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Chemistry for coal-fired power plants: Experiences and challenges VGB PowerTech 3 l 2017

Author

Kurzfassung

13 Jahre Erfahrung auf dem Gebiet der Chemie für ein Kohlekraftwerk und anstehende Herausforderungen

Produkthersteller liefern oft ihre Technik mit einer Beobachtungszeit von nur zwei Jahren, sprich nur während der Garantiezeit. Kraft-werksbetreiber mit deutlich darüber liegenden Perspektiven für die Laufzeit ihrer Anlagen se-hen sich mit mittel- und langfristigen Heraus-forderungen konfrontiert, für die sie ihre eige-nen Lösungen entwickeln bzw. entwickeln müssen.Vorgestellt werden zwei für den Betreiber wich-tige Herausforderungen sowie dafür entwickel-te Lösungen aus dem Bereich der Chemie, die den Betrieb von zwei 660-MW-Kohlekraftwer-ken in der Türkei betreffen. Zudem sind stetig sinkende Grenzwerte für Emissionen aufgrund behördlicher Auflagen eine weitere Herausforderung für die Kraft-werkschemie.Produkthersteller sowie Forschung und Ent-wicklung sind insgesamt gefordert, für Proble-me, wie den dargestellten, Lösungen zu entwi-ckeln und damit die Weiterentwicklung der Kraftwerktechnik zu fördern. Dies auch im Sin-ne des Know-how-Austauschs innerhalb der Branche und unter den Kraftwerksbetreibern. l

13 years operational experience with a coal fired power plant in the area of chemistry and the challenges aheadMehmet Topeli and Ceren Davutluoglu

Mehmet TopeliChemical Engineer, MBACeren DavutluogluChemist, Msc Isken Energy Planning Manager Isken, Turkey

Introduction

İsken Sugözü Power Plant is the first im-ported coal fired power plant, which is owned by 51 % Steag GmbH-Germany and 49 % Oyak Conglomerate-Turkey. The net installed capacity is 1,210 MW (2 x 605 MW) and the units have been in com-mercial operation since 2003. The annu-al  coal consumption is approximately 3.5 Mtons and imported mainly from Co-lombia. The working hours of the units are more than 8,000 hrs per year and the effi-ciency is around 40 %. The main characteristics of the Sugözü PP are (F i g u r e 1 ):

– The boilers are Once-through Benson boilers with a dry ash removal system.

– The flue gas cleaning system is starting with electrostatic precipitators and fin-ished with wet limestone FGD system. NOx emissions of the power plant are within the valid limits with the help of the Low-NOx-burners. However High Dust Selective Catalytic Reaction (SCR) DeNOx units will be retrofitted and will be in operation in 2019, because of the coming stricter emission limits.

– There is an open seawater cooling sys-tem, therefore there is no cooling tower installed.

Main part

Within 13 years of operation period, the O&M team of the power plant faced a cou-

ple different problems in the area of power plant chemistry and have developed their own remedies. As its well-known every power plant, even sometimes every unit in the same power plant may react different to more or less same conditions. Therefore the cases and the relevant remedies, which will be dis-cussed could be specific to our power plant and may not be directly applicable to the other power plants. However the 4 differ-ent cases which have been discussed in this paper will not only be helpful for power plant operators to develop their own rem-edies and but also for technology providers to develop their technologies. Moreover the e(i)mmission limits in Tur-key, have already become stricter therefore new air pollution controlling technologies will have to be built in order to cope with the new regulations. Accordingly High Dust Selective Catalytic Reaction DeNOx retrofit project is in the pipeline, which will be a challenging task for the contractor and power plant operator.

Case 1: Scale problem with sea water disinfection linesMicroorganisms are found everywhere in the nature. There are both physical and chemical conditions that define a healthy environment for aquatic organisms. Gener-ally aquatic life prefers moderate tempera-ture and alkaline environment (not acidic). Microbial life affects many industrial pro-cesses. Organisms much larger than the

Stack •Flue gas

desulphurisationplant

•

Precipitator•

• Clean air fan

Turbine•

•Generator

• Transformer

High voltage• transmission line

Coal storagearea •

•Coal Bunker •

•Coal

crusher•

Boilerfeed pump

Furnace CondenserCooling water

• pump

Cooling water system

Seawater

Fluegasfan

Airheater

Boiler

Fig. 1. Functional diagram of the power plant.

