IMPROVED WATER TREATMENT FOR HIGH-PRESSURE BOILERS

ABSTRACT
Accurate testing, monitoring, and treatment of highpurity water is essential to minimize the corrosion in the operation of high-pressure boilers. Based on BetzDearborn field studies, this paper addresses system variables that affect feedwater quality and system corrosion, and it outlines practical water sampling and treatment strategies. These factors are critical in developing procedures to protect equipment, prevent costly overfeed of treatment, meet governmental regulations, and provide the optimum balance between corrosion control effectiveness and cost. pure water should be performed with the utmost care. References for sampling water include ASTM D3370, Practices for Sampling Water, and ASME Power Test Code Supplement, Part PTC 19.11. Water must be cooled to 90F (32C) or lower before sampling. If the water is sampled at higher temperatures, the sample absorbs carbon dioxide as it cools. This changes the characteristics of the sample and may alter values obtained from sample testing. To prevent this carbon dioxide absorption, the flow control valve should be placed on the exit of the cooler. On some systems, this requires a pressure-reducing flow control valve. In field trials, all sample points were cooled to less than 90F (32C). At all of the sample points, the water was flowing continuously and with a consistent flow rate. This was accomplished by means of a pressure reducing station (Figure 1), which consisted of a variable capillary pressure reducing valve, a rotometer, a back-pressure regulator, a safety pressure-relief valve, and temperature and pressure gauges. The stations allowed samples at 2.7 bar (40 psig) to go to the in-line instrumentation used for information gathering. Sample lines should be made out of 316 stainless steel, if possible. This prevents corrosion products from the sample lines from interfering with the test. The line size (diameter) should be approximately 1/4 in. (6 mm). The velocity of the water in the lines should remain constant at 6 ft/sec (1.8 m/sec). Correct pH values are difficult to obtain from samples that have been cooled after sampling. If the water cannot be cooled before sampling, precautions must be taken to ensure credible test data. The sample con-

INTRODUCTION
Ammonia plants are large users of steam. The highpressure steam, 60 to 100 bar (900 to 1,500 psig), is first used to generate electricity and then used in the process. Steam must be as pure as possible when used as a raw material for the manufacture of ammonia. This minimizes the risks of unscheduled downtime due to catalyst problems and ensures the purity of the product. The high purity of the water is also necessary because of the high pressures of the steam generating systems. The purest steam comes from the demineralizer-quality water in the waste heat steam generators. The supply of boiler feedwater can be treated by demineralizers, reverse osmosis units, polishers, electrodialysis reversal, or any combination of these treatments. In highpurity boiler feedwater, iron oxides are the main contaminants. The iron is introduced into the system from preboiler heaters and the condensate system. The best way to handle the iron is to prevent it from entering the boilers. However, even small amounts of iron invariably enter the boiler and must be treated. Several field trials were conducted by BetzDearborn to determine the most effective ways to minimize iron contamination and handle the problems it can cause in steam generating systems. Because most high-pressure steam generators have high heat fluxes and use coordinated pH/phosphate programs, iron deposits can cause failures. Concentration of caustic under these deposits leads to caustic gouging and rupture of the tube.

0 to 1000 mL/min Temperature Rotometer Variable Capillary PRV Pressure 40 psig (2.7 bar) Back Pressure Regulator 40 psig Sample to Analyzer

High Pressure Cooled Sample from Cooler Outlet 50 psig (3.5 bar) Safety PRV

Rotometer Flow Valve

SAMPLING/TESTING
High-purity water is highly susceptible to contamination during sampling or testing because of the low buffering capacity of the water. Therefore, sampling of
Excess Sample for Grab Sample

Figure 1: Pressure Reducing Station.

tainer must be sealed to prevent air intrusion. It should then be cooled and the pH taken as soon as possible, to ensure the best data point possible. If the sample is tested hot, the pH will be lower than the actual pH (see Table 1). On boiler feedwater, this could lead to an overfeed of chemicals used to control pH. Testing of the various pure water streams in the steam generating area can be performed manually or by continuous on-line instruments. Samples in the field trials were tested using in-line instrumentation and bench model spectrophotometers. Duplicate samples were taken and sent to the BetzDearborn water testing laboratory. Confirmation was done for both the in-line testing and the bench testing. Although in-line instruments can be very accurate, some of the analyzers are very maintenance intensive. A regular preventive maintenance program is required. If the plant is already using in-line instrumentation, an expanded maintenance program is beneficial in the water treatment area. If testing is performed manually, care must be taken in the selection of proper equipment. New instruments that can provide accurate measurement in the ppb (g/L) range of parameters such as phosphate, silica, iron, and low level hardness are available. The main sample points in the system are the preboiler area, the condensate area, the steam itself, and the boiler water. The preboiler area sample points are the makeup water stream, the outlet of the deaerator (before and after the boiler feedwater pump), and the boiler feedwater (after all boiler feedwater preheaters). The condensate stream is sampled before it mixes with the makeup water and after some of the critical condensers. The steam is sampled on the saturated steam header so that steam purity can be checked. The boiler water is typically sampled from the continuous blowdown line.
Table 1: Comparison of pH of the Same Sample at Different Sample Temperatures. Day 1 2 3 4 5 6 7 8 9 10 pH at 46C (115F) 7.9 8.0 7.9 8.1 8.4 8.5 8.5 8.4 9.0 9.0 pH at 29C (85F) 8.2 8.5 8.3 8.5 8.7 8.8 8.9 8.9 9.4 9.5

