The chemistry in cogeneration and power plants (CHP)

Recommendations for the chemical equipment and for the quality criteria for the water chemistry of drum boilers

990.62 Translated by Kemotron with permission by FLLESKEMIKERNE 1996 Authors: Rudolph Blum Kate Wieck-Hansen Hans Mller Erik Smitshuysen Karol Daucik Fynsvrket Midtkraft Nordjyllandsvrket Vestkraft Skrbkvrket

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Translation of section 3.2 and appendix 1 "KEMIEN P DECENTRALE KRAFTVARMEVRKER" Version 1996

3.2 Steam turbine plants

Steam turbine plants generate superheated steam (max. 60 bar, 450C), i.e. drum boiler plants with a relatively high heat flux load and plants having steam a temperation with direct feed water injection. 3.2.1 Steam quality The specifications for make-up water, boiler feed water, boiler water, and district heating water are given in table 3.3.The requirements are made in accordance with our own experience and the VGB requirements according to section 3.1.1. Table 3.3 Specifications for steam turbine plants Make-up water, boiler feed water, steam, boiler water, and district heating water. Makeup water L (S/cm) Lk (S/cm) PH Fe (mg/kg) Cu (mg/kg) SiO2 (mg/kg) O2 (mg/kg) NH3 (mg/kg) < 0.2 Boiler feed water 5-7 0.2 9.4 < 0.02 0.02 0.003 < 0.02 0.02 0.02 1 1 0.02 <4 Boiler water < 50 < 150 9.4-10 10 District heating water < 25

Steam 5-7 0.2 9.4 0.02

In order to obtain sufficiently low contents of oxygen in the boiler feed water, it is assumed that the make-up water for the feed water tank is added where the deaeration is taking place. 3.2.2 Chemical dosing The water-steam circuit has to be alkalized in order to minimize the iron transport and to reduce corrosion. For the conditioning of feed water and steam, only volatile alkalization remedies are to be used. Flleskemikerne recommend the use of ammonia.

The addition of diluted ammonia to the condensate system or the feed water boiler is done continuously or periodically. The aim should be a pH-value of 9.4, corresponding to an ammonia concentration of 1 mg/kg. The dosage speed is best controlled in accordance with the conductivity of the feed water or the steam, which should be between 5 and 7 S/cm. When dosing periodically, the ammonia dosing pump and the make-up water pump are to be started at the same time. For boiler water, solid-state alkalization (caustic soda or trisodium phosphate) or volatile alkalization (ammonia) can be used. Solid-state alkalization with NaOH will give the best corrosion protection. Alkalization with NaOH should not be used in plants where there is a risk of an increasing concentration of substances dissolved in the boiler at places of high thermic load and mechanical stress, e.g. in roller gaps, or in plants without sufficient boiler water level control, or in plants where the water circulation may fails to an extent resulting in local dry out of boiler water. An evaporation of the boiler water will give concentrated alkali solutions, which are aggressive to steel. That will lead to stress corrosion and possibly to comprehensive grooving. If conditioning with NaOH, this attack will happen quickly. Normally NaOH conditioning creates no problems in cogeneration plants with water tube boilers. However, boiler circulations may be so poor that the evaporator pipes dry out, resulting in NaOH-initiated stress corrosion. Insufficient boiler water circulation is a serious construction fault, which has to be corrected. Up to such reconstruction, the boiler should be operated with ammonia alkalization only. Control of this conditioning system is as simple as the conditioning system with caustic and ammonia. Even this kind of conditioning involves a certain risk of corrosion damages due to concentration of salts from the boiler water at the places of dry out. However, such damages will occur considerably later than the case is when using the nonvolatile alkalization. The general corrosion protection during ammonia alkalization is reduced due to the volatility and low alkalization ability of the ammonia. Alkalization with trisodium phosphate of the boiler water is also commonly used, but for the below reasons it is not recommended by Flleskemikerne: - in boilers with a good circulation, the trisodium phosphate will not give a protection as good as NaOH. - in boilers with a poor circulation, the concentration of phosphate will also lead to corrosion damages. - phosphate conditioning is difficult to control. That has to do with its contribution to the acid conductivity of the boiler water and with its tendency to hide out in boiler deposits.

