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IBP1209_12 Inerting Ballast Tanks Gabriel L. Baes1, Jos Bronneberg 2, Maria A. S. D.

de Barros3

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

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Abstract
This report expands upon the work conducted by SBM Offshore to develop a tank preservation treatment, which is intended to achieve a service life of 30 years. This work focuses on the corrosion problems, in the ballast tanks, based on new built hulls, both for the Gas Exploration Market, the FLNG - Floating Liquefied Natural Gas, and for the Oil Exploration market – FPSO’s – Floating Production Storage and offloading Units. Herein, the corrosion rate input comes from the various references related to the process of nitrogen injection, which is expected to extend the vessel’s time life. The essential elements of this solution comprise the deoxygenation process, corrosion models, coating effects, tests from laboratory, shipboard tests, corrosion institutes and regulations applicable to the operation. The best corrosion protection system for ballast tanks area combines a coating system and an inert gas system. The condition of the tanks will be dependent upon the level of protection applied to the steel structure, including, but not limited to coating, cathodic protection, etc. There is a need for products which extend the life time. It is not sufficient, only have good theoretical base for the corrosion and an excellent treatment system. In addition, the design of the ships structure must also eliminate the presence of local stress concentrations which can result in fatigue cracking and rupture of the protective coating barrier starting the corrosion. As a direct result of this, more problems in corrosion can be mitigated, vessels can have a better corrosion performance with less maintenance and repairs to coating systems in ballast tanks. Furthermore ships will be positively impacted operationally due to less frequent drydockings. There is a huge potential in the application of inert gas to combat the corrosion rate inside the ballast tanks, one of the most corrosive environments on earth. This application can have a direct impact on vessel structure, reducing operational expenditure.

1. Introduction
The world demand for gas is growing rapidly. The world’s primary energy needs are to grow by more than 50% between 2005 and 2030 and liquefaction capacity will need to increase fivefold to meet this increased demand. Such a capacity increase requires fields conveniently located close to large onshore facilities to make such facilities economically viable. Floating LNG production, storage and offloading concepts (FLNG) have a number of advantages over conventional liquefaction plants for offshore resources, not least the ability to station the vessel directly over distant fields thus avoiding expensive offshore pipelines and the ability to move the production facility to a new location once the existing field is depleted. The technology has been discussed and evaluated in various forms for several decades, but has yet to reach commercial reality. Herein, a FLNG model was used to mitigate the corrosion rate inside the ballast tanks. One of the most important considerations in controlling corrosion, it is to minimize investment and operational costs through life. There are many materials that are used for ships structure, outfitting and piping, etc. Often corrosion problems arise due to the materials or coatings that are incompatible with the operating environment.

______________________________ 1 Chemical Engineer - SBM Offshore 2 Manager, Chemical Engineer - SBM Offshore 3 Ph.D., Chemical Engineer – Universidade Estadual de Maringa