BOILER FEEDWATER TREATMENT Test Parameters and Ranges

Most of the iron contamination entering a steam generator comes from the preboiler system. The water is aggressive to metal surfaces because it is pure, i.e., low in dissolved ions. It can dissolve the piping and equipment through which it travels. This aggressiveness is compounded by the fact that preboiler water captures waste heat before it enters the boiler. The heat increases the corrosive nature of the water. Optimum conditions dictate that the water be as pure as possible and recapture as much heat as possible. Therefore, other variables must be changed to minimize iron corrosion in the boiler feedwater circuit. If the characteristics of the water are changed, the parameters must be monitored. At the very minimum, the boiler feedwater should be tested for silica, conductivity, pH and oxygen.

Silica
In-line instruments are available to provide reactive silica measurements. Such instruments may need regular maintenance but are accurate when operating properly. Silica can also be tested manually by operators using a very good spectrophotometer. All of the testing equipment should be made of plastic (not glass). When dealing with ppb (g/L) levels of silica in boiler feedwater, it is critical that every precaution be taken to minimize error. The silica level in the boiler is dictated by the pressure of the system and ASME guidelines1. These, in turn, dictate the required level of silica in the boiler feedwater.

Conductivity
Conductivity testing on high-purity boiler feedwater should be performed using in-line instrumentation. Because of the low ion content of high-purity water, any dissolved substance introduced during sampling would alter the conductivity of the sample, resulting in false readings. The instrument should be specifically designed for high-purity water. If an in-line instrument is not available for use, then a bench model must be used. This instrument should only be used for the purer waters being tested (boiler feedwater, condensate, boiler water). When this equipment is used to measure other streams, such as cooling towers, contamination alters the true values of the pure water samples. Care should be taken whenever a pure water sample is tested. Using the pressure reducing station, it is possible to compare a continuous sample with a grab sample. Normally, the continuous sample shows a slightly higher value (+4%) than the grab sample. Whichever method is used, the consistency (trend) of the readings should be used as a troubleshooting tool. 2

pH
The pH of demineralizer-quality water is difficult to measure. One factor is the temperature of the sample. If the sample is too hot, the measured pH of the sample will be lower than the actual system pH (see Table 1). This could lead to an overfeed of the chemicals used for controlling boiler feedwater pH. In BetzDearborn field tests on a 115F (46C) and a 85F (29C) sample, the temperature differential caused a difference of 0.3 to 0.5 pH units. Using the pressure reducing station, an additional cooler was placed on the sample. When the samples were equalized to the lower temperature, the difference in pH disappeared. Another problem is the low buffering capacity of the water. This makes the water susceptible to contamination, which alters the pH value of the water. The principal contaminant is carbon dioxide, which lowers the pH of the sample. It is advantageous to measure feedwater pH using an in-line probe, for two main reasons: the error introduced by the sample contacting the air is eliminated, for more consistent measurement the signal from the instrument can be tied into a feed system controlling the pH of the boiler feedwater

100 80 Iron (ppb) 60 40 20 0 Time Figure 2: Boiler Feedwater Iron vs. pH.

