Leak Detection Safeguarding Stamicarbons High Pressure Urea Vessels

Urea solutions are not very corrosive, but ammonium carbamate, an intermediate in urea synthesis is highly corrosive. To protect the carbon steel high pressure synthesis equipment from corrosion, stainless steel loose liners are commonly applied. With a loose liner a hazardous situation may arise if a leak occurs and carbamate containing fluids enters the space between liner and carbon steel. For this reason Stamicarbon designed a system which continuously monitors for leaks to allow safe operation of said equipment.

Alex Scheerder Stamicarbon BV, the Netherlands

Introduction

rea is synthesized from ammonia and carbon dioxide at pressures of about 145 bar (2200 psi) and temperatures of 183 C (360 F). In a modern Stamicarbon world scale (~ 3500 mtpd) urea plant the synthesis section consists of three high pressure vessels; Pool Condenser, Urea Reactor and HP Stripper, see Figure 1. Ammonia, carbon dioxide and urea are not very corrosive, but the synthesis solution becomes highly corrosive due to ammonium carbamate formed as intermediate step in the synthesis of urea. For instance, ammonium carbamate solutions in contact with carbon steel will cause corrosion rates in excess of 900 mm per year.
Figure 1: Modern Stamicarbon (Avancore) Urea Plant highlighting HP Urea Synthesis equipment

Undetected carbamate corrosion of the carbon steel pressure shell of urea vessels can lead to catastrophic failures. To avoid corrosion of the carbon steel shell Stamicarbon applies special steel grades such as Safurex, strict

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specifications as to the quality and welding of these steels and strict design requirements with respect to the application of the protective corrosion resistant layer. This corrosion resistant layer can be applied as a loose liner, a weld overlay or as an explosive cladding. A weld overlay is commonly used on carbon steel tube sheets of heat exchangers (Pool Condenser, HP Stripper) or on small surface areas such as for instance hemi-heads, nozzles, etc. For larger surface areas (shell of Pool Condenser or Urea Reactor) it is economically more feasible to apply a loose liner. Having a loose liner, a hazardous situation may arise if a leak occurs and carbamate containing fluids enter the space between the liner and carbon steel pressure shell. This leads to corrosion of the carbon steel and will weaken the pressure vessel wall. Vessels having a liner installed are equipped with an early warning system for carbamate leakages. Stamicarbon designed a leak detection system with continuous monitoring to allow safe operation of the said vessels.

Passage ways underneath loose liner Loose liner plates are welded onto the carbon steel pressure shell, forming liner compartments. The confined space of each compartment is monitored for leakages. The liner weld is the most critical part with respect to the risk for leakages. To enhance the probability to detect a leak each liner compartment is equipped with passageways including two leak detection holes through the pressure shell. The passageways are machined in the pressure vessel wall parallel to the buffer layer to fix the liner plates, see Figure 2 and Photo1.

Figure 2: Principle of leak detection in HP urea vessel with loose liner

System outline
The leak detection system consists of three parts: Passage ways underneath loose liner Piping system and headers Monitor system

Photo 1: Leak detection passageways machined in c-steel hemi-head

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Piping system and headers The confined space of each liner compartment is connected to the leak monitor with pipes and headers, see Photo 2. The piping must be gas tight, in order to avoid false indications. To avoid crystallization of the urea / ammonia carbamate solution the temperature of the piping system must be kept above 135 C (275 F). This can be done by heating or insulating the piping.

feature for reliable leak detection is the property of ammonia to emerge readily through moisture.

Photo 3: Ammonia gas detector

Features
The features of the Stamicarbon leak detection system are: 1. Accurate detection. 2. Detection of a gas leak of 1 x 10-7 STD.cc /sec1 is possible. 3. The response time (i.e. the time elapsing before a leak is detected) is less than 60 minutes. 4. The location of the leak can be traced. 5. The leakage rate can be calculated. 6. More than one piece of equipment can be connected to the gas monitor. It should be taken into account that the synthesis composition varies throughout the HP loop. Therefore the composition of fluid leaking behind the liner will also differ from one place to another and thus the ammonia concentrations will differ. This will influence the ammonia

Photo 2: Header of Pool Condenser

The headers of all vessels are connected in parallel to the main header, which in turn is connected to the leak monitor. In each pipe line towards the header a block valve is installed to make it possible to isolate circuits and to localize any leaks detected. Also block valves are mounted on the main header in order to determine which vessel is leaking. Monitor An electrochemical sensor that allows continuous ammonia gas detection is used for leak detection, see Photo 3. Ammonia is chosen as leak agent since it is present throughout the whole synthesis section of the plant and is easy to detect. Also carbamate leaking behind the liner will dissociate into ammonia and carbon dioxide since the pressure behind the liner is atmospheric. An important

