NACE International, Vol. 48, No. 10 October 2009 MATERIALS PERFORMANCE 39

Case History

Caustic Treatment of

Electric Utility Drum Boilers

K. Anthony Selby, Water Technology Consultants, Inc., Evergreen, Colorado

Until recently, caustic water treatment was not

used in high-pressure electric utility drum boilers in

the United States because of concern over caustic

gouging. Meanwhile, it was being used successfully

in other countries. Many U.S. electric utilities have

now converted their drum boilers to caustic

treatment. This article describes the basics of caustic

treatment and presents two case histories of

successful use in the United States.

In looking back at the history of boiler water treatment, chemical treatment has been designed to control either deposit accumulation (e.g., scale)

or corrosion. The original phosphate treatment programs for scale prevention in boilers used high levels of phosphate. As boiler pressures increased, tube dam-age attributed to caustic attack was expe-rienced and phosphate levels were de-creased.

Phosphate Treatment Phosphate treatment has long been

the staple for treating drum boilers. Be-fore the advent of ion exchange makeup water treatment, phosphate provided both pH control and protection against the ingress of scale-forming ions.

At that time, there were no “high-pressure” boilers (by today’s standards) and “raw” untreated or partially softened waters were used for makeup. Since these waters contained calcium and magne-sium, the formation of mineral scales was a serious problem. Internal “softening” treatments were used to prevent the for-mation of the least desirable scales such as calcium sulfate (CaSO4) and silica scales. Caustic soda and soda ash (sodium carbonate [Na2CO3]) were commonly used. The so-called “carbonate cycle” caused calcium carbonate (CaCO3) to precipitate preferentially over CaSO4 (a more adherent scale). The high pH of boiler water also protected boiler surfaces from corrosion. The carbonate cycle re-actions are represented by Equations (1) and (2).

Ca+2 + SO4–2 + Na2CO3 →

CaCO3 + Na2SO4 (1)

CaCO3 + H2O + Heat → Ca(OH)2 + H2CO3 (2)

Later, it was found that phosphate chemistry could completely prevent the formation of CaSO4 scale and would

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Caustic Treatment of Electric Utility Drum BoilersC H E M I C A L T R E A T M E N T

form a sludge (calcium hydroxyapatite) that was more “free flowing” than CaCO3. The calcium hydroxyapatite sludge could be removed by blowdown. The calcium hydroxyapatite reaction is represented by Equation (3):

10Ca+2 + 6PO4–3 + 2OH– →

3Ca3(PO4)2{Ca(OH)2 (3)

As boiler pressures increased, the hy-droxide levels led to problems such as caustic gouging. This is caused by the

Typical CPT control chart.

Schematic of PT, CPT, and EPT.

FIGURE 1

FIGURE 2

dissolution of iron oxide by high levels of caustic, particularly underneath deposits. In conjunction with an improvement in makeup treatment techniques, the phos-phate control regimen changed to protect against caustic attack. This regimen was coordinated phosphate treatment. The coordinated phosphate treatment pro-gram was designed to eliminate the free hydroxide formed by the reaction of phosphate and water in Equation (4):

PO4–3 + H2O → HPO4

–2 + OH– (4)

Mixtures of trisodium phosphate (Na3PO4) and disodium phosphate (Na2HPO4) or monosodium phosphate were fed to maintain phosphate in the range of ~5 to 15 ppm as PO4 and a pH range equivalent to a sodium-to-phos-phate ratio of 2.85:1 to 3.0:1. This was no longer a precipitating program. This program required a high-purity and con-sistent feedwater. The primary purpose was to control pH but some protection against the ingress of hardness salts was maintained.

So-called “caustic attack” (some of this could have been acid phosphate corro-sion) was still experienced, especially as boiler pressures increased to >1,500 psig. As a result, congruent phosphate treat-ment (CPT) was developed to further re-duce boiler water pH and ensure against caustic attack. CPT operated with a phos-phate concentration of ~2 to 5 ppm PO4 but possibly up to 10 ppm. The sodium-to-phosphate ratio was often in the range of 2.3:1 to 2.6:1 but this varies from a low of 2.1:1 and a high of 2.8:1. In many cases, but not all, CPT was linked to severe “phosphate hideout” and boiler tube failures due to acid phosphate corrosion.

Figure 11 is a chart showing a typical CPT control range. This chart shows the CPT control “box” with a phosphate concentration of 2.0 to 4.5 ppm PO4 and a sodium-to-phosphate ratio of 2.3 to 2.6:1.

Equilibrium phosphate treatment (EPT), utilizing low levels of phosphate and allowing a small amount of free caus-tic, was designed to minimize phosphate hideout and prevent acid phosphate cor-rosion. EPT was typically operated using Na3PO4. The phosphate control range was <2 ppm PO4 with up to 1 ppm free hydroxide. EPT does minimize phos-phate hideout but provides little protec-tion from corrosion resulting from an-ionic species such as chloride and sulfate. According to the Electric Power Research

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NACE International, Vol. 48, No. 10 October 2009 MATERIALS PERFORMANCE 41

C H E M I C A L T R E A T M E N T

Institute (EPRI), EPT has been associated with incidences of hydrogen damage.