Table 2: Comparison of Boiler Feedwater pH vs. Iron Pickup in the Preboiler Circuit. The Deaerator Outlet had a Constant Iron Value of 5 ppb (g/L). Boiler Feedwater pH 8.0 8.1 7.9 8.0 7.9 8.1 8.1 8.0 8.5 8.5 8.6 8.6 8.5 8.4 8.4 8.5 9.1 9.1 9.0 9.0 9.1 9.0 9.0 9.0 Boiler Feedwater Iron (ppb [g/L]) 83 64 70 78 57 69 81 79 60 47 33 39 44 36 40 35 11 9 <5 6 <5 <5 <5 6

Day 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

There are several instruments with electrodes that can read pH in-line. Gel-filled electrodes are normally used. If pH is measured manually, only one meter should be used for the pure water streams (external treatment plant, boiler feedwater, boiler, condensate). Precautions mentioned in the Sampling/Testing section apply to these measurements. Currently, there are several liquid-filled probes on the market that function in pure water. However, these probes all require that an ionic strength adjuster be added to the sample before it is measured. The enhancer adds conductivity to the sample without affecting the sample pH. This allows the probe to function properly and not drift with the dissolving of carbon dioxide in the sample. Measurement of boiler feedwater pH is critical because of the corrosive effect of pure water. The corrosion potential of the pure water can be minimized by maintenance of the correct pH range in the feedwater, which is 9.0 to 9.2 (see Figure 2 and Table 2). This range normally contributes to an iron level that meets ASME guidelines and provides the optimum balance between corrosion control and cost. Regular pH measurement is also important because it minimizes the cost of using neutralizing amines. An 3

erroneously low pH causes amines to be overfed, increasing costs and wasting expensive treatment. For maximum pH elevation in pure water, amines with a high basicity rating should be used. The basicity of an amine reflects the amount of that amine required to raise the pH of a pure water stream after the carbon dioxide is neutralized. Cyclohexylamine has the highest basicity of any amine used in the water treatment industry today and is the amine used in the referenced field trials. Only a small quantity of cyclohexylamine is required to elevate pH in boiler feedwater. In one test,

a mixture of cyclohexylamine and a low distribution ratio amine (monoethanolamine) was used in the boiler feedwater. The cyclohexylamine is for pH elevation and the low distribution ratio amine is for condenser protection in the first drops of condensation.

Oxygen
The oxygen content of boiler feedwater should be held at or below 10 ppb (10 g/L). Oxygen removal is a mechanical function. Normally, the deaerator is extremely efficient and chemical removal is required for a very small amount (ppb [g/L] level) of oxygen. This is accomplished with the use of an oxygen scavenger that does not add dissolved solids to the boiler water. In several systems observed, hydroquinonebased products were used. The pH of boiler feedwater exiting the deaerator has a significant effect on the performance of oxygen scavenging chemicals. All oxygen scavengers work better at correct pH levels the higher the pH, the better the activity of the chemical. Therefore, the pH of the boiler feedwater should be approximately 9.1 to optimize oxygen scavenging and minimize corrosion. In-line oxygen analyzers should be installed on the boiler feedwater for continuous monitoring. Such an arrangement allows the oxygen scavenger chemical feed pump to be connected to the monitor for automatic control. Also, continuous monitoring is extremely useful for troubleshooting oxygen excursions. Steadystate operation usually produces effective oxygen control. However, excursions can cause damage in systems during operations. Historically, the vast majority of oxygen-induced corrosion in boiler systems has occurred during layup of the equipment. The oxygen scavenger can be fed neat (undiluted) or diluted in a day tank. If a day tank is used, deaerated water should be used to dilute the mixture. Also, there should be minimal air contact with the product in the day tank.

maximum retention time, while allowing the most thorough mixing of the chemical and the water. The chemical should be added through a quill into the stream. If this location cannot be accessed, the feed point should be located in the storage section. In the storage section, the quill should be located where it will maximize mixing time. The oxygen scavenger of choice in all of the field tests was hydroquinone.

BOILER WATER TREATMENT Test Parameters and Ranges

High-pressure boilers have historically used the coordinated phosphate/pH control system for internal treatment (Figure 4). The pressure of the system dictates the control range of the phosphate and the pH. When the program is run correctly, caustic gouging is prevented.

Phosphate and pH
Caustic gouging occurs when there is a deposit in the boiler and caustic concentrates beneath the deposit. In high-purity systems, the deposit is usually iron oxide. To prevent caustic gouging from occurring, a coordinated phosphate/pH program with an organic, polyDeaerator

Heater

Neutralizing Amine

Oxygen Scavenger Storage

Figure 3: Chemical Feed Points.

Feed Points
A single feed point is used for the oxygen scavenger and the neutralizing amine. Chemicals can be fed together into the deaerator through a T next to the shell of the equipment. The oxygen scavenger and the neutralizing amines used in these trials must be fed through separate lines until they reach the point of entry into the equipment. At the point of entry, the chemicals can mix in the T. The optimum point of injection is the piping that connects the heater section of the deaerator to the storage section (Figure 3). This feed point allows the 4

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10.8 10.6 10.4 10.2 10.0
Free" Caustic Region

pH at 25C

9.8 9.6 9.4 9.2 9.0 8.8 8.6 8.4 8.2

X MA

IMU

O MB

UN

RY DA O4 a/P N :1 2.7

:1 3.0

IO AT RR 4 LA O MO Na/P 4 /PO 2.8:1 Na

Control Area 901-1500 psig

Control Area 900 psig

Control Area 1501-2000 psig

2.6

:1 N

Control Area 2001-2500 psig

L RO NT CO

Vector Control Diagram

Control Area >2501 psig

n ow wd Blo

Control Area 2501-2600 psig

1.0

5 6 7 8 10

15

20

30

ppm Orthophosphate, as PO4

Figure 4: Coordinated Phosphate/pH Control.

