Water Chemistry Measures to Improve Steam Generator Performance

S. Odar Framatome-ANP GmbH, Germany

E-mail: suat.odar@framatome-anp.com

Abstract: World wide the majority of unscheduled plant shut-downs induced by steam generator failures are caused by corrosion problems. Such steam generator degradation problems arise from the continuous ingress of non-volatile contaminants, i.e. corrosion products and salt impurities accumulated in the steam generators. These impurities have their origin in the secondary side systems. The corrosion products generally accumulate in the steam generators and form deposits not only in the flow restricted areas, such as on top of tube sheet and tube support plates, but also build scales on the steam generator heating tubes. The concentration of salt impurities within these deposits at top of tube sheet and in the tube to tube-support-plate crevices can induce a variety of corrosion mechanisms on steam generator tubes. In addition, the tube scales in general affects the steam generator thermal performance, which ultimately cause a reduction of power output. The most effective ways of counteracting all these degradation problems, and thus of improving the steam generator performance is to keep them in clean conditions. This paper presents the water chemistry issues to improve the steam generator corrosion and thermal performance. In particular the subjects of operating water chemistry, cleanliness criteria for steam generators and steam generator cleaning results with this respect will be discussed. Introduction: Steam generators (SG) of Pressurized Water Reactors (PWR) are key components. Their reliability affects greatly the overall plant performance and availability. World-wide experience shows that significant number of operating PWRs have now corrosion or mechanical degradation problems in their SGs [1]. These SG problems often force unscheduled or extended outages for preventive and corrective maintenance, which are costly in terms of repair work, loss of power and personnel radiation exposure. In addition to SG corrosion problems, which are experienced mainly on the secondary side, deterioration of SG thermal performance is also experienced in most of the plants, which is caused by growing SG tube scales affecting the primary to secondary side heat transfer. Based on field experience, corrosion product fouling in SGs has been identified as a major cause of heat transfer degradation in PWR plants, with the power output at some plants being decreased to as low as 80% of full power. The origin of these tube scales is again the corrosion products generated in the secondary side of the plant and transported into SGs. All these secondary side SG problems can be minimized or even be prevented by adopting suitable design and secondary side water chemistry operation concepts. The main prerequisite is the careful adaptation of the water chemistry to the existing the SG design and the structural materials used. In the following chapters the water chemistry measures on the secondary side of the PWR plants to achieve this goal will be described and the experienced results at field with respect to improvement of the SG performance will be presented and discussed. Secondary side SG tube corrosion: Secondary side SG tube corrosion is caused in all cases due to the presence of corrosion product deposits adherent on the SG tubes and of the concentrated impurities within these

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deposits. Non-volatile impurities, which are always present in trace quantities in the feedwater, enter into the SGs with the feedwater and concentrate within the deposits on the tube sheet, in the tube support crevices and on the tube surfaces. The concentration mechanism is illustrated in Figure 1. Figure 1: Impurity concentration mechanism

control was applied by stringent water chemistry specifications. In addition, world wide different water chemistry modifications or changes were performed: For example, In USA and Japan, water chemistry modifications like molar ration control and boric acid treatment Figure 2: SG tube corrosion as a function of pH and redox potential [2,3]

The outer surface and upper part of these deposits are wetted by SG water containing trace amount of impurities. Accordingly impurities penetrate in those areas. The lower part of the deposits is usually dry due to heating by primary side. Between wet and dry zones exists an alternate wetting and drying zone, where the water starts to evaporate and release this area as steam. In those alternate wetting and drying areas salt concentrations can reach corrosive levels and compositions. Depending on the prevailing beneath deposit local environmental conditions, i.e. pH and redox potential, various corrosion mechanisms, like Secondary side Stress Corrosion Cracking (OD-SCC), Inter Granular Attack (IGA), denting, pitting and wastage can occur (see Figure 2). Water chemistry measures: These corrosion problems can be counteracted by keeping the SGs impurity clean (especially the crevice areas at top of tube sheet and in tube supports). For these purpose world wide effort was done to implement improved water treatment systems to achieve so far technical possible impurity free condensate, feed and make-up water in the plants. The impurity

