POWER

PART 2: WATER TREATMENT STRATEGIES FOR FOSSIL-FIRED POWER PLANTS

for producing electricity by the Rankine cycle. The water is purified using ion exchange, filtration and other processes to remove the impurities before the water is added to the steam cycle. However, occluded regions such as the areas underneath deposits, can lead to the accumulation of trace levels of impurities, resulting in aggressive environments. Operators of power plants must be diligent in controlling the water chemistry to ensure that any problems that degrade water quality are corrected quickly. Organic and inorganic additives are used to provide further corrosion protection. Oxygen is one of the main corrosion agents in the steam cycle. Adding an oxygen scavenger, such as hydrazine directly to the condensate water is a useful apfYroach to remove residual oxygen. Ammonia or organic amines are added to the feedwater to control the pH. Maintaining alkaline conditions throughout the steam cycle can minimize the general corrosion rate of carbon steels that are widely used in piping systems. Corrosion inhibitors, dispersants, and other chemicals are also used in some power plants to control corrosion and to minimize fouling of heat transfer surfaces. Sodium phosphate is currently used in many smaller fossil plants to buffer the pH because of impurity ingress excursions. Buffering with phosphate salts generally follows either a 'coordinated phosphate' or 'congruent phosphate' regimen. In the coordinated phosphate/pH control regimen sodium phosphate salts are added to the boiler water in an attempt to maintain a sodium-to-phosphate ratio of 3:1. In the congruent phosphate/pH control regimen, a sod ium-to-phosphate ratio of between 2.4 and 2.8:1 is maintained. The ratio is held closely to 2.6: 1 in most congruent phosphate/pH control programs. Leakage of sodium from deionizer systems can create difficulties with maintaining the sodium-to-phosphate ratio in coordinated or congruent phosphate/pH control programs. In traditional fossilfired power plants where the deionizer effluent is polished using mixed-bed polishing units, sodium leakage is minimized. However, a relatively small proportion of utility systems use phosphate/ pH control treatment programs. Most use all-volatile treatment (AVT) programs based on hydrazine with ammonia addition in some cases. Amines are also used in a relatively small number of units. Phosphate-based programs are commonly found in cogeneration systert;ls operating at lower pressures and in smaller utility units.. More recently, under deposit corrosion associated with the presence of acidic phosphate salts has been recognized. This has lead to the development of an alternate ~pproach called equilibrium phosphate control, which uses lower phosphate residuals with appropriate pH control to minimize the potential for under deposit acid phosphate corrosion. Water Treatment Strategies It must always be recognized that water treatment can mitigate but not correct corrosion due to improper design or incompatible metallurgies. The primary approach to protecting a steam generator system is by minimizing impurity

n Part 1, we examined how corrosion can be a major cause of equipment failures in power plants. One aspect to improve facility operations is internal surface passivation where operators control water chemistry on the waterside of the boilers to encourage magnetite formation, which can effectively control corrosion. However, in utility superheaters the magnetite formation is different because ofthe temperatures that are above 662F. In these cases, the magnetite is less stable and it can break down in the cooling and heating cycles associated with boiler shutdowns. Magnetite particles can then be carried to the superheater and into the turbine with the steam after a shutdown and cause excessive wear on the nozzles in the high-pressure turbine. Part 1 also reviewed corrosion mechanisms that can be caused by oxygen, flow-accelerate corrosion, heat recovery steam generator (HRSG) metal loss in economizer tubes, deposit-induced corrosion, caustic corrosion, deposition, and stress corrosion cracking. In this article, we will review water treatment strategies and monitoring in fossil-fired utility plants.