T Ph riso os diu ph m at e

a/P

Caustic

O4

RY DA UN BO

O a/P :1 N 2.2

TIO RA AR OL M 4

Captive" Alkalinity Region

Disodium Phosphate

m diu so te no pha M o h os P

40 50 60

Usually, pH and phosphate levels are tested manually. Equipment for measuring the pH of the boiler water must be the same as that used for measuring the pH in the boiler feedwater, condensate, and other pure water streams a liquid-filled probe specially designed for pure water. Phosphate should be measured with a spectrophotometer. Ranges of values for a particular pressure are controlled by the coordinated pH/phosphate diagram. The key to the control of this type of program is consistent boiler feedwater quality. If the external treatment system does not provide water of consistent quality, control of internal treatment is difficult. Steadystate boiler operation contributes to better control of phosphate and pH.

Iron (ppb [g/L])

meric dispersant is used. The range of the phosphate and the pH are set by the specific boiler pressure (Figure 4).

1000

500

100 0 Time Figure 5: SCP Dispersant Level vs. Iron.

1200 1000 Iron (ppb [g/L]) 800 600 400 200 0 Time Figure 6: HTP Dispersant Level vs. Iron.

Dispersant
In addition to a coordinated phosphate/pH program, a dispersant may be used to prevent caustic gouging by minimizing iron deposition. If there are no deposits on the inside of the water tubes, there is nothing under which the caustic can concentrate and cause metal corrosion. Even if iron content is within ASME guidelines (< 10 ppb [g/L]), large amounts of iron can accumulate in the boiler. If a boiler has a steaming rate of 500,000 lb/hr (220,000 kg/hr) and the boiler feedwater contains 10 ppb (g/L) iron, the boiler will gain 45 lb/yr (20 kg/yr). Over a period of 5 yrs, this can amount to a serious deposition problem. Organic dispersants minimize particles of iron agglomerating and depositing on the walls of the tubes. Some polymeric dispersants are effective in all pressure systems; others are effective only in lower-pressure boilers. With high-pressure boilers, it is extremely important that the dispersant perform well. With the characteristically high heat fluxes, boiler tubes with deposits are likely to rupture and cause unscheduled downtime. Tests were performed with 2 different dispersants on systems of 100 bar (1,500 psig). The results of one of the studies are shown in Figures 5 and 6 and Tables 3 and 4. High feedrates of the conventional polymer, SCP, did not produce the desired iron removal in these systems. When the HTP-2 polymer was used, iron rejection increased dramatically while iron levels of 5 to 10 ppb (g/L) in the boiler feedwater were constant throughout the trials. It was concluded that HTP-2, which is specially designed for high-pressure high-purity water 5

Table 3: Comparison of SCP Dispersant Levels in the Boiler with Iron Levels in the Blowdown. Ten Days Elapsed from One Level to the Next. Then Samples Were Taken and Tested. Boiler Feedwater Iron Levels Were Constant Throughout. B l SCP Dispersant o w d o w n

Day (ppm [mg/L]) Iron (ppb [g/L]) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 X X X X 2X 2X 2X 2X 4X 4X 4X 4X 6X 6X 44 38 40 37 73 51 65 56 96 114 119 100 109 115

systems, is the preferred dispersant. It provides a higher degree of cleanliness in the boiler and, therefore, higher reliability.

Iron (ppb [g/L])

Table 4: Comparison of HTP Dispersant Levels in the Boiler with Iron Levels in the Blowdown. Ten Days Elapsed from One Level to the Next. Then Samples Were Taken and Tested. Boiler Feedwater Iron Levels Were Constant Throughout. Day 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 HTP Dispersant (ppm [mg/L]) X X X X X 1.3X 1.3X 1.3X 1.3X 1.3X 1.6X 1.6X 1.6X 1.6X 1.6X 3.3X 3.3X 3.3X 3.3X 3.3X Blowdown Iron (ppb [g/L]) 382 311 346 361 333 487 511 530 492 481 671 634 660 628 647 1031 1006 1025 1013 1046

120 100 80 60 40 20 0 Time Figure 7: Polymer Feed vs. Iron Throw.