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the advantage of trisodium phosphate - its power to bind hardness - is not relevant in decentralized heating and power plants, since the risk of hardness ingress in boilers is minimal.

connection with the addition of make-up water, and the NaOH-quantity is controlled by means of conductivity measurement (25 mS/cm) or in accordance with the quantity of make-up water added. In the construction of equipment for dosing of ammonia and NaOH, it is important to take the carbon dioxide in the air into account. Ammonia as well as NaOH reacts willingly to carbonates with the carbon dioxide in the air. It already happens where the air penetrates through the breather pipe of the storage tank. When the carbonates are added into the system, the acid conductivity of the boiler water and of the steam increases. This may increase the frequency in the need of blowdowns, or it may prevent the steam from reaching its specified acid conductivity of 0.2 S/cm. It is thus important to keep the carbon dioxide out of the storage tanks. Both chemicals mentioned are dosed in amounts so small that the available trade concentrations cannot be used. For the above reasons as well as for safety reasons, the construction of dosing systems have to be made in such way that the dilution is taking place in closed systems in which all breather pipes are gathered and led to a carbon dioxide filter. Instead of a carbon dioxide filter, a siphon can be used, but in such case only small portions of the diluted solution should be prepared at the time (e.g. 24-48 hours). 3.2.3 Monitoring of the water chemistry in steam turbine plants The monitoring of the water chemistry is done partly by means of continuous conductivity measurements, partly by periodical measurements of pH, Fe, Cu, SiO2, O2, NH3, and conductivity. The necessary sampling equipment is described in Appendix 2.

Good flow conditions in all parts of the boiler are an indispensable condition for uncomplicated operation. To avoid future problems, it is recommended to test the flow conditions of the evaporator part of boilers conditioned with NaOH and of boilers suspected for poor circulation .One simple and efficient way of surveying the flow conditions is to add isotope-labeled Na to the boiler water. If there is a satisfactory circulation in all evaporator panels, optimum conditioning with NaOH can be used. In case of insufficient circulation, all kinds of solid salts or conditioning substances will eventually lead to serious corrosion damages, and the circulation conditions of the boiler should consequently be improved. Until this improvement has taken place, only ammonia should be used as pH-regulating conditioner, and the salt contents should be kept at a minimum, i.e. direct conductivity L < 20 S/cm and acid conductivity Lk 2 S/cm with suitable blowdown. The dosing of ammonia is to be controlled on the basis of the direct conductivity of feed water and/or steam. In boilers with satisfactory circulation, the boiler water is alkalized with natrium hydroxide (NaOH), dosed to one of the downcomers in order to secure a proper mixing. A pHvalue of 9.4-10 is the aim, corresponding to NaOH contents of 1-4 mg/kg. The periodical dosing is controlled on the basis of direct (L) and acid (Lk) conductivity measurements. Those two measurements give a unambiguous indication of the pH and the purity of the boiler water. In figure 3.2, the normal and acceptable operation area for connected measurements of L and LK is shown. Outside the normal operation area, corrections have to be made, either by addition of NaOH or by blowdown. If the acceptable limits are exceeded, the error should be found and eliminated immediately. An example in appendix 1 illustrates this procedure. The amount of added NaOH should be equal to the amount lost. The losses are mainly due to the blowdowns, but also during sampling some NaOH will disappear. To improve the chemical control, it is thus recommended to check up after every blowdown if further addition of NaOH is required. It may be useful to automate the NaOH-dosing to the boiler water, which can be done by connecting the dosing to the make-up water pump. In such case, the velocity of dosing has to be determined by means of conductivity measurements. The district heating water is alkalized by means of caustic soda to pH = 10, corresponding to NaOH-contents of 4 mg/kg. The chemical dosing is done most simply in

Continuous measurements Conductivity meters are the only suitable instruments for reliable and robust continuous monitoring of the water chemistry. For a boiler plant, four conductivity meters and one meter for district heating water are required. Suggestion for locations is shown in figure 3.3. In samples from the boiler water, the direct conductivity and the acid conductivity are measured. These measurements are used for control of the NaOH-dosing and the boiler blow-down. Appendix 1 describes the control procedure by use of fig. 3.2 (see next page). In samples from feed water or steam, direct conductivity is measured for control of the ammonia dosing.