Rio Oil & Gas Expo and Conference 2012 Many methods can be employed to protect marine structures from corrosion, such as paints, other forms of coatings and cathodic protection. However, there are no perfect long lasting corrosion protection systems or methods, which are used in the marine environment and it is inevitable for vessels to experience corrosion to some greater or lesser extent. Careful attention and consideration to the potential corrosion should be provided during a ship design stage, fabrication, subsequent in-service maintenance and inspection. On this subject, the inert gas will be introduced as one of the most effective corrosion control methods in enclosed marine structures, more specifically in the ballast tanks. The most important role of a corrosion model is to enable an operator to estimate; at what time in the future ships structures will require maintenance by replacing corroded plates, renewing coating, anodes, etc. If the plate thickness or coating condition is below the level required by classification rules, then the replacement or upgrade must be carried out. An economical decision for the next maintenance and replacement period can be planned and facilitated when the rate of future corrosion degradation can be estimated properly. Uniform corrosion is the most common form of corrosion found in the many grades of mild steel, which is mainly used for marine structures. Normally uniform corrosion is calculated from weight loss or sampled thickness measurement from test plate coupons. Many researchers have done considerable effort to develop time-based predictive mathematical models. Many data was obtained from large numbers of thickness measurements made on many vessels that have been in-service for some years. Such thickness measurements are typically made using ultrasonic techniques and several point measurements may be made over the surface of a plate in order to arrive at an assumed average value. Obviously thickness measurements must be made by approved technicians by using approved methods in order to ensure that there is a good degree of confidence in the obtained data. Much difference was often found in each set of corrosion data, even though corrosion data was sampled in same type of vessels. This means that any generalized models will have a fairly high level of uncertainty. Most of recent corrosion models are based on measured data. Normally, it should be considered that the most reliable corrosion models are those that are based on actual measurement on hundreds of vessels, this means that a large degree of scattered data is unavoidable in sampled values. The reason is that there are many factors which accelerate individual levels of corrosion. Examples are: sediment removal, type of coating, humidity, temperature, inert gas quality, ballast frequency and presence of sacrificial anodes. Thus reliability and safety assessment considering corrosion degradation is very important in ageing ships. This is clearly very significant especially when the level of corrosion exceeds the corrosion margins that are required by the relevant classification society. In the case of uniform corrosion, the stiffened and unstiffened plates can be easily estimated by reducing the plate thicknesses from their original values. It is very important to have a better understanding of the causes of corrosion, the proper corrosion prevention methods, the corrosion rate estimation models, the structural capacity, etc.. One reason is to facilitate repair decisions for a vessels inspection and maintenance program. Another possible broad reason may be to support a structural life extension decision later in life.

2. Corrosion
Sea water is an aggressive corrosive environment because it is a good electrolyte and contains corrosive salts. The marine environment means that corrosion in marine structures, which are generally fabricated with various grades of mild steel and low alloy steel, is very severe not only under immersed conditions in ballast tanks but also under general exposure to atmospheric conditions. Corrosion eventually reduces the thickness of ships structure which results in a corresponding reduction in both local and overall strength of the structure. Improperly maintained ageing ship structures could finally lead to disastrous failures in rough seas and heavy weather. Many investigations and research studies show that the mean value of the annual corrosion degradation in typical ballast tanks varies from 0.027mm to 0.21mm per annum. Furthermore the maximum annual corrosion degradation can reach up to 0.807mm. Similarly some excessive pitting corrosion of up to 2.0mm per year was found in the uncoated bottom plating in cargo tanks and this was considered to be due to a complex microbial induced corrosion process. The rusting of ordinary carbon steels is generally called corrosion. This form of attack attributes to the major part of the maintenance and repair costs for its control. The costs may arise from a huge amount of steel renewals, or from the repair/renewal of coating. This form of corrosion is the most common and is typified by steel rusting in air, and generally appears in cargo and ballast tanks. General corrosion means that it proceeds at more or less at the same average rate over the whole surface of the metal that is exposed to the corrosive environment, but actually the loss of metal is not completely uniform and there is typically a slight difference over the surface. The loss of thickness leads to the loss of local strength and integrity of structure. Although this kind of corrosion usually takes place slowly it should be inspected at regular intervals in order to ensure that it does not exceed any critical values in the structure which is assumed in the (classification society) rules. 2

Rio Oil & Gas Expo and Conference 2012 However it is difficult to investigate and judge the thickness loss until there is excessive metal loss on the structure. Typically several measurements would be made over the surface of a discrete plate element. The corrosion degradation rate varies according to operating sea area, ships type and corrosion location.

