Initially this warm purge was near 350F (176.7C) as indicated at the HTS inlet. At 12:15 p.m. water stopped draining from the 103-C and 104-C bleeds and nitrogen was redirected to purge through the remaining downstream equipment. This warm purge at approximately (1415 cubic meters) continued until 4:00 p.m. On June 15 when process gas blinds were installed for the replacement of the 101-C. At the conclusion of this continuous purge the nitrogen temperature had decreased to approximately 200F (93.3C). Investigation of the removed WHB revealed three leaking tubes adjacent to one major tube rupture.
PRECAUTIONS TAKEN
As a final measure to improve chances of salvaging the HTS catalyst, a nitrogen pressurization and release/dump sequence was initiated. This procedure established a high-pressure limit of 15- psig due to upstream blind limitations. The procedure also allowed a 1-hour hold period at pressure in order to allow time for some nitrogen diffusion into the pores of the catalyst.
At each pressure dump/release, some moisture was noted at the drains. This process continued for 10 sequences at which time the bleeds began to dry.
The sequence was then modified to hold pressure 4-6 hours and was continued throughout the duration of the outage. Purging was discontinued at 8:00 a.m. on June 19 in preparation for start up. Start up procedures were followed with slower heat up rates for the HTS to guard against excessive moisture vaporization. During outage a spare charge of HTSC catalyst was purchased in case a second outage is needed but catalyst regained full functionality.
INTRODUCTION
GPN is the leading French producer of Nitrogen fertilizers. The site is the largest fertilizer facility in France. The Ammonia plant, known as AM2, was started in 1978 which a capacity of 1000 MTPD which after revamping was increased to 1170 MTPD . In September 2009 a catastrophic fire took place in the compressor deck onsite .resulting in a total loss of 20 million US dollars and a plant shutdown of 11 months. The plant took a turnaround in 2008 and next turnaround was planned in 2014.
SEQUENCE OF EVENTS
On Wednesday, September 28, 2011, the ammonia plant start-up was in progress after 10 days of cold shut-down for maintenance work. The synthesis gas compressor was started at 5:30 p.m., Liquid ammonia product export to the storage spheres started at 4:30 a.m., the morning of September 29. At 6:00 a.m., the morning shift operator and the shift supervisor did their routine synthesis gas compressor check. Nothing abnormal was observed.
At 8:30 a.m., the production rate was stable at 865 MTPD and the team was preparing the start-up of the purge gas treatment unit.
The plant was in steady state operation, and all process parameters of the ammonia synthesis section were normal.
SEQUENCE OF EVENTS
At 8:33 a.m., three fire detectors located in the compressor room alarmed simultaneously. On the video monitor in the control room, the flames could be clearly seen, thus confirming the fire alarm.
At 8:34 a.m., the synthesis section emergency shut-down was activated manually from the control room. At the same time, the site fire brigade left the fire station.
At 8:43 a.m., as the fire was developing, the operators realized that there was a risk of extension of the fire. The plant was tripped completely and the natural gas cut-off valve was isolated. The control room operators started to depressurize the process gas through the vents.
SEQUENCE OF EVENTS
Around 8:45 a.m., the emergency management team was set up in the administration building. On site, the firemen identified a very noisy, high pressure gas leak, located on the discharge side of the compressor, along the wall of the building. The firefighting strategy consisted of establishing water curtains to protect the machine and the piping inside the building in order to limit the extent of the fire. At 8:57 a.m., the roof of the building, partly consisting of transparent polycarbonate plates, began to burn producing a heavy, black smoke. At 9:00 a.m., the west wall of the compressor room, made of concrete blocks, collapsed, and the gas fire, which up to now was contained inside the building, escaped outside, threatening the main pipe rack.
SEQUENCE OF EVENTS
All the plant personnel, with the exception of the firefighting team, were evacuated and sheltered inside the blast-proof control room building. At 9:06 a.m., the civil fire brigade arrived on site and up to 70 firemen were prepared to support and replace the site firemen At 9:17 a.m., the site firemen established fire hoses outside the building to protect the main pipe rack. At 9:24 a.m., the synthesis loop residual pressure was less than (150 psig). At this point (300 psig) nitrogen hose was connected to the loop in order to inject inert gas. At 9:55 a.m. (1 hour and 22 minutes after the incident start) the fire was totally extinguished
DAMAGE DONE
DAMAGE TO BUILDING
Wall in front of compressor collapsed from bottom The steel structure of the building was damaged and effected Roof plates on top of compressor deck were partially burnt The outside wall covering in Eternit was destroyed and broken into small pieces, which were sprayed all over. This contained asbestos so it had to be cleaned causing 3 weeks delay in repairs
DAMAGE DONE
DAMAGE TO PIPING AND VALVES The main compressor discharge line was apparently intact, only the small bore piping was damaged. Two small process lines were broken (see Figure 2). The piping in the main pipe rack was impacted by the fire but had not failed (except for small steam tracing and instrument air lines). DAMAGE TO THE INSTRUMENTATION Inside the deck the instrumentation was badly damaged including actuators of control valves The instrumentation in piping rack was also partially effected
ANALYSIS
The immediate cause of the incident appears to be a hydrogen-rich gas leakage on a 1 inch ASME class 2700 lb., welded bonnet, forged steel valve (Figure)located on the by-pass line of the synthesis gas compressor main discharge valve. This manual valve is operated during each plant start-up in order to pressurize the synthesis loop. The investigation concluded the only possible failure mechanism was as follows: 1. Grooved rivet (#35) was missing. 2. Nearly complete unscrewing of the yoke bushing (#11) during operation of the valve. 3. Rupture of the last thread as a consequence of the internal pressure rise during the normal start-up process. 4. Vibration of the stem (#4) and loss of tightness of the packing. 5. Gas leakage and ignition.