EPRI also had a phosphate treatment (PT) regimen with phosphate in the 2.5 to 10 ppm as PO4 range and a pH gener-ated by Na3PO4 +1 ppm OH.

Figure 2 is a chart that summarizes the control ranges that were used for PT, CPT, and EPT.2 It should be noted that CPT and EPT are no longer part of EPRI’s recommended programs.

Current Phosphate Treatment Concepts

Once acid phosphate corrosion was identified, the use of CPT in high- pressure boilers was greatly reduced. EPT replaced CPT in many cases. However, EPT has been associated with the occur-rence of hydrogen damage. EPRI has now developed the concept of a “phosphate continuum” where the phosphate concen-tration is a function of feed water and steam purity. EPT as such no longer exists in the EPRI phosphate continuum. An important aspect of the EPRI recommen-dations is that only Na3PO4 was used rather than mixtures containing Na2HPO4 or monosodium phosphate and that poly-mers not be used.3

The phosphate continuum establishes a minimum phosphate concentration of 0.2 ppm PO4. The treatment range is bounded by the Na to PO4 molar ratio line of 3.0 and the Na3PO4+1 ppm so-dium hydroxide (NaOH) line. The phos-phate continuum provides for a range of phosphate levels depending on feedwater purity. At low phosphate levels, feedwater purity requirements are the same as the all volatile treatment (AVT) programs. High phosphate levels are used in re-sponse to poorer feedwater quality (e.g., 0.3 µS/cm cation conductivity).

Importance of Feedwater Control

Good control of feedwater chemistry is a prerequisite to controlling boiler

water chemistry. This is because the common enemy of all boiler water treat-ment programs is the production of cor-rosion products in the condensate/feedwater cycle and subsequent transport to the boiler. Deposit accumulation in the boiler creates an environment where concentration cells accumulate harmful ions such as chloride, sulfate, phosphate, caustic, etc.

Modern electric utility boilers operate the condensate/feedwater systems on some type of AVT. Current approaches to AVT attempt to balance iron trans-port, copper transport (if present in the system), and flow-accelerated corrosion (FAC). In all-ferrous condensate/feed-water systems, EPRI currently recom-mends a program where ammonia (NH3) is added to increase pH into the 9.2 to 9.6 range but no reducing agent (oxygen scavenger) is used. This results in a posi-tive oxidizing reduction potential (ORP). EPRI labels this program AVT(O) for oxidizing. The purpose of the AVT(O) feedwater program is to minimize FAC and minimize iron transport to the boiler.

If the condensate/feedwater train utilizes feedwater heaters with copper alloy tubes, the typical feedwater pro-gram operates at a lower pH (9.0 to 9.3) and utilizes a reducing agent to maintain

a negative ORP. This program is labeled AVT(R) by EPRI. Note that both of these programs rely on low air inleakage (<10 ppb dissolved oxygen) and a cation conductivity (acid conductivity) of <0.2 µS/cm.

Caustic Treatment Basics

Overseas Experience For many years, power plants in the

United Kingdom, Ireland, Hong Kong, and South Africa reported operating high-pressure electric utility drum boilers with 1 to 2 ppm NaOH in the boiler water. This elevated boiler water pH and protected against corrosion caused by acidic salts such as chloride. They used an empirical relationship of NaOH being equal to 2.5 times the chloride level. This would result in a boiler water pH of 9.2 at ~20 ppb chloride and a pH of 9.5 at ~500 ppb chloride.

Caustic treatment of high-pressure electric utility boilers is therefore rela-tively simple. Low levels of NaOH are added to maintain pH within the target range. NH3 does have some impact on the pH, especially below 9.2. As pH in-creases above 9.2, NaOH becomes the major driving force. This is shown in Figure 3.4

Solution pH vs. pH due to NaOH for various concentrations of NH3.

FIGURE 3

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Caustic Treatment of Electric Utility Drum BoilersC H E M I C A L T R E A T M E N T

This shows that at pH 9.0, the impact of NH3 can be significant. A measured pH of 9.0 with 0.2 ppm NH3 means that the actual pH due to NaOH is only 8.65. Above a pH of 9.2, the NH3 impact is much less. At a pH of 9.6, the impact of 0.2 ppm NH3 is ~0.1 pH unit.

Case Histories— Caustic Treatment in United States

Case History #1 Barnes reported on the conversion of

Northern Indiana Public Service Co. (NIPSCO) drum boilers from phosphate treatment to caustic treatment.5 NIPSCO operates four drum-type boilers in the 2,400 to 2,600 psig range (16.6 to 17.9 mPag). These boilers utilized NH3 and hydrazine (H2NNH2) for feedwater treat-ment and CPT (5 to 30 ppm) depending on drum pressure. The CPT was used because of fear of caustic gouging. It was difficult to control the CPT, and boiler tube failures were generally attributed to this problem.

