Ion chromatographic identification and quantification of glycol degradation products.
In water-based heat transfer systems, frequently glycols are added to the water to obtain freeze protection. For this purpose, ethylene glycol (EG) is the most common substance used. When heated, the glycol will slowly degrade and the pH of the glycol-water mixture will decrease, leading to corrosion and foaming problems. Carboxylic acids were identified as the main degradation products. Quantification of the carboxylic acids is of importance to monitor the degradation reactions in order to identify hot spots or overheating, caused by severe heat exchanger scaling, where pH measurements will not be sufficient due to buffer substances added for corrosion protection. In this work, ion chromatographic methods havebeen developed to identify the main degradation products of EG in heat transfer systems and to monitor the degradation process. Possible acidic reaction products of EG are glycolic acid, glyoxylic acid, oxalic acid, acetic acid and formic acid. Separations with a Dionex AS9-HC column with Na2CO3 eluents of differing concentrations showed that only trace amounts of carboxylic acids are present in aged heat transfer media. Oxalic acid can be quantified simultaneously to nitrite or molybdate which are added as corrosion inhibitors. A Dionex AS10 separation column with Na2B4O7 eluent enabled base line separation of glycolic acid, acetic acid and formic acid. Heat transfer media, which are operated in different heat transfer systems under different conditions, were analysed. A system was identified, where severe overheating due to fluid maldistribution in the heat exchanger took place.
Madera
M
M
Institute for Chemical Engineering, Fuel and Environmental Technology, Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria. martin.madera@omv.com
Höflinger
W
W
Kadnar
R
R
D019342:Acetic Acid / Q000032:analysis; D002264:Carboxylic Acids / Q000032:analysis; D002852:Chromatography, Ion Exchange / Q000379:methods; D003451:Cryoprotective Agents / Q000032:analysis / Q000737:chemistry; D019855:Ethylene Glycol / Q000032:analysis / Q000737:chemistry; D005561:Formates / Q000032:analysis / Q000302:isolation & purification; D006016:Glycolates / Q000032:analysis; D006018:Glycols / Q000032:analysis* / Q000737:chemistry*; D006038:Glyoxylates / Q000302:isolation & purification; D006358:Hot Temperature; D006863:Hydrogen-Ion Concentration; D019815:Oxalic Acid / Q000032:analysis
D002264:Carboxylic Acids; D003451:Cryoprotective Agents; D005561:Formates; D006016:Glycolates; D006018:Glycols; D006038:Glyoxylates; C031149:glycolic acid; C030544:formic acid; D019815:Oxalic Acid; D019855:Ethylene Glycol; C031150:glyoxylic acid; D019342:Acetic Acid