The Adsorption of Oleyl Propylenediamine (OLDA) on Metal Surfaces Under Dry Steam Conditions

ABSTRACT

The technology of film forming amines (FFAs) has been successfully applied for many years in water/steam cycles. Due to the intense research in recent years, many concerns have been clarified, such as the mechanism of corrosion protection. It is commonly agreed that a film is formed on the metal surfaces which prevents or at least reduces the contact of corrosive species with the metal.

The adsorption of oleyl propylenediamine (OLDA) from aqueous solution and wet steam has been thoroughly studied. However, it is still disputed whether OLDA also adsorbs from dry steam, and thus would be able to protect the inner surfaces from the superheater and reheater sections.

This paper presents a study carried out in a pilot boiler equipped with an electrically heated superheater and specially designed removable test specimens for subsequent analysis. Since the dry steam flow to the test specimen could be quickly turned off and on, the period of wet conditions during the trials could be reduced to ca. 2 · 10^–3 % of the total trial time.

Two different chemical treatment programmes were applied in the water/steam cycle: first all-volatile treatment under oxidizing conditions (AVT(O)) with ammonia and thereafter a film forming amine product (FFAP) (Fineamin 90), which is a combinative product of OLDA as FFA and alkalizing amines. During the trials, the operational parameters boiler pressure and steam flow were kept constant.

Three different analytical techniques (droplet test, infrared spectroscopy, and photoelectron spectroscopy) consistently confirmed the presence of OLDA on the surface of the test specimen exposed to dry steam treated with FFAP chemistry. Solvent extraction with subsequent liquid chromatography/mass detection provided an upper limit of the surface coverage by OLDA. Moreover, OLDA adsorbed on the inner surface of a tube from the last part of the superheater was semi-quantitatively determined by photometry.

The tests in the pilot boiler with a superheater presented clear proof that OLDA also adsorbs on metals from dry steam. Thus, it can be concluded that also the superheater and reheater sections of a steam generator are protected by water/steam cycle chemistry that uses OLDA.