were developed and implemented in the field to mitigate the SG tubing corrosion [3]. The aim of these SG chemistry modifications is to control the crevice chemistry at a neutral pH range for a satisfactory environmental conditions with respect to tube corrosion (see Figure 2). Unfortunately, even based on some promising laboratory data these modifications were claimed to be helpful, they were not sufficient to stop or to remarkably mitigate the SG tube corrosion and still numerous SG tubes had to be repaired (plugging and/or sleeving). For example, loss of capacity factor attributed to SG corrosion problems in US PWRs was with decreasing tendency in the range of 2-8 % for the years 1980 through 2000 causing billion of dollars cost for the nuclear utility industry [4]. In contrast to USA and Japanese approach another water chemistry strategy was selected in Germany, which aims to prevent or suppress the impurity concentration mechanism beneath SG deposits by minimizing the corrosion product deposition in the SGs. Those corrosion products have their origin in the secondary side of the

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pH-value

plant, where they are produced mainly in two phase flow steam systems by erosion corrosion of the carbon steels. To counteract the erosion corrosion High AVT chemistry (All Volatile Treatment with high pH values ) for the entire secondary side including the SGs was developed and implemented at the beginning of the 1980s in the plants. This water chemistry considers the injection of only hydrazine to maintain the reducing conditions in SGs, whereas the high pH values, necessary to counteract the erosion corrosion is adjusted by ammonia (see Figure 3), which is produced by thermal decomposition of hydrazine [5 - 10]. This new water chemistry was Figure 3: Carbon steel metal release by erosion corrosion as a function of pH values

chemistry from beginning on. All German PWRs now operating since last 25 years with High AVT without any corrosion problems in their SGs. Since implementing this high pH chemistry Tube Sheet Lancing (TSL) is no more performed Figure 4: Feed water iron concentration as a function of pH in Plant E
10,5 20

10

15

pH(NH3) Fe

Fe [ppb]

9,5

10

8,5 Jan 76

0 Sep 78 Jun 81 Mrz 84 Dez 86 Sep 89 Jun 92 Mrz 95 Nov 97 Aug 00 Mai 03

Figure 5: Feed water iron concentration as a function of pH in Plant H

10,2 20

10 15 9,8

Fe [g/kg]

pH-value

9,6

pH(NH3) Fe

10

9,4 5 9,2

9 Jan 79

Sep 81

Jun 84

Mrz 87

Dez 89

Sep 92

Jun 95

Mrz 98

Nov 00

Aug 03

0 Mai 06

very successful to prevent SG tube corrosion. In all old German PWRs operating under low pH conditions, where end of seventies with PO4 chemistry wastage corrosion was experienced in their SGs, the water chemistry is converted to this new chemistry after replacing copper bearing materials in their condensers. The conversion to high pH resulted in a drastically reduction of feed water iron concentrations. Within a short time of operation feed water iron concentrations in the range of ~ 1 ppb or less was achieved (see Figure 4 and Figure 5). This lead to drastically reduction of corrosion product transport into SGs. The new PWRs starting their commercial operation in early of eighties and after, applied High AVT

every year, but in average each three years.; and the removed amount of deposits range 3-4 kg per SG by each TSL cleanings. There are even some plants, didnt see the necessity of applying TSL after 6-7 years of operation.. Annual endoscopic visual inspections confirm the cleanness of the SGs. The reduction of feed water iron concentration improved also the SG thermal performance significantly. During the operation period with low feed water pH values having higher iron transport rates, remarkable steady increase of SG tube fouling was experienced in all plants. This was drastically reduced to almost no fouling growth after introducing high pH and in new plants with high pH from beginning on, it was insignificant (see Figure 6).