3. Inerting
The system being analyzed brings nitrogen with a relatively small fraction of oxygen in contact with ballast water. The oxygen level in the ballast water is assumed to have reached equilibrium with air as a result of prolonged contact, and therefore would contain a concentration of oxygen sufficient to support a wide spectrum of life forms. The objective is to reduce the oxygen content to a low level due to displacement by the nitrogen gas. The gas is bubbled through the ballast water, which assures uniform distribution of dissolved gas throughout the ballast tank. Therefore concentration differences in the tank can be neglected. Bubbles are assumed to be small and homogeneously distributed over the tank. The deoxygenation process follows Henry's Law with equilibrium achieved within the residence time of each bubble. As the gas is flushed through the system, the total content of oxygen in the ballast water will be reduced. Using high purity nitrogen, without sulphur and traces of oxygen in its composition means that such system can reduce corrosion rates significantly in enclosed steel structure in marine and offshore environments. The gas composition from the N2 generator depends on the design of the system, normally between 98% and 99.9% N2. Miyuki et al. have carried out laboratory simulations of corrosion in a wet inert gas environment (13% CO 2 , 5% O2 and a small amount of SO2 ) and they found that the corrosion rates increased with increasing levels of O 2 and SO2 contents in the inert gas. Matsuda et al. have introduced a new anticorrosion method that purges oxygen from ballast tanks by providing a continuous supply of nitrogen. The design concept is that liquid nitrogen, that is stored in independent tank, supplies nitrogen gas passing through an evaporator and a reduction valve into the ballast water. The pressure within the ballast tank is controlled by a pressure release device and the ballast tank is monitored by pressure, temperature and oxygen sensors. Subsequently they found that the rate of rusting on shot blasted steel test plates placed at the bottom of the nitrogen treated ballast tank was 0.039 mm/year, compared with 0.382 mm/year for the same type of plates at the bottom of a standard ballast tank with normal operating tank atmosphere condition. This means that the corrosion rate of nitrogen treated environment is approximately 10 % that of normal operating tank atmosphere condition. It also found that painted steel plates with the nitrogen atmosphere treatment the corrosion rate was reduced to 0.001 mm/year. Similarly, recently Ok and Pu et al. presented the economical and innovative solution to control corrosion in marine and offshore structures by using clean inert gas and concluded that clean inert gas can be advantageous, economical and innovative methods to control corrosion for marine and offshore structures. It is apparent that an oxygen content of below 1% will reduce the rate of corrosion significantly. A N2 generator can thus be used to control corrosion within cargo tanks and ballast tanks. A N2 generator could be an economic solution for vessels where an inert gas system is not compulsory by the Classification Society requirements. For offshore production units, which normally already have N 2 generation capabilities, this would mean a relatively small expansion of the N 2 production capacity to cater for corrosion mitigation in the ballast tanks. There is no additional piping, except for the cross over, necessary to put the inert gas into the ballast tank during an operation where the ballast tanks are empty. The provision of inert gas supply to the double hull space through existing ballast piping is carried out after completion of de-ballasting of the tanks. There are no specific rule requirements to supply inert gas to ballast tanks and some classification societies may be more conservative than others in the application and interpretation of this system. However considering the potential reduction of corrosion rates and the resultant increasing reliability of ship structure, a more optimistic interpretation is justified in order to apply this system. There are many factors which accelerate corrosion in marine structures. A temperature increase of 10°C may approximately double the electrolytic reaction rates. This means that the corrosion rate is approximately doubled for every 10 °C of temperature increase. It is thus apparent that the higher temperature potentially accelerates the corrosion degradation in a structure. A high quality inert gas can be used to reduce corrosion degradation in marine structures. There is no capacity restriction to apply to inert gas systems and the operator can adopt a smaller capacity considering individual operation concepts and can reduce equipment cost. Also, Ok and Pu et al. found that the clean inert gas can effectively control corrosion of marine and offshore structures, reduce overall maintenance costs considerably for replacement of steel structures, and possibly can reduce tank coating thicknesses for both new building and repairing ships. For the measurement of corrosion rate under deoxygenated situation, the empirical tests from Matsuda et al, where used for the results to this application. It is estimated that the corrosion rate can be reduced to 1/10 of the normal corrosion rate when applying an inert atmosphere. 3

Rio Oil & Gas Expo and Conference 2012 According Tamburri et al., the deoxygenation can dramatically reduce the survivorship of most organisms found in ballast waters. The oxygen tolerance of various organisms and larval forms vary. The comprehensive review for oxygen limits of invertebrate larvae shows that hypoxia or anoxia can only be tolerated at most a few days and commonly just a few hours. The representative sample review of all aquatic organisms found similar results but in a few cases adult animals were able to withstand near anoxia for over a week. However, the ability to withstand such extended periods of low oxygen appears to be the exception and was commonly the reason oxygen tolerance of some particular species.