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Fig. 3.2 L and Lk for boiler water In samples from steam, the acid conductivity is measured (after cation-filter) for control of the steam purity, for instance in order to recognize the point of time during startup at which the turbine can be taken into operation. In samples from the circulating district heating water, the direct and the acid conductivity can be measured to determine the water quality. This measurement is only required in plants with a high consumption of make-up water.

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Fig. 3.3. Example of chemical control and monitoring system. Steam turbine plant.

Table 3.4

Continuous measurements for steam turbine plants Value (S/cm)

Measurement Conductivity boiler water Acid conductivity boiler water Conductivity feed water/steam Acid conductivity steam Conductivity distr. heat. water Acid conductivity distr. heat. water Conductivity make-up water

Instrument Kemotron* type 3213 Cation filter + Kemotron* type 3213 Cation filter + Kemotron* type 3213 Cation filter + Kemotron* type 3213

Recommended < 40 < 50 57 < 0.2 < 25 < 50 < 0.2

Limit 50 150 57 0.5 50 150 0.2

The arrow indicates that the conductivity before and after the cation filter is measured by the same instrument. Kemotron* type 3213 can do this continuously with its two channels. *) Kemotron or corresponding quality equipment.

Periodical measurements For the periodical control of the water chemistry, the following sampling equipment should be available: 1. Feed water before ECO 2. Boiler water 3. Superheated steam 4. District heating water 5. Make-up water 6. Condensate All samplers except for make-up water should be provided with a cooler so that the samples have a temperature of 25C and be dimensioned to a flow of 1 liters/minute.

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Table 3.5. Suggestion for periodical measurements for steam turbine plants Periodical measurements for steam turbine plants Measurements Make-up water SiO2 (mg/kg) Fe (mg/kg) Feed water Ph (mg/kg) Fe (mg/kg) Cu (mg/kg) SiO2 (mg/kg) O2 (mg/kg) NH3 (mg/kg) Steam pH Fe (mg/kg) SiO2 (mg/kg) NH3 (mg/kg) Boiler water pH SiO2 (mg/kg) m (mval/kg) Disctrict heating water L (S/cm) Lk (S/cm) pH O2 (mg/kg) m (mval/kg) Cl(mg/kg) A d d d D k d k d d d d d d d u d d d k u u Frequency B m m u u k u k u u u u u u u m u u u k m m C k k m k m k k m m k m m m m k m m m k k k Value Recommended 0.01 0.01 9.4 < 0.02 < 0.003 < 0.02 < 0.02 1 9.4 < 0.02 < 0.02 1 9.4-10 <1 0.1 < 25 < 10 10 0.02 0.1 < 0.5 Limit 0.02 0.02 9-9.6 0.02 0.003 0.02 0.05 0.5-1.5 9-9.6 0.02 0.02 0.5-1.5 9.4-10.3 4 0.05-0.3 50 150 9.4-10.5 0.05 0.05-0.3 3

Note:

d m u k A

daily monthly weekly campaign Frequency during and after start-up until the values have fallen below the limit values. Frequency during the first period after having achieved the limit values. After the first start-up, this frequency of analysis is recommended for a one-year period. If exceeding the limit values, the A-frequency should be introduced while improvements are being made.

Frequency used when values have stabilized. If significant changes in the values are observed, frequency B should be used while improvements are being made.