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Figure 6: Influence of feed water pH on SG tube fouling

The German field experience with high pH operation verified the important influence of the secondary side on SGs and confirmed that if SG corrosion problems need to be prevented or arrested by control of water chemistry, this needs to be optimized for the entire secondary side, and not just in the SGs. Today this concept of reducing the corrosion product transport into SGs is worldwide well accepted water chemistry strategy to prevent SG corrosion problems. Since mid of nineties in other countries water chemistry modifications are ongoing by use of so called advanced amines (Morpholine, ETA, MPA, DMA, 5-AP) with the aim to reduce the feed water iron concentrations [11]. Published field experience indicating promising results [12, 13]. Steam Generator Cleaning Criteria: Since the generation of corrosion products in the secondary side and as a consequence of this feed water corrosion product transport into SGs cannot be completely eliminated, with the plant operating time the amount of deposits in SG will increase. This leads later to the necessity of corrosion product removal from SG for damage prevention. i.e. for improvement of SG corrosion and thermal performance. With this regard many plant operators are asking if they need the cleaning and when they need it. To answer these questions, several operating chemistry parameters can be used. The change in SG performance usually results in a change of some SG operating chemistry parameters, which are indicative of the increased SG deposits: One of the main chemistry parameters which can be used for this purpose is the change of SG and feed water hydrazine concentrations. The hydrazine concentration in SG is usually higher than in feed water due to concentration increase by evaporation; but is limited because of

volatility and thermal decomposition (SG temperature is higher than feed water temperature). Since the thermal decomposition of hydrazine is catalyzed by deposits, the decomposition rate will increase with increasing deposit amount. In other words, the hydrazine concentration ratio of SG to feed water, is expected to be decreasing with operating time of the plant. This is exactly what is experienced in many PWRs. In Figure 7 the behavior of hydrazine concentration ratio is given as a function of 12 years of operating time for one PWRs as a typical example. The purpose of using hydrazine is to maintain reducing conditions in SGs. Due to the increase of thermal decomposition of hydrazine in SG and limitation of feed water hydrazine concentration (because of environmental requirements), SG hydrazine concentration decreases with a operating time. In general, this, can lead to a situation where SG hydrazine concentration needed to maintain the reducing conditions in SGs can no more ensured; and accordingly a removal of the deposits may be necessary. For prediction this cleaning time the slope of SG/FW hydrazine concentration ratio decrease can be used. This easy evaluation using routine operating chemistry data, can help plant operators to establish SG cleaning strategy in advance and to perform performance oriented SG maintenance. Further examples of the thermal decomposition of hydrazine in SGs is given in Figure 8. Figure 7: Typical evolution of hydrazine concentration ratio SG/FW in a PWR

The use of hydrazine decomposition behavior for decisions regarding SG cleaning can be supported by evaluation of the SG hide out behavior during plant shut downs or during out of specification conditions, for example, due to condenser leaks:

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.Figure 8: Hydrazine decomposition examples

3 Plant G Plant I Plant K Plant M Plant P

2,5

N2H4 Concentration Ratio

1,5

During these tests, the constant SG Na-24 concentration (corrected by steam carry over, blow down and natural decay) is indicative for an insignificant SG hide-out behavior. If Na-24 concentration decreases remarkably, this is due to significant hide-out. In Figure 10 example of SG with significant hide-out is compared with the one without remarkable hide-out behavior. Figure 10: SGs with significant and negligible hide-out behavior

0,5

0 Jan 80 Dez 81 Dez 83 Dez 85 Dez 87 Dez 89 Dez 91 Dez 93 Dez 95 Dez 97 Dez 99 Dez 01 Dez 03

In the SGs the concentration of impurities are controlled by feed water impurity concentration, SG blow down rate, steam carryover and finally hide-out (absorption of impurities in the SG deposits). The contribution of steam carry over is very small and can usually be neglected. If the impurity concentration is controlled mainly by SG blow down rate, i.e. impurity input is same or similar to impurity out-put, there is no need for concern with respect to SG corrosion problems. Because the impurities are not remaining or concentrating in SGs. This can well be checked by impurity mass balance calculations during condenser leaks as indicated in an example given in Figure 9. Figure 9: SG Na concentration evolution during a condenser leak in one PWR
18 16 14 12
1000 900 800