REFERENCES

• Kahler, H. L., Method of Protecting Systems for Transporting Media Corrosive to Metal, 1946. United States Patent and Trademark Office, US2460259A.
• Forêt, C., Stoianovici, G., Chaussec, G., de Bache, A., zum Kolk, C., Hater, W., "Study of Efficiency and Stability of Film Forming Amines (FFA) for the Corrosion Protection of the Carbon Steel in Water Circuits", Proc., EUROCORR, 2008 (Edinburgh, UK). European Federation of Corrosion, Paper 1404.
• Forêt, C., Stoianovici, G., Blériot, P., Hater, W., Matheis, J., "Film Forming Amines for Closed Cooling/Heating Water Systems", PowerPlant Chemistry 2014, 16(6), 361.
  Available from https://ppchem.com/insight-search/.
• van Lier, R., de Smet, A., Olsen, L.-M., Halasa, M., Fjaerem, T. A., "Thirty Years of Experience with Film-Forming Amines at a Norwegian Fertilizer Production Site", PPCHEM 2019, 21(4), 232.
  Available from https://ppchem.com/insight-search/.
• Sylwestrzak, E., Moszczynski, W., Hater, W., de Bache, A., Dembowski, T., "Experiences with the Treatment of the Water/Steam Cycle of the Adamów Power Plant with Film Forming Amines", VGB PowerTech 2016, 96(8), 69.
• Rahman, M., Lensun, L., "A Corrosion Comparative Study Between Carbohydrazide and AFPB (Helamin 906H) in Power and Desalination Plant", presented at the EPRI Film Forming Product Users Group Meeting, 2019 (Charlotte, USA). Electric Power Research Institute, Palo Alto, CA, USA.
• Senecat, A., Poelemans, N., "Two Cases of FFA Use in Engie Power Plants", presented at the 7th International Conference on Film Forming Substances, (FFS2024), 2024 (Prato, Italy). Mecca Concepts, Melbourne, Australia.
• Technical Guidance Document: Application of Film Forming Substances in Industrial Steam Generators, 2019. International Association for the Properties of Water and Steam, IAPWS TGD11-19.
  Available from https://iapws.org/.
• Technical Guidance Document: Application of Film Forming Substances in Fossil, Combined Cycle, and Biomass Power Plants, 2019. International Association for the Properties of Water and Steam, IAPWS TGD8-16(2019).
  Available from https://iapws.org/.
• vgbe Standard: Feed Water, Boiler Water and Steam Quality for Power Plants/Industrial Plants, 2023. vgbe energy service GmbH, Essen, Germany, VGBE-S-010-00-2023-08-EN.
  Available from https://www.vgbe.energy/.
• Hater, W., "Film Forming Amines – An Appraisal", PPCHEM 2021, 23(4), 162.
  Available from https://ppchem.com/insight-search/.
• Dooley, B., "Film Forming Amines", presented at the 6th International Conference on Film Forming Substances, (FFS2023), 2023 (Prato, Italy). Mecca Concepts, Melbourne, Australia.
• Dooley, B., "Film Forming Substances – Research Need and Improved Operation", presented at the 6th International Conference on Film Forming Substances, (FFS2023), 2023 (Prato, Italy). Mecca Concepts, Melbourne, Australia.
• Bohnsack, G., "Korrosionsinhibierung durch das in Helamin "filmbildende" Amin", VGB Kraftwerkstechnik 1997, 77(10), 841 [in German].
• Pensini, E., van Lier, R., Cuoq, F., Hater, W., Halthur, T., "Enhanced Corrosion Resistance of Metal Surfaces by Film Forming Amines: A Comparative Study Between Cyclohexanamine and 2-(Diethylamino) Ethanol Based Formulations", Water Resources and Industry 2018, 20, 93.
  DOI: https://doi.org/10.1016/j.wri.2017.11.001.
• Disci-Zayed, D., Jasper, J., Hater, W., "Adsorption of Oleyl Propylenediamine on Metal Surfaces", PPCHEM 2019, 21 (3), 146.
  Available from https://ppchem.com/insight-search/.
• Jero, D., Caussé, N., Pébère, N., "Film-Forming Amines as Corrosion Inhibitors: A State-of-the-Art Review", Materials Degradation 2024, 8(111).
  DOI: https://doi.org/10.1038/s41529-024-00523-0.
• Hater, W., Smith, B., McCann, P., de Bache, A., "Experience with the Application of a Film Forming Amine in the Connah's Quay Triple Stage Combined Cycle Gas Turbine Power Plant Operating in Cycling Mode", PowerPlant Chemistry, 2018, 20(3), 136.
  Available from https://ppchem.com/insight-search/.
• Smith, B., McCann, P., Uchida, K., Mori, S., Jasper, J.,  Hater, W., "Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine, on the Surfaces of Water-Steam Cycles", PowerPlant Chemistry, 2017, 19(3), 129.
  Available from https://ppchem.com/insight-search/.
• Allard, B., Chakraborti, S., "Controlling Corrosion and Scaling with Aliphatic Amines in Steam Generating Systems", Svensk Papperstidning 1983, 86(18), R186.
• Ochoa, N., Moran, F., Pébère, N., Tribollet, B., "Influence of Flow on the Corrosion Inhibition of Carbon Steel by Fatty Amines in Association with Phosphonocarboxylic Acid Salts", Corrosion Science 2005, 47(3), 593. 
  DOI: https://doi.org/10.1016/j.corsci.2004.07.021.
• Graf, A., Method for the Determination of Polyamines, 1993. European Patent Office, EP0562210A1.
• Stiller, K., Wittig, T., Urschey, U., "The Analysis of Film-Forming Amines – Methods, Possibilities, Limits and Recommendations", Power Plant Chemistry 2011, 13(10), 602. 
  Available from https://ppchem.com/insight-search/.
• Yoshioka, H., Yoshida, K., Noguchi, N., Ueki, T., Murai, K., Watanabe, W., Nakahara, M., "Microscopic Structure and Binding Mechanism of the Corrosion-Protective Film of Oleylpropanediamine on Copper in Hot Water", The Journal of Physical Chemistry C 2022, 126(14), 6436.
  DOI: https://doi.org/10.1021/acs.jpcc.2c00526.
• Kuilya, S., Subramanian, V., Bera, S., Rangarajan, S., "Evaluation of Octadecylamine for the Corrosion Inhibition of Incoloy 800", Corrosion Engineering, Science and Technology: The International Journal of Corrosion Processes and Corrosion Control 2021, 56, 119.
  DOI: https://doi.org/10.1080/1478422X.2020.1815950.