Minimizing Corrosion Inconventionalfossil power plants, highpurity water is used as the working fluid

By Douglas I. Bain, Ph.D.,

Bain & Associates Consulting Ltd.

and Joe Bates

iSagacity Inc. Editor's note: Part I appeared in the December issue, 2005

TABLE A Quality Standards for HRSGs

Sample Point Make up Condensate Main steam pump discharge

ISSN:0747-8291. COPYRIGHT (C) Tall Oaks Publishing, Inc. Reproduction in whole, or in part, including by electronic means, without permission of publisher is prohibited. Those registered with the Copyright Clearance Center (CCC) may photocopy this article for a flat fee per copy.

Parameter silica (ppb) specific conductivity /Js/cm sodium (ppb) cation conductivity /Js/cm sodium (ppb) cation conductivity /Js/cm

Limit <20 <0.15 <6 <0.25 <6 <0.25 19

ULTRAPUREWATER@ OCTOBER 2006

TABLE B Solubility Product Constants and Additional Information for Iron-Containing Species LOG Ksp Compound (25C) Fe(OH)2 -14 -15.1
Crystallographic System

Color White

Comments

1. decomposes @ 100C to Fep (brucite)

2. dehydrates to FeO

+ H2

3. at room temperature + O2 can form goethite lepidocrocite and magentite.

Fe(OH)3 FeO (wustite)

Fe3O4 (magnetite)

-38.7

Unstable iron form rapidly dehydrates oxide form.

to

black

cubic (NaCI) cubic (inverse spinel)

Decomposes to Fe and Fep4

-14 -18

black

Oxide typical of "0" oxygen systems. Found in utility condens.ate systems using hydrazine.
Dehydrates to hematite at 200C. Forms hematite at lower temperatures in presence of Hp. This form is favored at high pH and has been identified by color in condensate systems. 6:>rthorhombic Dehydrates to hematite at 200C. tne presence of HP corlVerts to hematite at IQwer temperatures. Has been identified based on color in systems where .iron slugging is a problem. Has been mistaken for copper contamination. Decomposes to magnetite at 1,457C. Most common iron form in industrial system. Hematite formation favored by low pH and increasing temperatures. In

Alpha FeO(OH)-39.1 (goethite)

yellow

orthorhombic

ffiamma FeO( OH) (Iepidocrocite)

-39.1

orange

, <, Alpha Fep3 -42.7 (hematite) red to black trigonal (hexagonal unit cell)

Other Possible Iron Forms Beta FeO(OH)

light brown brown

cubic (spinel)

Dehydrates to hematite at 230C. Presence of water enhances dehydration. Transforms to hematite above 250C. Presence of HP enhances transformation.

Gamma Fe2O3 (maghemite)

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ingress. Sources of impurities include: condenser cooling water, process condensate, pretreatment/make-up water, chemical feed impurities, condensate polishers, regenerant chemicals, auxiliary heating steam, and sample coolers. Recording instruments for sodium, silica, chloride, dissolved oxygen, and organic carbon contamination are commonly used in plants to monitor makeup water, condensate, boiler feedwater, boiler water, and steam samples on a continuous basis to ensure that excursions are quickly identified and corrected by minimizing ingress of contamiULTRAPUREWATER@ OCTOBER 2006

