A HRSG Suppliers Water Chemistry Program Recommendations

Joseph E. Schroeder Nooter Eriksen Inc. 1509 Ocello Drive Fenton, MO 63126 Abstract
Various international standards as well as EPRI recommend starting with good feedwater. Nooter Eriksen has adopted the EPRI philosophy for their Heat Recovery Steam Generator (HRSG) water chemistry program recommendations. The EPRI Guidelines provide a simple means for treating and monitoring HRSG water chemistry. All volatile treatment and phosphate treatment programs are discussed. Some differences from the EPRI Guidelines are suggested depending upon the HRSG configuration.

Introduction
A number of chemistry related boiler tube failures in HRSGs has resulted in a need to be more specific with water chemistry recommendations. A good chemistry program starts with good feedwater. Various guidelines and standards [1][2][3] propose feedwater quality consistent with the ultimate steam purity. The basic EPRI chemistry program [1] was adopted because of its simplicity and ease for the end user to take ownership and handle the chemistry program alone. It is felt that the EPRI program is based upon current state of the art boiler water chemistry philosophy. The two chemistry programs of typical interest are an All Volatile Treatment (AVT) program and a Phosphate Treatment (PT) program. Both programs will be discussed.

Combined Cycle Plant Configuration Typical of most combined cycle plants, it is assumed that makeup water is demineralized, that there is no condensate polisher and that only ferrous components are used in the steam cycle. The following discussion is based upon these assumptions. Feedwater for high pressure (HP) and intermediate pressure (IP) sections of many HRSGs has the low pressure (LP) drum as the feedwater source. Because this water is also the source for desuperheating spray water, the LP sections must be treated with AVT chemistry where only the LP feedwater pH is appropriately adjusted. No solid alkalizing chemicals are to be added to the LP drum. Solids in the spray water would deposit in tubes and carryover into the steam turbine. The drum water of HP and IP systems can be operated under an AVT or PT program. If the HP system operating pressure is above 2400 psig (165 barg), an AVT program is recommended. The aim of high steam purity, minimizing corrosion and avoiding deposits is achieved by using good quality makeup, controlling the pH and phosphate concentration and by reducing the oxygen content. The ultimate steam purity will be consistent with the demineralized makeup
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water quality for sodium, cation conductivity (CC), silica and iron with minimal drum water blowdown. Auxiliary steam and returned condensate in cogeneration plants are sources of boiler and steam water cycle contamination. Care must be taken in design and operation to insure steam-water cycle integrity.

Feedwater Treatment Ammonia in the form of ammonia hydroxide (NH4OH) is the volatile alkalizing agent that is dosed continuously into the condensate system. If the HRSG has a NOx catalyst, the ammonia necessary for the catalyst operation can be used for the feedwater dosing. The use of oxygen scavengers is not recommended. Any discussion of an AVT program is therefore better identified as AVT(O). The correlation between ammonia concentration and pH is shown in Figure 1.
11.00 10.50 10.00

pH

9.50 9.00 8.50 8.00 0.01

0.1

10

100

Ammonia Concentration (ppm)

Figure 1

Correlation between ammonia concentration and pH at 25C

Measuring the pH of high purity feedwater can be difficult. If measuring the pH directly, it should be verified with the specific conductivity (SC) using Figure 2. This figure is to be used only for high purity water such as feedwater or steam samples. It is not to be used for drum water or water with a cation conductivity (CC) >0.5 S/cm.

Figure 2

Theoretical pH versus specific conductivity for ammonia and water at 25C

Ammonia is more volatile than water. When an ammonia-water mixture boils, ammonia is at a higher concentration in the vapor phase than in the liquid phase. The pH value in the boiler drum water thus depends on the concentration of ammonia in the feedwater and the ammonia distribution ratio. The ammonia distribution ratio is a function of the drum operating pressure and is defined as: Concentration of ammonia (steam) ----------------------------------------------------Concentration of ammonia (drum water)

Distribution Ratio =

Figure 3 shows the distribution ratio versus drum pressure. Please note that the ratio decreases with increasing pressure, i.e. higher pressure results in a higher concentration of ammonia in the boiler water phase for the same concentration of ammonia in the feedwater.

