MATERIALS FORUM VOLUME 30 - 2006 Edited by R. Wuhrer and M.
Cortie Institute of Materials Engineering Australasia Ltd
CORROSION AND MATERIALS SELECTION FOR AMINE SERVICE
S. Rennie Woodside Energy Ltd ABSTRACT Amines are used in refineries and gas plants around the world to remove both H2S and CO2 from feed gas. The corrosion in amine plants is not caused by the amine itself, but is caused by the hydrogen sulphide, CO2 and by amine degradation products. Amines are compounds formed by replacing hydrogen atoms of ammonia, NH3 by organic radicals. Problems with amine units can be corrosion or by cracking (sulphide stress cracking, hydrogen induced cracking associated with hydrogen blistering, stress-orientated hydrogen induced cracking, and alkaline stress corrosion cracking). Areas to have a close look at is where impingement erosion could occur, where there is elevated temperatures, where flashing off of CO2 could occur, and where heat stable salts could cause scaling. Carbon steel and stainless steel are suitable for most applications, with the choice of material being determined by the susceptibility to the damage modes in each location. Careful consideration should also be given to the repair of plant (controlling weldment hardness) 1. INTRODUCTION Amines are used in refineries and gas plants around the world to remove both H2S and CO2 from feed gas. The gas may be either feed gas in terms of a Gas plant, or it could be off-gases and olefinic and saturated liquefied Petroleum Gas (LPG) streams generated during the operation of Catalytic Crackers1. Sulphur recovery units in Refinery operations also use amines. CO2 can cause problems in gas processing plants and refineries alike. It may cause problems in hydrate formation, and affect specification of products such as ethylene in gas cracking units2 . The corrosion in amine plants is not caused by the amine itself, but is caused by the hydrogen sulphide, CO2, and by amine degradation products (Metals Handbook, Vol 13). The interest in amine units has been particularly strong by NACE and the like since the Unocal disaster in 1984. Amines are compounds formed atoms of ammonia, NH3 by chemistry of acid gas removal relatively complex, but the (exothermic) are: H2S + R2NH CO2 + R2NH by replacing hydrogen organic radicals. The by amine solutions is simplified reactions In the case of the Methanolamine (MEA), the methanol molecule loses an H bond and attaches to the amine molecule (which also loses an H bond. The formula is CH2OHNH2. Secondary amines such as diethanolamine (DEA) and diisopropanolamine (DIPA) are similar except that there are two alcohol molecules for the one amine molecule (i.e NHR2), where the R represents the alcohol radical. A tertiary amine has 3 alcohol radicals to the N atom (i.e NR3). MEA has been reported to be responsible for stress corrosion cracking (SCC) failure of vessels in the late 1980s3. Conversion to MDEA eventually leads to low corrosion rates and elimination of SCC 2. PROBLEMS IN AMINE UNITS Problems with amine units can be split in to two categories: Corrosion Corrosion of amine units is usually not caused by the amine itself, but more the dissolved acid gases, primarily hydrogen sulphide and carbon dioxide. Heat stable salts resulting from the amine degradation can also cause corrosion problems. API RP945, Avoiding Environmental Cracking in Amine Units,4 indicate that, in low pressure systems, corrosion of amine units used primarily to remove carbon dioxide has been historically more severe than that of units used to remove either hydrogen sulphide, or carbon dioxide and hydrogen sulphide. This is supported by Schmeal et al5. In high pressure systems
R2NH2+ + HSR2NH2+ + R2NCOO-
Types of Amines used include primary amines (NH2R) such as Methanolamine (MEA) and diglycolamine (DGA), and secondary (NHR2) and tertiary amines such as diethanolamine (DEA), (NR3) diisopropanolamine (DIPA) and methyldiethanolamine (MDEA). 126