nants. The primary objectives of the chemical treatment program are to minimize deposition and corrosion on internal surfaces in the boiler unit. The first step involvesminimizing contamination inthe boiler feedwater. Contaminants can enterthe feedwater eitherfromthe makeup water or the condensate. Make-up water pretreatment systems commonly use filtration, reverse osmosis, and deionization to minimize the ingress of contaminants. lron- and copper-based corrosion products are common contaminants in the condensate. In addition, hardness salts, silica, chloride, sulfate, and sodium can contaminate condensate as a result of condenser leaks. Condensate polishers are very helpful in removing this contamination. Additional contaminants such as oil or other organic materials are often found in cogeneration systems because of contamination of process condensate. In these systems, additional purification steps such as activated carbon filters are used ahead of the condensate polishers to minimize condensate contamination. The treatment approaches used in most conventional fossil-fired utility boilers are based on either AVT or oxygenated treatment. In lower-pressure drumtype units, phosphate treatment approaches are also used.
Combined Cycle HRSGs Modern HRSGs are built in a wide variety of designs. Traditional two-drum units had low-pressure (15 to 50 pounds per square inch gauge (psig) sections and high-pressure (600 to 1,500 psig) sections. In the three drum designs, intermediate pressure (50 to 400 psig) sections were added and the high-pressure sections operated at pressures up to 2,200 psig. Some modern designs employ once-through steam generators and combinations of once-through steam generating sections with one or two drum steam generating sections. The treatment approaches used generally involve either AVT or oxygenated treatment at the higher pressures with conventional phosphate treatment or equilibrium phosphate treatment in the intermediate pressure range. In some units, polymer-based treatment programs are used at the lower end of the pressure range (600 to 700 psig). For once-through steam generator designs, an all-AVT approach, or an oxygenated treatment approach is required. ULTRAPUREWATER@OCTOBER 2006

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r ABLE C QptilTlum"Sodium Phosphate Values and at Various Operating Pressures

'~

Operating Pressure (psig) 2,200 1,800 *,500 1,200 1,000 700

Optimum Phosphate Value (ppm) <4.5 <7 <10 <12 <15 <20 TABLED

Optimum Sodium Value (ppm) <4.5 <6 <8 <9 <13 <15

Optimizing boiler feedwater purity is the first step toward minimizing corrosion and deposition in the HRSG. Those steps can include guidelines for specific areas (Table A) or a general overview (Table B). Table B provides guidelines for make up water, condensate and steam purity for HRSGs in utility service. In phosphate control programs, the phosphate concentration range used varies, depending on the operating pressure of the unit. Using equilibrium phosphate control, the equilibrium phosphate co~entration must be determined for each individual unit. The Electric Power Research Institute (EPRI) has published a method for the determination of the equilibrium phosphate concentration. Table A provides guidelines for the concentration of sodium and phosphate in boiler water over a range of operating pressures. The actual sodium-to-phosphate ratio used in any specific case will depend on the boiler design and operating conditions and on the feedwater quality attainable with the equipment installed. It should be noted that 1.38 parts per million (ppm) of phosphate per ppm of sodium is required to obtain a sodium-to-phosphate mole ratio of 3 to 1. It should ~Iso be noted that in many industrial units operating in the lower pressure range, higher phosphate concentrations are used to maintain buffering capacity in the presence of elevated concentrations of sodium in make-up water bes::ause of sodium leakage from , deionizer units. The silica concentration in the boiler water must be controlled to minimize the potential for silica volatilization in the steam and chloride and sulfate concentrations must be controlled in order to minimize the potential for boiler waterside corrosion. Table C provides guidelines for the concentrations of silica, chloride, and sulfate in the boiler water with phosphate treatment over a range of operating pressures. In the AVT approach, only volatile chemical additives are used normally an oxygen scavenger such as hydrazine with either ammonia, or in many cases amines at lower pressures. Highpurity boiler feedwater is critical in the operation of AVT chemistry programs. Table 0 provides a review of the critical parameters monitored in boiler feedwater with guidelines for limiting values. Generally, the application of oxygenated treatment in drum HRSGs is advisable only if very pure feed water is available in the unit with all ferrous metallur-

Guidelines for Various;Qp~~ating "Pressures Drum Pressure (psig) 2,700 2,500 1,900 1,500 1,000 Silica (ppm) <0.08 <0.15 <0.35 <0.7 <1.0 Chloride (ppm) <0.5 <1.0 <2.0 <2.5 <3.5 Sulfate (ppm) <1.5 <1.7 <2.5 <2.7 <3.5
'il

'f'ASLEE BoilerFeedwater Guidelines AVT Chemistry, for

Parameter Sample Cation conductivity (fJs/cm) conti n!J~9jJs continuous Oxygen (ppb) continuous pH weekly Iron (ppb) continuous or shift Hydrazine (ppb) Target Value <0.2 1 10