Figure 1. Oxygen Level versus Time Life for Invertebrate larvae - Tamburri

Figure 2. Oxygen Level versus Time Life for Aquatic Organisms - Tamburri In the figures above, it is possible to see the behavior for the most usual invertebrate larvae and for the main aquatic organisms found in the world. 4

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Figure 3. FLNG Ballast Tank Arrangement According with the calculations, injecting a flow rate of 1 volume of Inert Gas for 2 1/3 of seawater intake, the percentage of oxygen in the water ballast tank after the physical displacement that would occur, for the Low Purity Nitrogen (98% N2) the oxygen level will be reduced to 4.5% and for the High Purity Nitrogen (99.9% N2) the same level will be 1.6%.

Figure 4. FLNG -Corrosion Rate Comparison In the scheme bellow we can have an idea about the system, the oxygen levels that could be achieved in this way (2-stage de-oxygenation). If we try to compare this situation with the one stage, we can see the differences on the final performance.

Figure 5. Inert Gas System Injection Scheme – one injection 5

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Using High Purity Nitrogen in the one step (mixer) arrangement the oxygen level is reduced to 1.63%, in the two steps Arrangement (figure 5) the level is reduced to 0.20% achieving the goal of less than 0.5% according to the results found in the literature. The picture bellow shows a schematic of the inert gas supply from an inert gas generator to a double hull ballast tank through an existing inert gas supply main and ballast piping line.

Figure 6. Inert Gas System Injection Scheme – two injection Looking the midship section of SBM FLNG, it is possible to have a better approach for the ballast tank structure.

Figure 7. FLNG Midship Section 6

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A weight saving calculation for the ballast tanks was made using high purity nitrogen as the inerting gas. The cost of the coating was kept the same as for the case where no inert gas is applied. The steel cost was calculated for the different corrosion rates that impact in the design of the structure, the thickness dedicated for the corrosion allowance could be change from 0.075 mm/year to 0.02 mm/year. Including in the steel price, the welding, cutting, fabrication, staging, lighting and also stiffeners, the total savings excluding the coating adds up to approx. 4,000,000 USD. Table 1. Comparing design savings

Design Weight (kg) Cost (USD)

20 (years) 650,000 2,600,000

30 (years) 1,000,000 4,000,000

4. Conclusions
The effectiveness of corrosion mitigation depends on the flow rate and the purity of the nitrogen. This means that we can always continue inerting until the required concentration or nitrogen threshold is obtained. The principal objective of designing a ship is to reduce the risks of structural failure in order to ensure the safety of life, environment and assets, and to provide adequate durability of the hull structure for the design life. The references used in this article focus on the effects of inert gas on the corrosion degradation. Some mathematical models and programs were developed to evaluate the corrosion parameters and to predict future maintenance requirements. This article concludes that a high purity inert gas generator system can be used to reduce corrosion degradation in marine structures in areas such as ballast tanks , and it has been found that high quality inert gas can be an effective economic solution considering the reduced corrosion rate, maintenance /repair/steel replacement costs and improved end of life value for the vessel. The results indicate the effectiveness of inert gas on the corrosion control of marine and offshore structures. This means that a well designed inert gas system can minimize corrosion rates of structures and accordingly can minimize section modulus degradation over typical service life. The proposals, investigations and methodologies reviewed and examined helped to evaluate suitable corrosion margins for marine structure during the design stage, to perform coating assessment under a corrosive environment, and to determine proper maintenance periods for double hull tankers as well as for other ship types. However, there are still many areas which deserve further attention and analysis as tank structural details might have a different time variant section modulus degradation ratios and associated stress change at upper deck and keel.