LP Drum Pressure (MPa) 0.0 14 13 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

NH3 Steam/NH3 Drum Water

12 11 10 9 8 7 6 0.0 50.0 100.0 150.0 200.0 250.0 LP Drum Pressure (psig)

Figure 3

Distribution ratio for ammonia of LP system

A minimum pH of 9.4 in LP drum water is very important in order to avoid flow accelerated corrosion in LP evaporators. In order to achieve the recommended LP drum water pH, the feedwater pH must be elevated because of the ammonia volatility. Figure 4 shows the recommended feedwater pH as a function of the LP steam drum operating pressure to achieve a drum water pH of 9.4. Figure 4 is applicable to a LP drum from which no HP/IP feedwater is extracted.
Drum Pressure (MPa) 0.0 10.10 10.05 10.00 9.95 9.90 9.85 9.80 0 50 100 150 200 250 Drum Pressure (psig) 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Figure 4

Feedwater pH

Recommended feedwater inlet pH (no feedwater from LP drum)

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The LP feedwater pH may be decreased depending upon the amount of LP steam leaving the LP drum. If no net LP steam leaves the LP drum then the recommended minimum feedwater pH will be 9.4. By defining the minimum drum water pH of 9.4 and knowing steam and water out flows and the distribution ratio, the minimum feedwater pH can be established by an ammonia mass balance around the LP drum. The recommended minimum feedwater pH would be between 9.4 and the value from Figure 4. An example of this is shown in Diagram 1. EPRI feedwater pH recommendations [1] are too low unless additional ammonia is added to the LP drum water. Ammonia feed can be controlled by controlling the HP/IP feedwater to a specific conductivity at some set point greater than 6.4 S/cm.

Diagram 1

Feedwater minimum pH determination

Drum Water All Volatile Treatment The EPRI [1] recommended drum water pH for AVT is a function of drum pressure. For LP and IP drum water the recommended pH is >9.4. For HP drum water the recommended pH is >8.7. Drum water coming from an LP drum and feeding HP and IP systems should have a minimum pH of 9.4. Figure 5 shows the feed water pH as a function of drum water pH and operating pressure taking into consideration the ammonia distribution ratio. Feedwater with a pH of 9.4 will result in a pH greater than 9.0 for HP systems operating above 800 psig (5.5 MPa). IP systems would require additional dosing of ammonia to achieve a pH of 9.4.

Drum pressure (MPa) 0 10.4 10.2 10.0 Drum Water pH = 9.8 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Feedwater pH

9.8 9.6 9.4 9.2 9.0 8.8 8.6

0 200 400 600

Drum Water pH = 9.4

Drum Water pH = 9.0

Drum Water pH = 8.5

800 1000 1200 1400 1600 1800 2000 2200 2400

Drum Pressure (psig)

Figure 5

Recommended Minimum Feedwater pH as a Function of Drum Pressure and Drum Water pH

Drum Water Phosphate Treatment Low-level phosphate treatment has been successfully used in HRSGs. Recommended [1][2][3] maximum phosphate concentration limits are between 2-3 ppm for HP drum water above 1450 psig (10MPa). It is important to realize that the solubility of phosphate decreases with increasing temperatures. This can lead to the precipitation of phosphates from oversaturated solution (hideout phenomenon). Low level phosphate treatments were designed for high- pressure fossilfired boilers that experience or are susceptible to phosphate hideout. Hideout may be a precursor to phosphate deposits and corrosion. The most common cause of phosphate hideout in HRSGs is due to the operation of the duct burner. Depending on the capacity of the duct burner, different degrees of hideout are possible. Testing during duct burner operation is necessary to determine the appropriate chemistry range for use. Boiler water chemistry is controlled by controlling the drum water sodium to phosphate ratio and the phosphate concentration. By knowing the drum operating pressure, the drum water pH, the feed water pH and phosphate concentration, an estimate of the sodium to phosphate ratio can be developed from Figures 6, 7 and 8. The drum water ammonia concentration can be estimated from Figure 6 knowing the feedwater specific conductivity and the drum operating pressure. The CC must be less than 0.5 S/cm to use figure 6 otherwise an alternate means of determining the ammonia concentration in the drum water should be used. The corrected drum water pH is determined from Figure 7 using the drum water ammonia concentration and the measured drum