9.2 - 9.6
<5 <20

TABLe:,F

Boilerlieedwater Guidelines OT for

Parameter Cation Conductivity (lJs/cm) Oxygen (ppb) pH Iron (ppb) Sample continuous continuous
contilillJJouS

Target Value <0.15

30 - 50
9.0- 9.6 <5

weekly

TABLE G Downcomer Chemistry GuideliJ;les

Parameter Sodium (ppm) Chloride (ppb) Sulfate (ppb) Silica (ppb) pH Cation conductivity Oxygen (ppb) Sample continuous or shift continuous or shift daily continuous continuous continuous continuous or shift

(IJS/cm)

Target Value < 0.7 < 30 <30 <100 8.8 - 9.2 <1~.5 <5

22

ULTRAPUREWATER@ OCTOBER 2006

gy in the system. Table E provides a review of the critical parameters monitored in boiler feedwater with guidelines for limiting values. Conventional Utility Boilers Oxygenated treatment has been used with much success in fossil-fired utility units. It has been helpful in reducing iron contamination in both the feedwater and the boiler water and in minimizing the need for chemical cleaning. Some basic conditions must be met to ensure successful application of the oxygenated treatment regimen to drum fired utility boiler units. Here is a summary: 1. It is important that no copper or copper alloy components be present in the feedwater system. 2. It is advisable to have a sample point available at the downcomers as well as at the economizer inlet. 3. Feedwater and steam cation conductivity must be maintained at less than 0.15 microsiemens per centimeter (flS/cm). 4. It is essential that feedwater purity be maintained to prevent corrosion in the system. Full-flow condensate polishers are recommended to ensure removal of impurities resulting from condenser leaks. Table F provides a review of the critical parameters monitored in boiler feedwater with guidelines for limiting values. Table G provides guidelines for the concentrations of sodium, silica, chloride, sulfate, pH, cation conductivity, and oxygen in the boiler water at the downcomers. Table H provides guidelines for the concentrations of sodium, silica, chloride, sulfate, pH, cation conductivity, and oxygen in the superheated steam. Oxygenated treatment has been used with great success in once-through utility units. It has been helpful in reducing iron contamination in both the feedwater and the boiler water and in minimizing the need for chemical cleaning. The guidelines for critical contaminant con-

TABLE H Superheated Steam Guidelines Parameter Sodium (ppb) Chloride (ppb) Sulfate (ppb) Silica (ppb) pH Cation conductivity, jJS/cm Oxygen (ppb)
Sample continuous continuous or shift or shift
.(y

daily

continuous or shift continuous' continuous continuous

Target Value <3 <3 <3 <10 8.8 - 9.2 <0.15 30 - 50

TABLE I Reheat Steam Guidelines

Parameter Sodium (ppb) Chloride (ppb) Sulfate (ppb) Silica (ppb)

~.

Sample continuous or shift continuous or shift daily continuous or shift TABLE J Boiler Feedwater for OTSG Guidelines

Target Value <3 <3 <3 <10

Parameter Cation cOJ'ilductivitY(jJS/cm) Oxygen (ppb) pH ferrous metallurgYJ' , , Copper (ppb) Iron (ppb) Hydrazine (ppb)

Sample continuous continuous continuous weekly weekly continuous or shift ."