RECONSTRUCTION
The reconstruction work started on November 28, 2011, and employed up to 250 people. It was completed on May 10, 2012. One third of the compressor room building, from the floor to the roof, was dismantled and rebuilt, including replacement of the steel frame.
A complete overhaul of the synthesis gas and the refrigeration compressors, including auxiliaries, was performed.
All electrical, instrumentation cables, and cable trays from the control room building to the compressor room were replaced. In total 40 km (25 miles) of cable was installed. The damaged piping and valves were replaced or repaired depending on the results of the inspections. A total of 150 m (500 feet) of piping (up to 40 mm, or 1.6 in thick) was replaced.
Example of leak detection system on high pressure flanges (each individual vinyl hose is connected to a flange, and identified with a metal tag. The tag number is referenced on the plant drawings).
INTRODUCTION
The startup heater is usually used during startup to heat up the gas to achieve a temperature required for the exothermic reaction of ammonia formation The SUH (fig 2) is a standard vertical gas fired heater with double helicoidal coils. The coils design is composed of 2 Cr 1Mo tubes, 101,6 mm outside diameter with 10,3 mm minimum wall thickness based on API RP530 .
SEQUENCE OF EVENTS
Ammonia plant start up was in progress and start up heater was in service Process gas pressure was 100 bar and temperature at startup heater outlet was 420o C where as flue gas temperature was 825 o C
At about 1845 hrs on the day of incident small flames were observed on the coil outlet of SUH. This observation led to the immediate S/D of the plant with the following conditions Stoppage of the fuel gas flow to the SUH Isolation of the synloop from the syngas compressor with automatic safety ball valves Depressurizing of the synloop was started
The flames increased as the SUH could not be isolated from the synthesis reactor and finally the inlet process manual valve to the SUH was closed.
SEQUENCE OF EVENTS
Suddenly, a loud noise was heard, and big flames could be observed in the bottom of the SUH, in the area where the coils exit the SUH and from the top of the chimney. Internal and external fire brigades were called and took appropriate actions to protect the surrounding equipment's, such as the ammonia converter and the related inlet piping.
SEQUENCE OF EVENTS
When entering the SUH after the incident, it was clear that one of the coils exiting the heater had ruptured as shown in fig 6 and 7. The shell area in the conical part of the heater where the coils exit was bent aside, and a strong thinning of the shell was observed.
WHAT HAPPENED ?
The fracture of the coil was caused by high temperature due to radiation from the refractory and the lack of cooling as the flow through the coil was closed (fig 10,11) As the leak in the coil was discovered during start-up of the plant, the flow of syngas through the coils was interrupted as the valve was closed. The lack of internal cooling immediately led to overheating of the impaired area of the coil from the hot refractory resulting in the rupture. As the coil was already leaking and the leak was increasing, it is difficult to predict the development of the fire in case the flow through the coils had not been interrupted.
WHAT HAPPENED ?
Due to local dramatic thinning of wall caused by external corrosion the coil suffered creep damage in the area where the damage took place. The thin walled areas suffered much high mechanical stresses and creep damage in startups
PREVENTIVE ACTIONS
Inspection of the other synthesis process piping which have process conditions around 100C (210 F) should be investigated. When done in Yara Tertre, some other externally corroded piping was found and repaired.
Due to the long exposure at high temperatures, the coils may have been subject to swelling that could lead to cracks in the future. The possibility of hydrogen attack was also suspected. According Nelson curves (API941), the operating conditions of hydrogen partial pressure and temperature are within the recommend limits but it is not the case for the design conditions Protection against humidity and a permanent small flow through the coils in order to maintain a constant temperature around 120C (250 F) should be considered for the future
CHEMISTRY
Ni(CO)4 is produced when reduced nickel is exposed to CO containing atmosphere under specific temperature & pressure conditions. Favourable conditions are low temperature & high pressure. Figures 1 to 3 show the equilibrium curves for Ni(CO)4 at a range of pressures, CO concentrations and temperatures. The equilibrium amount of nickel carbonyl is temperature dependent. For example if part of a catalyst bed is twenty degrees cooler than the point of measurement, you could make ten times as much nickel carbonyl.
PROPERTIES
Its high vapour density relative to air means that the vapour can gather in low spots. Its vapour pressure suggests that it can be condensed causing accumulation in cold dead spots or legs. The fact that liquid nickel carbonyl is denser than water and sparingly soluble in water means that it is possible to trap a liquid spill under water.
Catalysts
The main sources of available nickel are the hydrodesulphurization, prereforming, primary reforming, secondary reforming and methanation catalysts. The main catalysts types that incorporate nickel in order of typical nickel metal content are shown in table
Controlling of the physical conditions is the key to avoiding the formation of nickel carbonyl in a syngas plant.
However the partial shutdown lasted longer than anticipated and the methanator cooled down to 25C. It became necessary to fit a slip plate to complete some other essential maintenance work.
It is suggested that during S/D the Methanator be purged with nitrogen while it is still above 200C (390F). It is suggested that during start-up the methanator should be heated at low pressures until the temperature is above 200C (390F).