Table 5: Comparison of Polymer Feed Location and Iron Throw in the Preboiler Circuit. The Deaerator Outlet Was a Consistent 5.0 ppb (g/L) Iron or Less. Day 1 2 3 4 5 6 7 8 9 10 11 12 Polymer Feed Location Boiler Feedwater Iron (ppb [g/L]) 62 90 81 88 112 85 16 7 <5 <5 8 7

Boiler Feedwater

Steam Drum

The amount of dispersant necessary in a boiler is system dependent (i.e., the characteristics of each individual boiler system will dictate the amount of dispersant needed to provide the highest reliability).

Feed Points
Polymer and phosphate can be fed together or separately. They can be fed neat from the storage tank or diluted in a day tank. The day tank has an advantage of allowing additional chemicals to be added in the event of short-term upsets in the external treatment system. The disadvantage of day tanks is the human error which may be introduced in the mixture of chemicals. The preferred method of delivery for neat or diluted chemicals is through a dilution water line to the steam drum. A small line off the discharge of the boiler feedwater pump can serve as a dilution line. The line discharges into the steam drum or into the boiler feedwater line just before the steam drum. The chemicals should not be fed to the boiler feedwater line before any heat recovery equipment. This would cause the polymer to pick up iron in the preboiler system (Figure 7 and Table 5). To prevent this condition, chemicals are fed into a dilution water line which discharges into the 6

steam drum or into the boiler feedwater line after all heat recovery equipment. The dilution water provides a high-velocity stream to carry the chemicals into the boiler water as quickly as possible.

CONDENSATE TREATMENT Test Parameters and Ranges

The condensate system can introduce iron contamination into the boiler. Neutralizing amines are fed to the condensate system to minimize iron corrosion by increasing system pH. The practical pH range for optimum protection is 8.8 to 9.5. This range allows the best corrosion rate in relation to cost of chemicals. The pH measurement of the condensate stream must be obtained using the same pH meter and probe used for the boiler feedwater and boiler water. As discussed previously, use of one pH meter and probe for all measurements, including those on contaminated samples, can give errors for the pure water streams. Dedicated equipment for pure water is required.

Neutralizing Amines
Condensate returning to the boilers can also return iron with the water. The amines used in one of the tests were monoethanolamine and cyclohexylamine. The cyclohexylamine was used for pH elevation in the boiler feedwater. It also enters the boiler, vaporizes with the steam, condenses with the condensate and provides overall corrosion protection throughout the system. The cyclohexylamine has a very high basicity rating in comparison with other neutralizing amines, providing an excellent pH elevation in the condensate stream. If cyclohexylamine is not used in the system, other amines with very high basicity values should be used. The other amine in the program must have a very low distribution ratio. This amine condenses with the first drop of steam that condenses. Protection is needed in the turbine at the Wilson line, the point at which the first condensation of steam occurs. An amine with a very low distribution ratio provides protection in the turbine at the point of initial condensation.

SUMMARY
Based on several field studies, the following conclusions were made: Sample points should be adequate to characterize the entire steam generating system. Sample points must be cooled and be continuously flowing at 6 ft/sec (1.8 m/sec). Testing variables in pure water is difficult and precautions must be taken to ensure accuracy. Boiler feedwater corrosion is minimized with an oxygen content of less than 10 ppb (10 g/L) and a pH range of 9.0 to 9.2. Feed points for both the oxygen scavenger and the neutralizing amines are at the deaerator leg between the heater and storage section with the use of a T. The internal treatment program consists of an organic, polymeric dispersant, HTP, and a coordinated phosphate/pH scheme. The key to good control of the boiler treatment is consistent boiler feedwater quality. Internal treatment chemicals must be fed to the steam drum or to the boiler feedwater line after all preheat equipment. A condensate pH range of 8.8 to 9.5 minimizes corrosion. Two amines, one with a high basicity factor and one with a low distribution ratio, are used to achieve condensate results. Those recommended are cyclohexylamine and ethanolamine.

Feed Points
Neutralizing amines are fed to the deaerator. The amines should be fed together with the oxygen scavenger into a T at the equipment wall. This feeding arrangement maximizes the effectiveness of the amines (for boiler feedwater pH control and for condensate corrosion control).
Internal Treatment (Via Dilution Water)

Boiler

Steam Drum

REFERENCES
1. American Society of Mechanical Engineers. Consensus on Operating Practices for the Control of Feedwater and Boiler Water Quality in Modern Industrial Boilers, (1979).

Boiler Feedwater Figure 8: Chemical Feed Points.