water pH. The pH must be corrected for the ammonia contribution in order to obtain pH contribution from the phosphates and free sodium hydroxide only. The advantage of this approach is that the drum water ammonia concentration does not have to be measured.
Drum Pressure (MPa) 0.0 1 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0

Drum Water NH 3 Concentraton (ppm)

FW SC=4 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 Drum Pressure (psig) FW SC=6 FW SC=8 FW SC=10 FW SC=12

Figure 6

Drum water ammonia concentration as a function of the feedwater specific conductivity and drum operating pressure

9.80 9.70

Corrected pH

9.60 9.50 9.40 9.30 9.20 9.10 9.00 9.20 9.30 9.40 9.50 9.60 9.70
Drum Water Ammonia Concentration 0.0 ppm NH3 0.2 ppm NH3 0.4 ppm NH3 0.6 ppm NH3 0.8 ppm NH3 1.0 ppm NH3

9.80

9.90

10.00

Measured Drumwater pH
Figure 7 Corrected pH as function of measured pH and drum water ammonia concentration

10.10 10.00 9.90 9.80 9.70 Na3PO4+ 2 ppm NaOH

Corrected pH

9.60 9.50 9.40 9.30 9.20 9.10 9.00 8.90 8.80 8.70 8.60 0 1 2 3 Phosphate Concentration (ppm) 4 5 6 Na/PO4=3.0 Na/PO4=2.8 Na3PO4+ 1 ppm NaOH

Figure 8

Phosphate control diagram

The minimum sodium to phosphate ratio recommended is 3.0 with an upper limit of 3.0 +1 ppm sodium hydroxide. The operating conditions can be compared to the recommended limits by Figure 8 based on corrected pH value and measured phosphate concentration. The minimum recommended pH is 9.0. The minimum phosphate concentration is 0.2 ppm phosphate. The maximum phosphate concentration is a function of the operating pressure. Phosphate control is achieved by the addition of tri-sodium phosphate only. In the absence of drum water contamination and with low drum water pH, phosphate should be added first within the limits of concentration. If the pH is still low, sodium hydroxide should be added in small quantities. Care must be taken in adding sodium hydroxide so that it is not over fed. Dosing feed lines should be flushed with demineralized water to insure no residual hydroxide remains in the lines. Due to problems with carryover and phosphate hideout, phosphate treatment is not advised for HRSG drums operating above drum pressures of 2400 psig. The advantage of a phosphate program is that the drum water is chemically buffered to control feedwater contamination. The disadvantage is that it is more complicated to control a phosphate treated unit than with an AVT program. With a phosphate program there can also be hideout and caustic corrosion. With low sodium to phosphate ratios there can be acid phosphate corrosion. The equations used to develop the charts in this section are included in the Appendix. The equations can be programmed into a plant computer and the sodium to phosphate ratio can be monitored continuously.

Operation Startup operation and load changes may affect the water quality adversely for a short time until constant plant conditions are reached. During these periods of time the operation of the boiler blowdown is normally required. During normal operation the boiler blowdown flow should be minimized in order to minimize heat losses, chemical costs and makeup water requirements. Minimizing blowdown will keep the drum chemistry consistent especially for cycling operation. Prior to shutdown in order to minimize corrosion, the feedwater pH should be elevated to 10.0 (SC=25 S/cm). This is equivalent to an ammonia concentration of 10 mg/l. Unit should be closed up steam side and gas path side in order to maintain internal heat as long as possible. While unit is cooling, drum levels are not to be adjusted if incoming feedwater oxygen concentration is higher than 10 ppb. Drum level should ultimately be adjusted just prior to restarting the unit. To minimize oxygen ingress during shutdowns, nitrogen should be introduced into each steam drum as the drum pressure decays. A minimum pressure of 5 psig (0.3 barg) should be maintained through the addition of nitrogen. Steam from auxiliary boilers may be used for brief periods at startup, used to maintain vacuum during longer outages or used for sparging of the HRSG. Steam purity from auxiliary boilers should be the same as the steam produced in the HRSG. Contaminants in auxiliary steam may make cleanup of the steam-water cycle more difficult at a subsequent startup.