7. Acknowledgements
I would also like to thank my family for the support they provided me through my entire life and in particular, I must acknowledge my father and best friend, Feliciano Baes, without whose determination, encouragement and assistance. In conclusion, I recognize that this opportunity would not have been possible without the SBM Offshore and express my gratitude to this company.

8. References
C. GUEDES SOARES, Y. GARBATOV, A. ZAYED, G. WANG, Influence of environmental factors on corrosion of ship structures in marine atmosphere, Centre for Marine Technology and Engineering, Technical University of Lisbon, Instituto Superior Técnico, Portugal, 2009 C. GUEDES SOARES, Y. GARBATOV, A. ZAYED, G. WANG, Non-linear corrosion model for immersed steel plates accounting for environmental factors, Transactions of the Society of Naval Architects and Marine Engineers 113 (2005) 306– 322. C.P. GARDINER, R.E. MELCHERS, Corrosion analysis of bulk carriers Part I: operational parameters influencing corrosion rates, Department of Civil, Surveying and Environmental Engineering, The University of Newcastle, Australia, 2003 C.P. GARDINER, R.E. MELCHERS, Enclosed atmospheric corrosion in ship spaces, British corrosion Journal 36 (4) (2001) 272–276. 7

Rio Oil & Gas Expo and Conference 2012 H. MIYUKI, A. USAMI, K. MASAMURA AND Y. KOBAYASI, Corrosion Resistance of TMCP Steels for VLCC cargo Oil Tanks, Industry Seminar held at the Baltic Exchange in London, 8 and 9 October 1998. J AZEVEDO, Protecting Off shore Investments against Corrosion with Innovative Epoxy Technology, OVERFLATEDAGENE 2003 The Surface Protection Conference & PCE Marine and Off-Shore Conference, Stavanger, Norway, November 2003. J AZEVEDO, A new approach for steel structures protection using UHP hydroblasting and a solvent-free and humidity tolerant epoxy system with edge-retentive properties‟, EUROCORR 2005. The European Federation of Corrosion Conference, Lisbon, September 2005 J. K. PAIK, A. K. THAYAMBALLI, A time-dependent corrosion wastage model for seawater ballast tank structures of ships, Department of Naval Architecture and Ocean Engineering, Pusan National University, South Korea, 2003. J.K. PAIK, A.K. THAYAMBALLI, Ultimate Limit State Design of Steel-plated Structures, John Wiley & Sons, 2003. MATSUDA, M., et al., An anticorrosion method for ballast tanks using nitrogen gas. Ship and Ocean Foundation Technical Report, 1999. M. N. TAMBURRI, Ballast water deoxygenation can prevent aquatic introductions while reducing ship corrosion, Monterey Bay Aquarium Research Institute and Monterey Bay National Marine Sanctuary, USA, 2001. M.T. GUDZE, R.E. MELCHERS, Operational based corrosion analysis in naval ships, Centre for Infrastructure Performance and Reliability, School of Engineering, The University of Newcastle, Australia, 2008 OK, D. AND Y. PU. Corrosion control method by using clean inert gas to ballast tanks and permanent void spaces in marine and offshore structures. In: 3rd International Marine Science and Technology for Environmental Sustainability (ENSUS) Conference. 2005. Newcastle upon Tyne, UK. R. E. MELCHERS, Examples of mathematical modelling of long term general corrosion of structural steels in sea water, Institute of Materials, Minerals and Mining, Australia, 2006 R.E. MELCHERS, Mathematical modelling of the diffusion controlled phase in maritime immersion corrosion of mild steel, Department of Civil, Surveying and Environmental Engineering, The University of Newcastle, Australia, 2002. R.E. MELCHERS, T. WELLS, Models for the anaerobic phases of marine immersion corrosion, Corrosion Science 48 (7) (2006) 1791–1811

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