The hide-out behavior of SGs changes also with the operating time; i.e. hide-out increases with increasing deposit loading in the SGs, as demonstrated by hide-out test performed two years later in the same SG without hide-out shown in Figure 10 (compare Figure 11). The hide-out increase rate can also be used for decision making when the SG cleaning should be scheduled. Figure 11: SG hide-out increase with operating time confirmed by hide-out tests

Na input
Na output
Power

700 600 500

10 8 6 4 2 0

400 300 200 100 0

31.08.96 00:00

05.09.96 00:00

10.09.96 00:00

15.09.96 00:00

20.09.96 00:00

25.09.96 00:00

Hide-out is the only mechanism in SGs, which may lead to impurity concentration up to corrosive levels; and therefore needs to be monitored and evaluated carefully. Increase of deposit levels increases the SG hide-out behavior. When hide-out starts to be dominant for impurity control in SGs, it results in a high corrosion risk. This situation of SG hide-out behavior can be monitored either by hide-out return tests during plant shut downs (release of impurities hiddenout during operation) or by hide-out tests (injection of Na-24 tracer into feed water).

Power (Mwe)

Na [g/h]

Finally, in addition to chemistry parameters, several outage inspections results can also be used as criteria for making a decision on SG chemical cleaning:

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Heavy hard deposits are the locations for impurity concentration to corrosive levels. This can be confirmed by visual inspections: Different colors of deposits are direct indication for salt concentrations (see Figure 12). If the color of the deposit are uniform black, in such cases only chemical analysis can help to assess their risk for tube corrosion. Figure 12: Colored SG deposits

Steam generator chemical cleaning: Since mid eighties, SG chemical cleanings are performed numerous times for improvement of SG performance with respect to corrosion or thermal efficiency [14]. As of today two different main SG chemical cleaning technologies are used. The one is low temperature non proprietary EPRI SGOG process applied at 95-120C mainly in USA. The another is the high temperature FANP proprietary SGCC process, which is applied in more than half of all chemical cleanings world wide. This high temperature process is applied under hot standby conditions at 160-175C during plant shut down or start-up operations. Most of these applications were in preventive nature but some were also active to arrest the SG corrosion. The process description is published numerous times in the literature some examples are given in [15, 16]. In the following several application results with respect to improvement of SG performance are presented. As discussed in previous chapter, deposits in SG increase the thermal decomposition rate of hydrazine. Accordingly with increasing deposits in the SG, the hydrazine concentration ratio SG to feed water decreases. This hydrazine ratio value, as one of the SG cleanliness criteria, was improved after all SG chemical cleanings except in one case (see Figure 13). In this case (KKS: NPP Stade,), SG chemical cleaning was applied in SGs only partially, excluding the U-bend area. Figure 13: Influence of SG chemical cleaning on N2H4 SG/Feed Water ratio
2,5
N2H4 ratio (precleaning) N2H4 ratio (postcleaning)

Finally, increase of tube scales (fouling) may deteriorate the primary- to secondary-side heat transfer, resulting in a steam pressure decrease. Monitoring of pressure decrease is the best tool to assess the SG thermal performance. For decision regarding establishing SG cleaning strategy and applying performance oriented SG maintenance, all these data evaluation, as described above, should be used. Table 1 summarizes these SG cleanness criteria used by Framatome-ANP in Germany for SG chemical cleaning. Such data evaluation results and criteria were used to make decisions for SG chemical cleaning in German NPPs. Table 1: Yes and No decision criteria for SG cleanness

N2H4 SG/FW Ratio

Parameter
N2H4 ratio Out of Spec. Conditions Hide-Out HO-Return Tube Fouling Visual Inspection TSL Tube scale thickness