Conclusion
The ERPI recommendations are a simple and cost effective way to chemically treat a HRSG. Keeping LP drum water pH to a minimum of 9.4 is important to avoid flow accelerated corrosion. Accounting for ammonia in HP and IP drum water can be simplified so that it is easy to monitor drum water sodium to phosphate ratios.

References [1] Cycle Chemistry Guidelines for Combined Cycle/Heat Recovery Steam Generators (HRSGs), Report 1010438, Electric Power Research Institute, March, 2006. [2] VGB Guidelines for Feed Water, Boiler Water and Steam Quality for Power Plants / Industrial Plants VGB-R 450 Le, VGB Power Tech e.V., Second Edition 2004 [3] Water Tube Boilers and Auxiliary Installations Part 12: Requirements for Boiler Feed Water and Boiler Water Quality, EN 12952-12:2003.

Appendix - Calculations
Determination of Feedwater pH from Ammonia Concentration CNH3 = Ammonia Concentration in mg/l MNH3 = Molarity =

C NH 3 17031

Reference: CRC Handbook of Chemistry and Physics, 55th Edition, 1974, CRC Press Dissociation Constants KNH3 0.00001774 @25C KWater 1.01E-14 @25C
2 K NH 3 4 * K NH 3 * M NH 3

C[OH] = Hydroxide Concentration = pH = log C[OH ]

log KWater

K NH 3

Determination of Feedwater pH from the Specific Conductivity Applicable Range pH from 9 to 10.25 CC <0.2 S/cm

pH = 0.4508 * ln SC

8.5625

Determination of Distribution Ratio from the Drum Operating Pressure P = Drum Operating Pressure (psig) DR = Distribution Ratio =
1.79553 * ln P 16.0404

Determination of Feedwater Inlet pH from the Drum Operating Pressure Assumes all water into drum leaves as steam Drum Water pH = 9.4 Drum Water CNH3 = 1.05 ppm Steam CNH3 = 1.05 * DR Feedwater CNH3 = Steam CNH3 Calculate Feedwater pH as a function of CNH3 from section above.

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Determine the Drum Water Sodium to Phosphate Ratio

R (1/ P ){Kw / H 3P / D 2HP / DK3 t t t

Where:

H 2 P /((DK3 )K2 ) H t

At Kb /[(Kw / H ) Kb ]}

R = Sodium to Phosphate Ratio H = Hydrogen Ion Concentration = 10-pH At = Ammonia Concentration in moles/L = (ppm NH3)/(17,030.61) Pt = Phosphate Concentration in moles/L = (ppm PO4)/(94,971.4) Kw = Dissociation Constant for Water = 1.008 x 10-14 Kb = Dissociation Constant for Ammonia = 1.7742 x 10-5 K1 = First Dissociation Constant for Phosphoric Acid = 7.1121 x 10-3 K2 = Second Dissociation Constant for Phosphoric Acid = 6.2373 x 10-8 K3 = Third Dissociation Constant for Phosphoric Acid = 4.571 x 10-13 D = Ionization Fraction = H3/(K1K2K3) + H2/(K2K3) + H/K3 + 1 To use this equation, the ammonia concentration in the HRSG must be determined by separate analysis. The above equation assumes that ammonia is used to control the feedwater pH. Determine the Amount of Drum Water Free Sodium Hydroxide: ppm free NaOH = (R-3) x (ppm PO4) x 0.42139 R = Sodium to Phosphate Ratio