Leakage rates are normally indicated in STD.cc/sec. (standard cubic centimeters per second)

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concentrations measured and must be taken into account for calculating the leak rate. A quick response time is needed because the synthesis solution leaking away between liner and carbon steel pressure shell not only contains the corrosive ammonium carbamate but also urea. This synthesis solution will partly dissociate and finally crystallize as biuret or triuret, with the risk that detection becomes impossible due to blockage of the passage ways.

Flow type leak detection system The flow type leak detection system can be used in all new equipment since they are equipped with the grooved passageways system and at least two leak detection holes in each liner compartment. In the gap between liner and pressure shell instrument air is circulated, see Figure 3. The air must be dried before entering the gas monitor.

Operating principles
The annular space between the carbon steel pressure shell and liner, together with the leak detection holes, is connected to the gas monitor via headers/coolers. The air present in this system is brought to the monitor with help of plant instrument air. The monitor provides a continuous indication of gaseous ammonia concentrations. The monitor operates with help of an electrochemical sensor, allowing analyzing ammonia concentrations up to 1,000 ppm in a mixture of gases. Stamicarbon has two concepts for leak detection available. - A flow type leak detection system. - A vacuum type leak detection system. Whether a flow or a vacuum type leak detection system should be utilized, depends on the possibility to circulate gas through the liner compartments. The vacuum type leak detection system is suitable for older equipment having no passage way grooves and only one leak detection hole. Circulation of air is not possible in this case.

Figure 3: Flow type leak-detection system

During circulation, the resistance is not the same in each liner compartment. To equalize this, a flow meter and a control valve are required in the piping to the header to optimize the flow in each liner compartment. The piping of each liner compartment ends in a header/cooler in which the air is cooled down to ambient. A small part of the air is fed into the gas monitor to analyze ammonia continuously. The remaining air is released to atmosphere. A reducing valve permits supply of instrument air into the system. If the pressure drops as a result of a leak developing in the connecting tubing or as a result of a shut-down, air will be supplied too. A flow meter is used to signal such a pressure drop.

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A safety valve prevents that the pressure in the system becomes too high. Vacuum type leak detection system In case no passageway system is present between lining and pressure shell, it is advisable to use the vacuum system, see Figure 4.

Operations & Maintenance

It is of importance to commission and operate the leak detection system according to the guidelines. During commissioning and plant shut down, care must be taken not to over pressurize the leak detection system. The system is safeguarded at 0.5 barg. Higher pressures may lead to bulging or even rupture of liner segments. Small leak indications must be monitored closely and in case the leak becomes big enough to locate, the plant must be stopped to find and repair the leak. In this way corrosion damages to the carbon steel pressure shell can be avoided. A leak indication which suddenly stops is of potential risk for corrosion damage of the carbon steel shell. The plant must be stopped immediately to locate and repair this leak. Proper function of the system must be checked on regular basis. Blockage of the leak detection system (for instance due to crystallized product leaking behind the liner) will hamper leak detection and may lead to a dangerous situation. Stamicarbon does not recommend using steam condensate to open up blocked leak detection systems, see chapter 6.

Figure 4: Vacuum Type Leak Detection System

Fluids leaking from a liner are continuously sucked to a monitor by means of a vacuum pump. The piping of each liner compartments ends in a header/cooler, in which the air is collected, dried and cooled down. Then the air is sucked into a gas monitor in which the ammonia concentration is continuously measured. Air leaving is discharged through the flow indicator and a seal vessel. The seal vessel prevents air contaminated with ammonia from entering the leak detection system.

Locating leaks
The liner compartment, in which a leak occurs, can be traced by searching each compartment with help of the valves on the header. When the leaking compartment and the ammonia content are known, the leak rate can be calculated. This rate gives an indication about the probability to find the leak and which method to use.