Yes
<< R Impurity control by HO Significant Acidic / Caustic Power loss Colors Hard sludge High growth rates

No
>R

1,5

Impurity control by Blow down Minor ? Neutral Insignificant Black No hard sludge Low growth rates

0,5

0 KKU KKS KWG KBR GKN-1

R: N2H4 SG/FW ratio value for plant specific SG reducing conditions

Almost in all applications main steam pressure increase was reported by plant operators after SG chemical cleanings (see Table 2). These steam pressure increases have corresponded to ~ 0.5 to 1.6 % heat transfer tube surface gains.

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Table 2: SG thermal performance improvements by chemical cleanings

Plants Steam pressure increase [bar] ~ 0.45 ~ 1.22 ~ 0.85 ~ 1.6 ~ 0.5 Data not available Data not available Other observations

addition to main steam pressure increase, a simultaneous coolant temperature decrease of 0.5C was also experienced (see Figure 16). Figure 16: Thermal performance improvement by SG chemical cleaning in NPP Neckarwestheim Unit-1
Steam Pressure (bar)
62
BEFORE SG Chemical Cleaning

Unterweser Stade Atucha Neckarwestheim-1 Almaraz-1 Point Lepreau Paks-1

1.7% heat transfer surface gain 4.6% heat transfer surface gain 4.3% heat transfer surface gain Simultaneous ~ 0.5C coolant temp. decrease

Coolant temperature (C)

AFTER SG Chemical Cleaning

308

61

307

Steam Pressure (bar)

60

306

3.6C coolant temperature decreased Complete fouling recovery

59

305

58

304

57

303

Several detailed results of thermal performance improvements are given for the application of NPP Stade (see Figure 14) and Neckarwestheim Unit 1 cleaning (see Figure 15) as examples. Both plants were cleaned twice chemically; where as the first applications were in both plants only partial cleanings. After partial cleanings fouling improvement was not significant, this was experienced only in Neckarwestheim Unit 1 after complete SG cleaning. Figure 14: Pre- and post cleaning SG fouling behavior in NPP Stade
2000
Phosphate treatment with low pH
AVT pH < 9.5
AVT pH = 9.6

56 11:00 19:00 21.03.2002

302 03:00 11:00 19:00 03:00 11:00 23.07.2002 19:00 03:00 11:00

1500

Chemical Cleaning
(Partially)

Chemical Cleaning 6
Rf [10 -5 m * K/W]
4

m Fe;SG [kg]

1000
mFe,SG

Not only the thermal but also the corrosion performance of SGs can be improved by chemical cleaning, as it was confirmed by field experience several times world wide. An example for this is given in Figure 17: Due to sodium increase into SG by malfunction in the condensate demineralizer system ODSCC (secondary side stress corrosion cracking) was experienced in one PWR in 1988, which made necessary to plug 371 tubes [17]. SG chemical cleaning using FANP high temperature process could arrest ODSCC in the following operating cycles. The number of plugged tubes was reduced in the following outages till it was zero in three years after the sodium incident. Figure 17: Improvement of SG corrosion performance by chemical cleaning
450 400

500
Rf

2 0 -2 00 02 04 06 08 10 12 14 16 18 20 22 24 26 t[a]

0 -500

371
Plugged tubes Cumulative

350

Plugged Tubes

Figure 15: Pre- and post cleaning SG fouling behavior in NPP Neckarwestheim-1
4200
Chemical Cleaning SG10

300

250

SGCC

200

3600

2,5

150

Accum. Iron Ingress into SG [kg]

3000

100

2400

1,5

50

47 0
1987 1988 1989 Year

2
1990

0
1991

1800
Chemical SG Cleaning 2002

1200 accum. Fe ingress Fouling Factor

0,5

600

-0,5

-600 Jan 76

-1 Jun 81 Dez 86 Jun 92 Nov 97 Mai 03

In Neckarwestheim unit 1 cleaning case in

The field experience with chemical cleanings confirmed the feasibility of improving the SG corrosion performance; but also showed that if the corrosion is wide progressed the efficiency of the process will be limited (i.e. deep cracks cant be completely cleaned). Therefore it is