Throughout the 1990s, NIPSCO in-stituted compliance with EPRI action levels, significantly improved water qual-

ity instrumentation, and began monitor-ing corrosion product transport. Hydra-zine treatment was eliminated in all-ferrous drum boiler systems. These steps significantly reduced corrosion product transport.

Another factor was higher than nor-mal steam cation conductivity in one boiler. Since there was no appreciable sodium in the steam sample, it was likely that the elevated cation conductivity was due to carbon dioxide (CO2). In order to keep the CO2 in the water phase, some caustic was added along with the Na3PO4

to elevate pH. The addition of caustic was then implemented in the other boilers as well. It was felt that operation at the higher pH was providing additional pro-tection against acid phosphate corrosion.

Finally, all boilers transitioned to an all-caustic program. Phosphate swings were still occurring and the utility felt that feeding only one solid alkali would simplify the program. Reductions in total tube and turbine deposits have been observed.

Control of the caustic treatment pro-gram is relatively simple. The utility is also planning to add boiler water cation conductivity instrumentation. This will

serve to better track boiler water impuri-ties and facilitate impurity control via blowdown.

Case History #2 Verib discusses the FirstEnergy Corp.

conversion to caustic treatment in drum boilers.6 FirstEnergy Corp. operates 23 coal-fired boilers. Of these, 16 are drum boilers and seven are once-through boil-ers. Boiler pressures range from 2,000 to 2,400 psig (13.8 to 16.6 mPag). All boilers utilize once-through condenser cooling.

All of the drum boilers were on a low-level phosphate treatment. One boiler experienced a chronic inability to main-tain an adequate phosphate level, and was converted to caustic treatment as a trial. The caustic treatment was found to be easy to control. As a result, all of the boilers at this station were converted to caustic treatment. Finally, all drum boil-ers were converted.

The utility is operating with a pH range of 9.1 to 9.6, a specific conductivity range of 5 to 20 µS/cm, and a cation conductivity range of <10 µS/cm. Figure 4 shows boiler water specific and cation conductivity for the first boiler switched to caustic treatment.

The utility has found the caustic treat-ment program much easier to control than the phosphate programs that pre-ceded it.

Conclusions In the past, operation of high-pressure

boilers with free caustic was strictly avoided. Due in part to experience in the United Kingdom, operation of electric utility boilers with low levels of caustic in the boiler water is becoming common. Electric utility boilers lend themselves to caustic treatment for several reasons:

• The cycle is simple—steam is gener-ated in the boiler, powers the tur-bine, is condensed, and returns to the boiler.

Specific and cation conductivity trends, 2,200 psig drum boiler.

FIGURE 4

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C H E M I C A L T R E A T M E N T

• Pathways for impurities to enter the feedwater/boiler cycle are limited. The main pathways are the makeup treatment system and the main condenser. If good makeup treat-ment control is exercised and con-denser leakage is controlled, an electric utility boiler will operate with minimal impurity ingress.

• Because of high-quality feedwater, deposit accumulation within the boiler is minimized. This limits un-der-deposit corrosion and the con-centration of boiler water impurities (and caustic) underneath deposits.

There are other types of industrial boilers where caustic treatment would not be appropriate. Many industrial boilers do not operate with the level of makeup

and feedwater purity needed to allow caustic treatment to function.

References 1 S.T. Costa, L.O. Brestel, “Managing a

Captive Alkalinity Boiler Treatment Program,” Calgon Corp. Technical Bulletin 10-345.

2 B.R. Dooley, W.P. McNaughton, “Appropriate Controls for Phosphate Boiler Water Treatments to Avoid Acid Phosphate Corrosion and Hydrogen Damage,” PowerPlant Chemistry 3, 3 (2001).

3 B.R. Dooley, S.R. Paterson, J.M. Pearson, “HRSG Dependability,” PowerPlant Chemistry 5, 12 (2003).

4 G.J. Verib, “Caustic Treatment in Boilers at FirstEnergy Corp.,” ASME Research Committee on Power Plant & Environmental Chemistry, April 2008.

5 S. Barnes, “Evolution to Caustic Treatment in NIPSCO Drum Boilers,” 27th Annual Electric Utility Chemistry Workshop (Champaign, IL: University of Illinois, 2007).

6 Verib, op.cit.

This article is based on CORROSION 2009 paper no. 62, presented in Atlanta, Georgia.

K. ANTHONY SELBY is president of Water Technology Consultants, Inc., PO Box 249, Evergreen, CO 80437-0249, e-mail: tselby@comcast.net. He has a B.S. degree in chemistry from Wichita State University and has more than 40 years of experience in the field of water and wastewater technology. He has been a member of NACE International for 24 years.

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