14th International Conference on the Properties of Water and Steam in Kyoto

Water Treatment Trouble and Its Countermeasure

in Combined Cycle Heat Recovery Steam Generator

Kazuo Nakatsu and Tetsuo Yamamoto Design Engineering Group, Engineering Center, Fossil Power Division The Kansai Electric Power Co., Inc. Osaka, 530-6591, Japan E-mail: k828671@kepco.co.jp

Since the Heat Recovery Steam Generators (HRSG) of a combined cycle plant are different in the structure and design from those of conventional boilers, a number of troubles due to erosion caused by water have been reported. Especially, the problem of Flow Accelerated Corrosion in the low pressure Eco(Economizer)-circulation line has been highlighted[1]. From startup of the combined cycle power plant in the Kansai Electric Power Co., Inc., some valve erosion troubles have arisen in feed water system and steam system. Therefore, deep investigation and countermeasure have been required. As a result of various studies, Flow Accelerated Corrosion was considered as the main cause. In response to that, measures were taken to change the water treatment method, leading to a reduction in troubles including valve erosion.

1. Introduction Kansai Electrics Himeji No. 1 Power Station has two multi-shaft re-heating type combined cycle power generation plants, Units 5 and 6 (Fig. 1).
fuel. combustor

Water control for HRSG has been performed based on the JIS B8223 Water conditioning for Boiler Feed Water and Boiler Water. However, valve erosion troubles have arisen in the steam system, feed water system and condensate
evaporator to chimney To stuck superheater regenerator

main steam

Heat Recovery Steam Generator

steam condenser

Fig. 1. Schematic

diagram of

multi-shaft

re-heating type combined cycle power generation plant.

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water system since the startup of plant operation. Also, leakage troubles from the mechanical seals of the feed water pump have happened. The erosion conditions are shown in Figs.2 and 3.

superheater tube and the secondary reheater tube. As a result of the electron microscopic observation of the surface of the milli-pore filter with which the sampled low pressure Eco-circulation water was filtrated, spherical iron particles were detected as shown in Fig. 5.

Valve Erosion

Fig. 2. Valve for high-pressure drum.

Fig. 4. Sample scale on No. 5 high-pressure third super heater tube (x1000 time).

Valve Erosion

Fig. 3. Drain valve before high-pressure steam stop valve.

As a result of inspection of the troubled valves, a small amount of iron scale was found sticking to the part where the erosion developed. As for the feed water pump, an accumulation of iron scale in the clearance on the inside of the mechanical seal caused the mechanical seal operating parts to fail, leading to leaks. The trouble seemed to be caused by the effects of iron scale accumulation or by feeding water containing iron scale as sealing water. However, since this kind of problem has never been seen with conventional boilers, investigations into the cause and protective measures were required. 2. Investigation into Cause
2.1. Results of Investigation into Particles in Steam Tubes and Low Pressure Eco-circulation Water

Fig.5. Sample scale in feed water of No. 6 lowpressure Eco- circulation line (x10,000 time).

2.2 Development Mechanism of Erosion

Parts of the HRSGs steam tubes were sampled for electron microscopic observation of the inner surface. As a result, the spherical iron particles shown in Fig. 4 were found sticking to the steamoxidized scale on the high pressure tertiary

It was confirmed that the spherical iron particles were sticking to just the high pressure tertiary superheater tube and the secondary reheater tube (Fig.6), which feed spray water to prevent temperature rise in the steam tubes. Those particles were also observed in the low pressure Ecocirculation water, which is the source of spray water, as shown in Fig.5. Judging from such circumstances, the spherical iron particles seem to have been supplied by the spray water.

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Low pressure Eco Condensate pump

Low-pressure drum

Middle-pressure drum

Spray to second Reheter .

Low pressure Eco-circulation line

High-pressure drum

Spray

to third Super Heater

Fig.6. Schematic diagram of low-pressure-Eco circulation line.

In the light of the above-mentioned findings, troubles including erosion seemed to have resulted from the circulation of spherical iron particles that were generated in the systems due to some cause in the HRSG from the steam system to the feed/condensate water systems.
2.3. Generation Mechanism of Spherical Iron Particles Our studies into available literature

solute

Supersaturation

Crystallization

indicated that spherical iron particles are used industrially. Fig.7 shows the magnetic iron particles used for videotapes, etc.; they are spherical in shape similar to the spherical iron particles sticking to the tertiary superheater tube and the secondary reheater tube. Industrial spherical iron particles are manufactured by a crystallizing operation shown in Fig.8. Crystallization means the phenomenon in which the solute dissolved in the solvent exceeds the solubility limit until becoming supersaturated due to the change in temperature or otherwise, leading to the deposition of crystals, which can grow by supplying solute and agitating continuously. Regarding the place of generation, we thought the

Supply of solute

Supersaturation

Agitation

Crystal growth

Fig.8. Mechanism of crystallizing operation.

most likely candidate was the low pressure Ecocirculation line (Fig.6), which is a characteristic of HRSG, and comparable with the generation requirements for crystallization.
2.4. State of Low Pressure Eco-circulation Line

Generally, conditions for the development of crystals by crystallization include the 1) supply of solute, 2) supersaturation, and 3) agitation. We confirmed whether the low pressure Eco-circulation line satisfied these conditions required for the generation of spherical iron particles. Condition 1 Supply of solute: Unlike conventional Eco-circulation, circulating water in the low pressure Ecocirculation line of HRSG causes a faster velocity of flow. The Flow-Accelerated Corrosion (Fig. 9) allows a ready supply of solute.