Target Value <0.15

1 - 10

9.2 - 9.6
<2 <5 <20

TABLE K Boiler 'Feedwater for Economizerlrilet Guidelines

Sample ct!J!nuous continuous continuous cOrc1tinuous weekly daily Target Value <0.15 50 - 150 8.3 8.5 <3 <5 0.04 0,05
~

Parameter Cation conductivity (jJs/cm) Oxygen (ppb) pH ferrous metallurgy Sodium(ppb) Iron(ppb) Ammonia (ppm)

TABLE L Control Parameters for Reheat Steam Parameter Sodium (ppb) Cnloride(~ppb') Sulfate (ppb) Silica (ppb) Cation conductivity (jJS/cm) Oxygen (ppb) Sample Continuous Daily Daily Shift continuous continuous Target Value <3 <3 <3 <10 <0.2 50 - 150

~.

centration limits in boiler feedwater boiler water and superheated steam are essentially the same as those listed in Tables E through G. All-volatile teatment. In the AVT approach, only volatile chemical additives are used normally an oxygen scavenger such as hydrazine with either amULTRAPURE WATER@ OCTOBER2006

monia or in many cases amines at lower pressures. High-purity boiler feedwater is critical in the operation of AVT chemistry programs. Table H provides a review of the critical parameters monitored in boiler feedwater for drum units with guidelines for limiting values. Table G also provides uidelines for

boiler water in drum units at the downcomers. Table I provides guidelines for the concentrations of sodium, silica, chloride, sulfate, pH, cation conductivity, and oxygen in the superheated steam. The table also gives guidelines for reheat steam quality. Table J provides a 23

-.

.
I

! I

review of the critical parameters monitored in boiler feedwater for oncethrough units with guidelines for limiting values.
II

I!

Field experience. In recent years, the treatment approach has changed from AVT to oxygenated treatment in a considerable number of utility units. In many cases, significant reductions in iron contamination in boiler feedwater have been reported along with a reduced requirement for chemical cleaning. One such case involves Unit NumII'

ber 2 at MerrimackStation - Public

III

Service of New Hampshire Merrimack Station Unit Number 2 is a universal pressure cyclone-fired unit burning a blend of high British thermal units (BTU) bituminous coals. The unit produces 2.3 million pounds per hour of steam at 2,620 psig at the throttle valve. The main steam and reheat steam temperature is 1,005F. The unit was operated with AVT chemistry for approximately 30 years and changed over to oxygenated treatment in 1994. Full-flow condensate polishing is employed to remove impurities from the condensate stream. Oxygenated treatment is employed only under normal load conditions. Full deaeration is used during start-up and shut-down operations. Under normal operating conditions using oxygenated treatment, the pH is controlled between pH 8.0 to 8.5 at the deaerator inlet. Under start-up and shutdown conditions without oxygen addi-

tion, the pH is elevated to pH 9.1 to 9.3. Table K illustrates the control parameters utilized for boiler feedwater at the economizer inlet. Table L illustrates the control parameters utilized for reheat steam. Prior to 1994 using the AVT program, Unit 2 was chemically cleaned every 2 to 3 years, based on an increase in boiler feed pump discharge pressure. Fouling of the orifice valves in the lower header system caused the increase in discharge pressure. Waterwall tube samples taken at regular intervals did not show any appreciable deposit accumulation. Following the change to oxygenated treatment in 1994, the unit has not required cleaning in a period of more than 7 years. Again, waterwall tube samples have not shown any significant deposit accumulation.

Advanced Monitoring Techniques

Technology advances over the past two
decades have led to an outpouring of 'varioys digital/computerized data logging systems that have the ability to control, trend, and monitor power plant processes. Water treatment and co.rrosion control softwqre are plentiful in today's power market. Often, the ability to monitor and store data greatly exceeds the resources required to analyze and assess that data in a timely fashion. This is a direct contrast to the purpose of collecting data, and thus the whole process can become a mere act of electronic cataloging of numbers.

