CASE STUDY ON SOME OF THE MAJOR CORROSION CATASTROPHES IN THE HISTORY.

A REPORT SUBMITTED AT COMPLETION OF THE COURSE ON CORROSION & ENVIRONMENTAL DEGRADATION OF MATERIALS (MT41013) .

SUBMITTED BY: NITIN SINGH 09MT3010

INTRODUCTION: While mankind has made remarkable progress in the last century,
there have been some instances in the past where innocent human lives were consumed due to some mishappenings as the unwanted byproduct of the same. Corrosion in itself is not important, but the consequences of corrosion failure may well be. While corosion is almost always unwanted, the consequences of corossion are very costly. Little surprise, therefore, that a substantial engineering effort is directed towards its prevention and control. In this report, those events are disucssed where corossion was responsible for taking the lives of hundreds of individuals. What lead to their occurrence and their causes are discussed aswell .

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BHOPAL GAS TRAGEDY

The Bhopal disaster, also referred to as the Bhopal gas tragedy, was a gas leak incident in India, considered one of the world's worst industrial disasters. It occurred on the night of 23 December 1984 at the Union Carbide India Limited (UCIL) pesticide plant in Bhopal, Madhya Pradesh. Over 500,000 people were exposed to methyl isocyanategas and other chemicals. The toxic substance made its way in and around the shantytowns located near the plant.Estimates vary on the death toll. The official immediate death toll was 2,259.

[ The above pictures show the aftermath of the Bhopal Gas Tragedy where individuals died within hours of the leakage of gas and its expansion in the atmosphere of Bhopal ]

FROM A CORROSION ENGINEERS STANDPOINT: The Bhopal disaster was the

result of a combination of legal, technological, organizational, and human errors. However, the immediate cause of the chemical reaction was the seepage of water (500 liters) into the MIC storage tank. Many investigators and researchers have agreed that corossion of pipelins, values and other safety equipments as the main culprit for this catastrophy. The following evidences are presented to support the argument.

MIC was stored in three double-walled, partly buried stainless steel tanks code named 610, 611 and 619. While thousands slept in their huts around the pesticide around the pesticide factory

factory on the night of December 2/3, a skeleton staff of 120 workers inside the factory ended its evening shift around 10.45 pm and a new shift took over around 11 pm. One of the workers then noticed that the pressure in tank 610 the tank from which all the MIC finally escaped had risen from the two lb per square inch (psi), recorded by the earlier shift, to around 10 psi. Corresponding tank temperatures were not available as they were not logged normally. The five-fold increase in pressure within an hour was dismissed in the belief that the pressure recording instrument could be faulty. Shakil Qureshi, the supervisor on duty, said later, Instruments often didnt work. They got corroded. Crystals would form on them. How the water entered the pipelines connected to the MIC containing stainless steel tank is altogether a different story, but its entry inside the MIC containing tanks could have been everted had the proper maintanince of the valves connecting the pipelines to the tank being done. Carbon steel valves were used for this purpose. Carbon steel valves easily corrode in acidic environment, which was actually happening in UCL plant. Moreover, slip-blind plates which would have prevented the entry of water through faulty valves were not installed. Once the water entered inside the MIC containing tanks through faulty valves, the MIC found its way to escape from the tanks as well and hence to the atmosphere. What happened inside the tank? The precise sequence of events still remains obscure. Carbides report has claimed that it was an unique combination of large amounts of water (120 to 240 gallons), higher than normal amounts of chloroform in the stored MIC (several per cent instead of a maximum of 0.5 per cent), and an iron catalyst, that led to the violent reaction in MIC, stored at a higher than specified temperature. The heat released by the reaction between the water and MIC raised the temperature in the tank. Simultaneously, MIC got polymerised, the reaction being catalysed by iron resulting from the corrosion of the tank walls due to the high temperatures. Carbide claims that the corrosion rate increased markedly because of the presence of an abnormally high level of chloroform. The rapid release of carbon dioxide in large quantities then helped to build up high pressures, which forced the foaming mass of chemicals out of the tank.