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There are two methods recommended for finding a leak: Bubble test Ammonia leakage test Bubble test In case the leak is big enough, a bubble test is an appropriate method. The pressure in the gap between the liner and carbon steel shell is increased to maximum 0.3 barg using air or nitrogen. Detectable leak rate using the bubble method is in the range of 1*10-3 STD.cc/s. Ammonia leak test For smaller leaks an ammonia leak test is advised. Ammonia is introduced behind the liner with a maximum pressure of 0.03 barg. Before applying the ammonia the air is evacuated behind the liner by a vacuum pump. The detection ability of small leaks depends on the time for the ammonia to penetrate the leak, as indicated in Figure 5. After a dwell time of 8 to 10 hours leaks with a leak rate as small as 0.02 to 0.03 cc/hr becomes detectable. Ammonia sensitive spray or paste is applied onto the welds to be inspected. Leaks are detected by a color change of the paste or sprayed solution. Detectable leak rate is about 1000 times better compared to the air bubble test; ~ 1*10-6 STD.cc/s. For finding smaller leaks (leak detection system is able to detect leaks as small as 1*10-7 STD.cc/s), other strategies must be tried, see chapter 6.

Figure 5: Detection sensitivity of NH3 leak test

Helium or Freon gases are not recommended for findings leaks. Helium is not able to pass through moisture, which will be present behind the liner after a leak. In case the leak path is completely filled with moisture, Helium will not indicate the leak. Furthermore with this method it is difficult to pinpoint (locate) the leak. Freon is not recommended since any Freon left behind the liner could lead to chloride stress corrosion cracking.

Case histories
Finding a very small leak In a urea plant the leak detection system indicated a very small leak in the Urea Reactor. Despite the fact that the leak was too small to localize plant management decided to stop the plant. However the leak could not be located by neither bubble nor ammonia leak test. In order to find the leak the following strategy was followed. It was decided to pressurize the vessel with carbon dioxide and to dip the leak

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detection tubes into a water schematically presented in Figure 6.

bottle

as

At a certain pressure the leak became visible by bubbling of carbon dioxide gas in the water bottle. Keeping the pressure at this level the urea reactor was subsequently filled with water until the bubbling stopped. Water filling was stopped and the water level indicated the area where to search for the leak (just below the water level).

condensate was used which was readily available in the plant. In this way it was possible to open up the leak detection system. For this particular Urea Reactor a partial relining of the top channel was scheduled during a planned turnaround. Relining was due since the liner (316L urea grade) became too thin due to the corrosion at process side. The lifetime of a 316L UG liner of nominal thickness of 8 mm is typically 20 years. Stamicarbon advises to remove the old liner before installing a new liner. This has two reasons: To have again a proper function leak detection system in place after re-lining. To have the opportunity to check the carbon steel pressure shell. After removing the old liner, severe corrosion was observed in the carbon steel pressure shell, see Photo 4. General corrosion resulting in wall thinning as well as Trans-granular Stress Corrosion Cracks (TRSCC) was observed. Except for this Urea Reactor no TRSCC in other Urea Reactors was established in the casuistry of Stamicarbon urea plants. The root cause of this corrosion most likely was the presence of potassium in the gap behind the liner, whereby the forming of KHCO3 / KCO3 KH causes the Stress Corrosion Cracking (SCC). It is believed that the potassium was deposited here by the steam condensate (conditioning system). The carbon steel pressure shell was repaired and after installing a new liner segment the Urea Reactor was put into service again. However the structural integrity of the Urea Reactor was not guaranteed anymore, since there was also risk for SCC in the bottom part of the Urea Reactor. The liner compartments in the bottom (not re-lined) were also cleaned with steam condensate.

Figure 6: Pressure test method to locate leak in Urea Reactor

Eventually the leak was located and repaired. Ultrasonic wall thickness measurements of the carbon steel pressure shell proved that no corrosion occurred and the reactor could be operated safely without any constrains. Opening of blocked liner segments One of the urea plants suffered from blockages of the leak detection system in the Urea Reactor. To open the leak detection system steam

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Plant management decided to replace the Urea Reactor.

Photo 4: Carbon shell after removing liner; overall corrosion & stress corrosion cracks visible

This example shows that steam condensate must not be used for cleaning the leak detection system.

Conclusions
In the high pressure synthesis section of urea plants the process conditions are very corrosive. To protect the carbon steel pressure shell from corrosion, stainless steel liners or weld overlay are applied. In the case when a liner is applied, Stamicarbon strongly advises to install a system for continuous monitoring of leaks in the liner. Early warning of a leak is essential. Undetected leaks could lead to catastrophic failure of the vessel. The leak detection system designed by Stamicarbon is reliable and able to detect very small leaks. Monitoring the leak rate is possible, which enables plant management to act timely to find and repair the leak. Reliability of the leak detection system depends on correct operations and proper maintenance.

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