The extent and frequency of the periodical analyses have to be adapted to the operation mode, the chemical quality, and the experience material of the plant. During the start-up period it is appropriate to make a daily analysis to determine whether the specifications are met. After a one-month period with satisfactory compliance with the specifications, the analysis frequency can be reduced to be weekly. A further reduction of the analysis frequency can be made after one year of satisfactory operation.

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Appendix 1. Example of correction procedure for boiler water during start-up

Fig. A.1 illustrates the course of the direct and the acid conductivity during the start-up. Point A (L = 70 S/cm, Lk = 150 S/cm) represents an example where the boiler water is contaminated with some salts before the start-up. To meet the purity requirements, the boiler has to be purged with pure water. During this replacement of water, the conductivity measurements will fall along line a. When reaching point S (L = 50 S/cm Lk = 108 S/cm), you will be within the area for acceptable operation and the boiler can be ignited. After the heating the draining will have the character of blowdown and continues until reaching point B (L =18 S/cm, Lk = 40 S/cm). At this point NaOH is to be dosed, since its concentration will have fallen to a minimum of 1 mg/l due to the immense dilution with pure water. The dosage is to be 3 g pure NaOH per m3 of water contained in the boiler and should be carried out over a period of at least 30 minutes. When dosing, the conductivity will change along line b. The dosing quantity has been adapted so that you will end at point C (L = 37 mS/cm, Lk = 40 mS/cm). From this point you are in the area of normal operation. Further changes in the conductivity will depend on the rate of salt entering the system and the salt removed by continuous draining (sampling). Every time the limits for normal operation are reached, a correction of the water chemistry should be made, either by a blowdown or by addition of NaOH. When blowing down, the status point will go towards 0 at the diagram, and when adding NaOH it will move horizontally to the right. When the conductivity increases beyond the normal operation area, the reason for the increase should be detected. When reaching the limits of the acceptable area, the conductivity should be decreased by all means. In rare cases the control of blow down can be assumed by a too high concentration of SiO2 in the boiler water.

Fig. A.1 Control of boiler water conductivity during start-up

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Appendix 2 Required sampling equipment Sampling equipment for water or steam: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Probe Block valve Sample pipe Cooler Regulation valve Conductivity analyzer Tee Two regulation valves Cation filter Conductivity analyzer

A sampling station containing all 10 components above is intended for the measuring points where beyond the laboratory analyses also direct measurements and sour conductivity measurements have to be made. A sampling station of this type is illustrated in figure A.2. An installation of the first 6 components can be used for the continuous measurement of direct (specific) conductivity only.

2 3 4 6 5 7 8 9
K

10

Fig. A.2 Station for steam or water sampling and monitoring Component description: 1. Probe A bias cut probe directed against the flow, with a 6 mm clearance, made from acid-proof steel AISI 316L or from the same material as the pipe. Block valve Preferably a ball valve with a 6 mm clearance, otherwise a needle valve. In any case the materials should be acid-proof steel AISI 316L. Sample pipe Of acid-proof steel AISI 316L 9. 4. Cooler Pipe cooler or coiled condenser Regulation valve Needle valve (acid-proof steel AISI 316L) with 4 mm clearance in the nozzle. 6. Conductivity analyzer Kemotron type 3213 monitor with type 4721 sensors. and type 71/2 flow chamber. Each monitor is connected to two sensors with automatic sensor shift, thus providing for the direct as well as the acid conductivity measurement simultaneously. 7. Tee Tee (acid-proof steel AISI 316L) to separate the sampling liquid going to the measurements of the conductivity and the laboratory test, respectively. The liquid for the conductivity measurement should be flowing perpendicularly to the direction of the other two flows. Two regulation valves Ball valves of acid-proof steel AISI 316L with a 6 mm clearance. Cation filter The filter should be of a transparent material with 1-3 liters of well-regenerated and rinsed cation-exchanger changing color by exhaustion.

2.

8.

3.

5.

10. Conductivity analyzer Kemotron type 3213 monitor with type 4721 sensors and type 71/2 flow chamber. Each monitor is connected to two sensors with automatic sensor shift, thus providing the direct as well as the acid conductivity measurement simultaneously.

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