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Coolant temperature (C)

In spite of ~ 500 tubes plugged

Fouling Factor [10^-5 m * K/W]

recommended not to delay the cleanings once the corrosion starts; better to perform cleaning as preventive using plant specific SG cleanliness criteria, before corrosion starts. Conclusions: Secondary side chemistry control programs and measures are essential for good SG performance: x Adequate chemistry program helps to reduce feed water iron concentration significantly, which leads to improvement of SG thermal and corrosion performance. x Operating chemistry data are indispensable to evaluate SG performance and can support to schedule SG performance oriented maintenance activities. x Finally poor SG performance can be improved significantly by chemical cleanings. Reference: [1] EPRI Steam Generator Progress Report, Rev 15 [2] Source: EPRI IGA/SCC Work shops [3] SG degradation: Current mitigation strategies for controlling corrosion, P. Millet, CNRA/CSNI Workshop on SG tube integrity in nuclear power plants, Oct 30 Nov. 02, 1995, Argon National Laboratory, USA [4] EPRI Steam Generator Progress Report Rev. 15, 2000 [5] Stages of Development of Secondary Water Chemistry in Pressurized Water Reactors, A. Drr, S. Odar, P. Schub, VGB Kraftwerkstechnik 66, No. 11 Nov. 1986 [6] The secondary side approach to preventing corrosion, R. Riess, S. Odar, Nuclear Engineering International, January 1991, page 33-38 [7] 2Strategies for High Steam Generator Performance, R. Bouecke, S. Odar, International Power Generation Conference, October 6 - 10, 1991. -San Diego, Ca. [8] Secondary Side Chemistry Operational Experience at Trillo Unit 1, K. Streit, F. Yague, SNE Conference, October 28-30, 1992, Jerez de la Frontera, Spain, P. 108-110.

[9]

10 Years of Field Experience with High AVT Water Chemistry, K. Streit, S. Odar, Steam Generator and Heat Exchanger Conference, Toronto 1994

[10] Experience gained with the steam generator tubing material Incoloy 800, S. Odar, G. Hoch, R. Kilian, Conference on Interaction of Non-Iron-Based Materials With Water and Steam, Piacenza, June 1996 [11] The use of advanced amines in US PWRs, P.J. Millett, G.D. Bruns, G.E. Brobst, Proceedings of International Conference on Chemistry in Water Reactors: Operating Experience and New Developments, Nice, France, SFEN, April 1994 [12] Ethanolamine experience at Koeberg Nuclear Power Station, South Africa, K.J. Galt, N.B. Caris, International Conference on Water Chemistry in Nuclear Reactors systems, FNES, April 2002, Avignon, France [13] Strategic elements of steam cycle chemistry control practices at TXUs Comanche Peak Steam Electric Station, B. Fellers, J. Stevens, G. Nichols, International Conference on Water Chemistry in Nuclear Reactors systems, FNES, April 2002, Avignon, France [14] Utility experience with steam generator chemical cleaning, EPRI TR-104553, Project S523-03, Final report, Dec. 1994 [15] KWUs High-Temperature Chemical Cleaning Process Application in German PWRs to Improve Steam Generator Performance, G. Jacobi, B. Markgraf, H.R. Sauer, K. Seidelmann, S. Odar, Water Chemistry of Nuclear Reactor Systems, 8th BNES, London 2000. [16] Chinon B1 SG Chemical Cleaning Application of Framatome ANP InhibitorFree High Temperature Chemical Cleaning Process. To be published in International Conference Water Chemistry of Nuclear Reactor systems, EPRI, San Francisco, USA, Oct. 2004 [17] EPRI Steam Generator Progress Report Rev. 13, EPRI TR-106365-R13, Oct. 1997

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