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A file picture of the plant at Bhopal, showing the plight due to corroded sections and components

 The series of misforfortune did not stop here as the final blow to the safety of the people of Bhopal came when it was found out that Flare Tower could not be used as the length of piping was corroded and and had not been replaced. The flare tower was designed to burn off MIC escaping from the scrubber. The tower, however, was inadequately designed for its task, as it was capable of handling only a quarter of the volume of gas released, but still it could have lessened the amount of damage incurred to human lives. The Bhopal gas tragedy took place because of the corroded pipelines and valves. Despite the importance of corrosion prevention and control, many people in India still prefer to ignore corrosion, which is considered to be a natural part of wear and tear. One might argue this as a result of UCLs negligience for corrosion control or for the value of human life, the relatives and friends of those who died are never going to return, added to this the environmental hazars that the MIC release had for years. The above amalysis of the Bhopal gas Tragedy proves how much corrosion control is important for an industry dealing with hazardous chemicals not just to avoid its own loss but also the loss of innocent lives as well.

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PRUDHOE BAY 2006 OIL SPILL

The Prudhoe Bay oil spill was an oil spill that was discovered in March, 2006 at apipeline owned by BP Exploration, Alaska (BPXA) in western Prudhoe Bay, Alaska.On March 2, 2006 a BP Extration well pad operator discovered a leak in the transit line that delivers oil to the trans-Alaska pipeline from Gathering Center 2 in the western operating area of the giant Prudhoe Bay oil field on Alaskas North Slope.The leak occurred in the transit line segment between GC-2 and the point where the production from Gathering Center 1 enters the line.BP launched an immediate response to what, with an estimated volume of around 200,000 gallons, proved to be the largest spill in the history of Prudhoe Bay. The cause of the leak became obvious within a few days of its discovery: internal corrosion had caused a one-quarter-inch hole in the bottom of the transit pipeline. The hole had formed in a section of line buried under what is termed a caribou crossing, a culvert designed to allow animals to cross over a pipeline as opposed to going under an elevated pipeline.The winter snow covered the leaking oil, so the spill remained undetected, probably for several days. It was odor the smell of oil that ultimately exposed the leak to a worker.

FROM A CORROSION ENGINEERS STANDPOINT: What happened in Prudhoe

Bay was Microbial Corrosion. All indications were that the corrosion that caused the hole in the transit line was biological in origin, caused by sulfate reducing bacteria inside the pipeline. The corrosion pits confirmed this and also the way in which the corrosion in the pipeline accelerated over time was characteristic of the way in which microbiological corrosion develops, as the bacteria grow and multiply. The bacteria forms in water, so that problems associated with microbiological corrosion were suspected to be associated with the water carrying pipelines, such as the lines which were used for waterflood operations .

Transit lines less corrosion prone: BP had viewed oil carrying transit lines, such
as the line from GC-2 that developed a leak, as much less susceptible to corrosion than a water bearing line. But the company had regularly monitored the Prudhoe Bay oil transit lines for internal corrosion using two techniques: ultrasonic testing and the use of corrosion coupons. Ultrasonic testing involves the use of an ultrasonic device to measure the thickness of the pipeline wall a thinning of the wall indicates the presence of corrosion. A corrosion coupon is a small metal plate placed inside the pipeline and inspected for corrosion every 90 days For straight 29 years, BP noted nothing of significance. It was only in fall of 2005 that evidence of increasing corrosion activity started to appear. The increasing amount of corrosion found in the fall of 2005 caused BP to step up the inspection program on the pipeline the company increased the number of inspection points, increased the frequency of inspections at some points and scheduled a smart pig inspection for the summer of 2006, according to the BP report. However, an inspection of the line after the March 2006 leak showed evidence of high rates of corrosion, even in place that had been free of corrosion in the fall 2005 inspection. Clearly, there had been an exponential growth of corrosion, culminating in the hole that caused the oil spill.

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Why did the corrosion accelerated so rapidly?