Fig.7. Magnetic iron particle used for videotape (x10,000 time).

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Peeling of

scale

flow velocity

material

material

Corrosion advanceiron ion of mother material begins to elute

Iron concentration

Scale scale

Temperature
material

Fig. 11. Relation between iron (magnetite) solubility, pH, and temperature [2].

Fig. 9. Flow accelerated corrosion.

The relationship between velocity and temperature for the Flow Accelerated Corrosion of carbon steel described in Fig.10 shows corrosion developing greatly at a water temperature of about 130-150C. The inner temperature of the low pressure Eco-tube is around 150C, hence easily allowing erosion to develop.

Condition 3 Agitation: The low pressure Eco-circulation line is of a structure that circulates condensate water with a pump, hence creating sufficient condition for agitation. As described above, the low pressure Ecocirculation line meets all the conditions for crystals to develop through crystallization. Under theses conditions, spherical iron particles are likely to form and develop. 3. Countermeasures
3.1 Examination of Proposed Countermeasures

The generation of spherical iron particles through crystallization may be prevented by eliminating any one of the conditions : supply of solute, supersaturation, or agitation. Inhibiting supply of solute: An effective countermeasure would be to reduce the flow of the low pressure Ecocirculation water, in order to inhibit Flow Accelerated Corrosion. However, since this would require us to examine the thermal efficiency of the plant and would affect equipment, we did not choose this approach. Inhibiting supersaturation: A fall in pH can increase the solubility as shown in Fig. 8. Therefore, we decided to reduce pH to a value lower than the current operation in order to confirm that no spherical iron particles would be generated. However, since excessive reduction in pH can lead to an increase in erosion, we kept pH as high as practical.

Fig. 10. Relation between loss rate and temperature in flow acceleration corrosion of carbon steel [2].

Condition 2 Supersaturation: Figure 11 shows the solubility of magnetite is the maximum at around 150C, and is reduced by the increase in pH. At the Himeji No. 1 Power Station, pH for the feed water / condensate water systems is controlled at around 9.5, which means the solubility of magnetite is low and iron solute is supersaturated.

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Inhibiting agitation: An effective countermeasure is to reduce the low pressure Eco-circulation flow, as it can inhibit agitation. However, in the same manner as inhibiting the supply of solute, it requires an examination of the thermal efficiency of the plant and the effects on equipment. Therefore, we did not take this approach.
3.2. Implementation of Countermeasures

manner as with Unit 5. Therefore, we believe that we did an appropriate investigation of the cause and took proper measures.
References [1] Takayuki Mizuno Thermal and Nuclear Power Generation (Feb., 2001), The 6th International Conference for the Thermal Plant Cycle Chemistry [2] R. R. Harries & M. J. Willett Flow Accelerated Corrosion in HRSGs: Interdependence of Cycle Chemistry and Design Session 11

The relationship between the solubility of iron and pH/temperature of Fig.11 indicates that the solubility of iron in the low pressure Ecocirculation water at 150C is about 5 g/L at pH 9.6, 7 g/L at pH 9.5, 10 g/L at pH 9.4, and 30 g/L at pH 9.2. As such, as pH falls, solubility rises. Therefore, a reduction in pH of the feed/condensate water was expected to raise the solubility of iron and mitigate supersaturation, which is one cause of crystallization, ultimately inhibiting the generation of spherical iron particles in the low pressure Ecocirculation line. Iron concentration in the low pressure Ecocirculation line of Unit 5 is 11 g/L on the average. We expected a reduction in the pH-controlled value of the condensate water from 9.5 to 9.4 would raise the iron solubility from about 7 g/L to 10 g/L and would inhibit the generation of the spherical iron particles. Verification tests were conducted for a period from December 2001 to July 2002.
3.3. Confirmation of Effects

After reducing the pH of the feed/condensate water systems of Unit 5 to 9.4, we investigated the shape of scale contained in the water of the low pressure Eco-circulation line. No spherical iron particles were observed. Instead, needle-like scale, which can be observed even in conventional power plants, was found to develop. On the other hand, as a result of investigations into the shape of scale in the water of the low pressure Eco-circulation line of Unit 6, in which feed/condensate water systems were operated at a pH of 9.5, both needle-like scale and spherical iron particles were observed. Before taking any measures, we periodically repaired Unit 5 because of a number of troubles including valve erosion and leaks from the mechanical seal of the feed water pump. However, since such troubles decreased after taking the measures, we stopped periodic repair except for some equipment. Furthermore, similar troubles were reduced at Unit 6, for which measures were taken in the same

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