Treatment of High Purity Boiler Feedwater? J ames Robinson Luis Carvalho Anthony Rossi GE Power & Water Volatile Alkaline Treatments Are Commonly Used To Treat High Purity Feedwater Boost Feedwater and Condensate pH Boost pH in AVT Treated Boiler Water Volatile Alkaline Treatments Ammonia Neutralizing Amines Morpholine Cyclohexylamine Diethylaminoethanolamine Methoxypropylamine Ethanolamine Advantages of Neutralizing Amines Distribution of Amines in 2- Phase Systems Ability of Amines to Boost pH at the Temperature of the System. Steam-Water Distribution Ratio as a Function of System Pressure -- Water pH 25C = 9.0 0 1 2 3 4 5 6 7 0 500 1000 1500 System Pressure, PSIG D i s t r i b u t i o n
R a t i o Ammonia Cyclohexylamine Ethanolamine Common 2-Phase Systems Boilers Flash tanks Heat Exchangers Lines mixtures of steam and condensate pH of Pure Water as a Function of Temperature 0 1 2 3 4 5 6 7 8 25 50 75 100 125 150 175 200 Temperature (C) p H Increase of pH at Temperature Compared to that of Pure Water as a Function of Boiler Operating Pressure When pH at 25 C is Adjusted to 9.0 with Various Alkalizing Agents 0 0.2 0.4 0.6 0.8 1 1.2 1.4 0 500 1000 1500 System Pressure, PSIG p H
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W a t e r Ammonia Cyclohexylamine Ethanolamine Where are the differences in distribution ratio and pH at temperature important? CMS Evaluates all constituents in the system Calculates at temperature Acid dissociation constants Vapor-liquid distribution constants Uses flow data to project the concentrations in the liquid and the vapor phases Calculates pH 25C and pH t of each stream LP Evaps in Gas Turbine HRSGs Many preclude the use of phosphate or caustic for liquid phase pH control Volatile chemicals used for pH control 2-phase FAC became a common problem LP Evap Flow Accelerated Corrosion Principally in the Risers and Steam-Water Separators 44 4/20/2010 Feedwater 3 ppb CO 2 530 ppb NH 3 pH 25 = 9.2 Blowdown pH 25 = 9.1 pH @T = 6.5 Riser Liquid pH 25 = 9.0 pH @T = 6.4 LP Evap Steam NH 3 = 1990 ppb pH 25 = 9.6 FAC 100 psig LP evaporator Blowdown = 90% of feedwater Replacing Ammonia with ETA Reduces 2-Phase FAC! 45 4/20/2010 Feedwater 3 ppb CO 2 1500 ppb ETA pH 25 = 9.2 Blowdown pH 25 = 9.2 pH @T = 6.6 Riser Liquid pH 25 = 9.3 pH @T = 6.7 LP Evap Steam pH 25 = 7.8 100 psig LP evaporator Blowdown = 90% of feedwater What if we increase the feed of ammonia to produce the same pH @T (6.7) in the riser as we have with ETA? 46 4/20/2010 Feedwater 3 ppb CO 2 2300 ppb NH 3 pH 25 = 9.6 Blowdown pH 25 = 9.5 pH @T = 6.8 Riser Liquid pH 25 = 9.4 pH @T = 6.7 LP Evap Steam NH 3 = 9890 ppb pH 25 = 9.9 100 psig LP evaporator Blowdown = 90% of feedwater 45 4/20/2010 Feedwater 3 ppb CO 2 1200ppb MEA 300 ppb NH 3 pH 25 = 9.3 Blowdown pH 25 = 9.2 pH @T = 6.6 Riser Liquid pH 25 = 9.3 pH @T = 6.7 LP Evap Steam pH 25 = 9.4 100 psig LP evaporator Blowdown = 90% of feedwater High Pressure Evaporators 47 4/20/2010 Feedwater 20 ppb CO 2 5 ppb Cl pH 25 = 9.4 Cat Cond = 0.17 uS/cm 0.5% Blowdown 1 ppm Cl Riser Liquid 1500 PSIG Steam 48 3/30/2010 Fe 3 O 4 Ammonia Feedwater Treatment to pH of 9.4 10 Concentrations Under Deposit Porous Iron Deposit Water Steam Heat NH 3 =560 ppb Cl = 1000 ppb pH 25 = 8.26 pH t = 4.95 pH 25 = 3.7 pH t = 3.8 49 3/30/2010 Fe 3 O 4 ETA Feedwater Treatment to pH = 9.4 10 Concentrations Under Deposit Porous Iron Water Steam Heat MEA =9500 ppb Cl = 1000 ppb pH 25 = 9.6 pH t = 6.0 pH 25 = 9.4 pH t = 5.3 48 3/29/2010 Fe 3 O 4 Ammonia Feedwater Treatment to pH of 9.4 10 Concentrations Under Deposit TSP to 0.5 ppm PO4 + 0.5 ppm NaOH Porous Iron Deposit Water Steam Heat NH 3 =400 ppb Cl = 1000 ppb pH 25C = 8.6 pH t = 5.4 pH 25C = 4.1 pH t = 4.4 Treatment Program pH t in Boiler Tube pH t Beneath Deposit Low-Level Phosphate-NaOH- NH 3 5.4 4.4 AVT - ETA 6.0 5.7 5 ppb Acidic Chloride Contamination of Boiler Feedwater 50 3/24/2010 Fe 3 O 4 Ammonia Feedwater Treatment to pH = 9.4 TSP to 6 ppm PO 4 in Boiler Water 10 Concentrations Under Deposit Porous Iron Water Steam Heat Cl = 1000 ppb pH 25 =9.8 pH t =7.7 pH 25 = 10.4 pH t 8.7 Steam Turbines Steam Inlet CO 2 20 ppb Chlorides 5 ppb pH 25C = 9.4 1 st Condensate Temperature 212F Effect of % Steam Condensation on the pH at Temperature of the First Turbine Condensate (St eam Inlet - pH 25C = 9.4 f or Ammonia and ETA, Chlor ide = 5 ppb) 0 2 4 6 8 10 0.001 0.01 0.1 1 Percent of Steam Condensed in the First Condensate p H
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T e m p e r a t u r e Pure Water Ammonia ETA Limitation of Neutralizing Amines Thermal Decomposition Boilers Superheaters and reheaters Thermal Decomposition Products Carbon dioxide Formate, Acetate, Proprionate, etc. Ammonia Affect of Decomposition Products on Corrosion Carbon dioxide corrosion problems are well known Limited reports of organic acid corrosion as well Priority for control of this corrosion is to maintain pH throughout. Affect of Decomposition Products on Cation Conductivity Carbon dioxide and organic acids contribute to cation conductivity Reduces effectiveness for detecting feedwater contamination Exceeds turbine manufacturers steam purity specifications Steam Purity Monitoring Turbine manufacturers specify steam cation conductivity limits, usually of 0.2 or 0.3 uS/cm. 0.2 to 0.3 uS/cm is equivalent to 16 to 25 ppb of chloride in otherwise pure water! Degassed cation conductivity measurement is gaining in popularity No form of cation conductivity detects caustic contamination Conclusions Yes, neutralizing amines provide improved corrosion protection compared to ammonia in many applications Thermal instability limits amine applications mostly because of the effect on cation conductivity measurements Improved steam purity monitoring methods are needed