BP investigation report theorized two main factors that came together at the same time. The first factor related to corrosion inhibitors. BP added about 3 million gallons per year of these inhibitors to Prudhoe Bay production fluids; the fluids carried the inhibitors into production facilities such as GC-2. But the corrosion inhibitors appeared to have been present in relatively low concentrations in the GC-2 production facilities, when compared with the other Prudhoe Bay facilities. It was thus concluded that the fluids passing down the GC-2 transit line from GC-2 contained only small amounts of the inhibitors, thus providing opportunities for corrosioncausing bacteria to grow. The corrosion inhibitor shortfall may have occurred

because GC-2 was the only facility at Prudhoe Bay which processed viscous oil. The viscous oil production introduces more solids into the processing facilities than traditional production and BP thought that these additional solids may have adsorbed some of the inhibitor. The second possible factor was the relatively low flow rate in the GC-2 transit line, upstream of GC-1. With Prudhoe Bay production in decline, the transit line was carrying much smaller volumes of oil than the line was designed to handle the resulting sluggish flow may have enabled an increased build up of water in the line and provided an environment conducive to the incubation of bacteria. There was much less corrosion downstream from GC-1, where the addition of the fluids from GC-1 would have increased flow rates in the line. There was also a build up of solids in the GC-2 transit line over a period of several years, as sediment carried by the fluids from the GC-2 processing facilities settled in the pipeline. It is not possible to discount the possibility that these solids contributed to the corrosion.

Page 5 [A file photograph showing clean up crews recovering more than 19,000 gallons of
crude oil leaked from athe pipeline leaken in Prodhoe bay]

Summary of what happened in Prodhoe Bay: Sulphate reducing bacteria (SRB)

are small anaerobic microorganisms. When conditions are right they can multiply to the level of millions of cells per gram and generate significant quantities of hydrogen sulphide (H2S). The H2S together with the stagnant conditions formed by the colony on the pipewall lead to enhanced pitting corrosion rates. The corrosion in these special cases caused by microbials is termed as Microbial Corrosion.

FLIXBOROUGH DISASTER
Built in 1972, the caprolactam unit (Section 25A) performed cyclohexane oxidation in a series of 6 successive reactors. Each reactor, equipped with a unit capacity of 45 m (5 m high with a 3.5 m diameter), was made of a 13-mm soft steel plated on the inside by stainless steel (3 mm) and featuring a central agitator. The oxidation step was carried out in the presence of a catalyst, by means of injecting compressed air. On March 27, a cyclohexane leak was observed on Reactor no. 5 at the level of a vertical crack within the sidewall. The facility operator decided to conduct a thorough inspection by removing it. In order to resume production as quickly as possible, it was decided to build a bypass between Reactors 4 and 6 and then implement the modified configuration without any specific preliminary study, based on a drawing produced on the shop floor.

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On June 1st, an explosion took place in the plant which killed 28 people and seriously injured 36.

FROM A CORROSION ENGINEERS STANDPOINT: The investigation commission

organized by organized by the Secretary of State for Employment found out that explosion took place due to the ignition caused in the cyclohexane which leaked from the bypass joints of rector 4 and 6, which later reached the reforming tower of H 2.

At the origin of the accidental sequence, the deficiency of Reactor no. 5 stemmed from cracking corrosion caused by nitrates contained in the water used in the past to spray the small cyclohexane leaks, in an effort to limit the risk of ignition. This water had penetrated into the insulation and, during evaporation, deposited nitrates onto the equipment steel. The cause of the leak on Reactor no. 5 should have been analyzed prior to any unit reactivation and the other reactors should have been verified with respect to the degradations sustained by Reactor no. 5. Such an approach however would have required shutting down the plant for a few days; the concern over minimizing plant downtime and production losses actually motivated the stopgap configuration that eventually gave rise to the accident. The crack in Reactor no. 5, which served as the source of the accidental sequence, stemmed from corrosion caused by spraying the reactor with drinking water (hence high in nitrates) in order to dilute cyclohexane discharge and limit the risk of ignition. The crack in Reactor no. 5 indicates that drinking water contains nitrates capable of causing steel corrosion when under tension. Thus, Nitrate-induced corrosion was held liable for Flixborough disaster.

GUADALAJARA SEWER EXPLOSIONS

The 1992 Guadalajara explosions took place on April 22, 1992, in the downtown district of Analco. Numerous gasoline explosions in the sewer system over four hours destroyed 8 kilometers of streets . Officially, by the Lloyd's of London accounting, 252 people were killed, nearly 500 injured and 15,000 were left homeless

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[ Aftermath of the Guadalajara sewer explosions]

FROM A CORROSION ENGINEERS STANDPOINT: The sewer explosion was traced

to the installation of the water pipe by a contractor sveral years before the explosions which leaked water on a gasoline line lying underneath. The cathodically protected steel gasoline pipeline had a hole inside a cavity and an eroded area, all in longitudinal direction. A second wall did not perforate the internal wall. The galvanized water pipe obviously had suffered stray current corrosion effects that were visible in pits of different size ( see the picture below ).