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Data requirements. The first consideration for data requirements is potential problems. Data are needed to assure that the power plant is operating within a certain set of criteria. As listed previously, corrosion and deposition are two main problems in a power plant that can occur from a variety of situations. There are measurement techniques that can be used to monitor and assess these problems both on and off line. Table A gives an example of common power plant c<11cernsalong with some data that are used to diagnose the condition. Locations in the plant for data monitoring are chosen based on the area of concern, the ability to sample, and the ability to accurately analyze for that species based on expected concentration levels. Algorithms and modeling can be used to calculate the corrosion or chemistry environment of an area that is not accessible to direct measurement. As with all data collection, the error in measurement or calculated measurement must be considered in evaluating the overall result. Also, the frequency of measurement plays a large role in proper diagnosis and the amount of data logging that is require~ to assure plant integrity. Online data acquisition can occur at frequencies greater than once per second. Manual, or grab data typically occur once per shift, day, week, month... The frequency of data collection repres~nts a combination of importance and dynamics of the data. A high frequency of data collection reflects an important or dynamic data and a low frequency of data collection reflects a less important or dynamic data. The reliance on in-line data such as pH, conductivity, and cation conductivity has, greatly enhanced the ability to monitor plant chemistry specifications for many power plant conditions. Still, the diagnosis of these conditions is often left to single-parameter conditions. Single-parameter diagnosis is reasonable for some conditions, such as an elevated pH in the boiler, or a lack of amine in the feedwater. However, there are multiple conditions that can contribute to a single data out-of-specification occurrence. This leaves single-condition diagnosis at a loss. Other technologies and algorithms have been developed to assess multivariable diagnostics. Some of these techniques include fuzzy logic, rulebased diagnostics, and pattern recognition techniques. Initial applications of
ULTRAPUREWATER@ OCTOBER 2006

24

these techniques were used in the power industry through EPRI member utilities (1, 2). Further development of technologies has lead to real time Internet-based diagnosis for systems, including a variety of steam cycles and cooling towers. Advanced techniques have been employed in the power industry to not only diagnose the condition of the plant in real time, but also to give guidance to power plant personnel on corrective actions and consequences of the current condition. Summary Corrosion in power plants is bounded by metallurgical susceptibility and design, driven by heat and stress, and advanced by the physical-chemical environment. Because of these relationships, chemistry programs have been developed to address a variety of metallurgies,temperatures, and designs in order to mitigate corrosion and ensure equipment integrity. There are many instruments and techniques available to improve control of chemistry programs and corrosion in fossil power plants. These approaches have proven

valuable in mitigating corrosion issues, which would have seriously undermined equipment integrity if not addressed. Recent advances with on-line monitoring. and diagnostic techniques are allowing power plant personnel to spend less time gathering and analyzing data, and more time proactively managing a program. Service providers with Internet based technologies are able to implement low cost, high value products to power plant workers that improve overall resource performance.. References 1. "EPRISMARTchemWorksTM", TR-108739V1, Electric Power Research Institute (June 1998). 2. Smith, D.J. "Remote Monitoring", Power Engineering (March 2004).

treatment experience in the refining, petrochemical, pulp and paper, electrical power generation, steel, and chemical plant utility operations. He received his Ph.D. in chemistry from University College Cardiff (The University of Wales) in Cardiff, Wales, Great Britain. Coauthor Joe Bates is the vice president of engineering and a principal consultant at iSagacity. He has 22 years of experience with companies that include Commonwealth Edison, Electric Power Research Institute (EPRI), and EPRI Solutions. He is a recognized expert in water treatment and corrosion control in the power industry. He is a patent holder of a polymer dispersant for nuclear steam generators as well as a developer and implementer of chemistry program optimizations at several power plants. Mr. Bates holds a B.S. in Chemical Engineering from the University of Illinois.
This paper was presented at the 24th Utility Chemistry Workshop, which was conducted May 11-13, 2004, in Champaign, III.

Author Douglas Bain, Ph.D., has more than 33 years experience in the water treatment industry, including 26 years with Dearbornand BetzDearborn and the last six years as an independent consultant. His work has involved all aspects of cooling systems, boilers, steam turbines, and ste~m/condensate systemoperation. Dr. Bain has water

Key words: ALL-VOLATILE TREATMENT, BOILERS, CORROSION, FOULING, OXYGEN, POWER, SCALING

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