Pits formed in water pipelines due to stray current corrosion

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The corroded water pipes lines lead to the leakage of water from them which further become responsible for the aqueous corrosion of gasoline pipelines. This lead to leakage of gasoline into the sewers.

CARLSBAD PIPELINE EXPLOSION

At 5:26 a.m., mountain daylight time, on Saturday, August 19, 2000, a 30-inch diameter natural gas transmission pipeline operated by El Paso Natural Gas Company (EPNG) ruptured adjacent to the Pecos River near Carlsbad, New Mexico. The released gas ignited and burned for 55 minutes. Twelve persons who were camping under a concrete-decked steel bridge that supported the pipeline across the river were killed and their three vehicles destroyed. Two nearby steel suspension bridges for gas

FROM A CORROSION ENGINEERS STANDPOINT:

Post-accident on sight inspection - The force of the rupture and the violent ignition of the escaping gas created a 51foot-wide crater and ejected three large pieces. Investigators visually examined the pipeline that remained in the crater as well as the three ejected pieces. All three ejected pieces showed evidence of internal corrosion damage, but one of the pieces showed significantly more corrosion damage than the other two. Pits were visible on the inside surface of this piece, and at various locations, the pipe wall evidenced significant thinning. At one location, a through-wall perforation was visible. No significant corrosion damage was visible on the outside surfaces of the three pieces or on the two ends of the pipeline remaining in the crater. Internal Corrosion in line 1103 - Interconnecting pits were observed on the inside of the pipe in the ruptured area of line 1103. Typically, these pits showed the striations and undercutting features that are often associated with microbial corrosion. A pit profile showed that chloride concentration in the pits increased steadily from top to bottom. Increased chloride concentration can result from certain types of microbial activity. All four types of microbes (sulfate reducing, acid-producing, general aerobic, and anaerobic) were observed in samples collected from two pit areas in the piece of line1103 where internal corrosion was discovered after the accident about 2,080 feet downstream of the rupture site. Though the individual contribution of various microbes in the corrosion process could not be estimated, the damage morphology and the corrosion product analyses data suggest that microbiological activity contributed to the corrosion process. Dissolved O2 in an electrolyte could cause pitting by creating concentration cells. CO2 is soluble in water and will form carbonic acid, which is corrosive to carbon steel. When dissolved in water, H2S forms a weak acid that could corrode carbon steel. In combination with dissolved O2, it could cause pitting. Though generally present in low concentrations, these potentially corrosive constituents were present in the gas that was being transported in line 1103. Also, upset conditions occasionally increased the concentrations of these constituents in the transported gas. Chlorides were observed in all corrosion product/deposit samples. Anions, such as chloride, cause pitting and, typically, chloride concentration in a pit may be much higher than the chloride concentration outside the pit (bulk concentration). Chemical analyses showed that the pH (6.7-6.8) of the liquid collected at the Pecos River compressor station plant inlet separator scrubber was more acidic than the pH (8.2) of the liquid collected at Keystone compressor station inlet scrubber. Also, the material collected at line 1100 and 1103 pig receivers (pH 6.2-6.3) and the inside material collected from a low spot on line 1103 west of the rupture (pH - 6.4) were more acidic than the material collected near the siphon drain area of the line 1103 drip (pH 8.9). The observed low pH in the samples could be a result of dissolved CO2, and/or H2S in the water, and/or intrusion of low-pH ground water into the gas supply. Typically, acidic (pH<7) water is more corrosive to carbon steel than basic water (pH>7).

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Thus, water and contaminants such as chlorides, O2, CO2, H2S and microbes all likely contributed to the observed corrosion damage.

CONCLUSION: While the occurrence of corrosion and environmental degradation of

the materials seems inevitable, It can be avoided to certainly a large extent. The timely measures taken on the part of engineers can result not only in cost reduction of the industry or organization but can also become a saving cause for hundreds of valuable human life. Histroy always has its way of delivering lessons, time has come that a developing contry like ours takes steps at every possible level to reduce the risk of any catastrophe occuring due to corrosional degradation.

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