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VGB PowerTech 3 l 2017 Chemistry for coal-fired power plants: Experiences and challenges

small unicellular types can also form de-posits in cooling systems, especially in once-through systems using surface wa-ters. These deposits are termed macrofoul-ing In addition to availability, macrofoul-ing costs include plugged lines, screens and traps, reduced water flow, under deposit corrosion, and impaired heat transfer lead-ing to higher turbine backpressure, dam-age to pumps impellers and high cost for manual cleaning during outages [1].In the power plant, there is once-through seawater cooling system. In order to pre-vent microbiological growth and macro-fouling, sodium hypochlorite is produced in the electro chlorination plant which is dosing 1,000 to 2,500 ppm active chlorine solution to the intake mouth and intake chamber continuously and intermittently (shock dosing). The cells employed for this purpose consist of an anode and a cathode without a separator or diaphragm. The pH of the electrolyte, which is maintained in the range of 10 to 12. The electrolytically generated chlorine reacts with sodium hy-droxide to form sodium hypochlorite. However, the hypochlorite ion, formed in the bulk, is easily reduced at the cathode to reform chloride. Therefore, only dilute so-lutions can be produced in the cell. Sodium hypochlorite is introduced into the seawa-ter intake of the plant where it also pre-vents fouling of the mechanical equipment, such as the seawater circulating pumps, bar screens and drum screens of the power plant. However, the salt content of pro-duced hypochlorite is very high and there had been serious scaling problems on dos-ing lines. Scaling issues was not foreseen during the design phase and commissioning period. After these periods, the first indication of the blockage was noticed following a rela-tively longer outage period (F i g u r e 2 ). The complaint was an unequal distribution of hypo solution among different lines and consequently the lines were thought to be blocked. Therefore the system was pressur-ised with water to open the lines, which was not successful. Finally, divers were asked to inspect the intake mouth, whether the chlorination system was still in func-tion. The inspection result shows that there was no flow to the intake mouth. Several methods had been tried to open the clogged

lines, but these methods were not success-ful and the piping had to be renewed. The blockages were found as calcium car-bonate. Therefore a proper type of antisca-lent was started to be dosed together with hypochlorite in order to prevent any more scaling. Moreover the hypo-chlorite solu-tion has a tendency for scaling. Therefore, before the long outages, the dosing lines have been flushed with sea water. With the help of these two simple preventive ac-tions, which were developed after the war-ranty period of the supplier, the lines have not been clogged again and they have been in operation without any problem for more than 10 years. Finally, during the planned outages, divers have been inspecting the lines and making mechanical cleaning if/when necessary.

Case 2: Effect of chlorine on ion exchange resinsThe power plant is producing its own ser-vice and demineralised water by desalina-tion of the sea water. Following a couple of mechanical filters the sea water is entering in the Multiple Effect Evaporator with Thermal Water Compression (MED-TVC) desalination units. There are three of them and each of them has a capacity of 1,750 m3 per day, and corresponding to 50 % of the water requirement of the power plant. The desalination units are powered by thermal energy, taken as bleed steam from the pow-er plants’ turbines, supplied at a pressure of 15 bar. Because the steam has already been used for generating power, its cost is mini-mised. The pressure energy of the steam is used in a thermal vapour compressor (TVC) to recycle and compress vapour in the sys-tem, which increases the heating energy available for the process. The water vapour generated from the last effect is condensed in the main system condenser cooled by sea water. The final conductivity of the desali-nated water is around 1 µS/cm. Following the desalination, the desalinated water is fed into the mix-bed resins for demineralisation. There are two mixed bed tanks are in operation, which have 800 m3 daily water production capacities. The con-ductivity of the demineralised water was around 0.05 µS/cm. After 3 years of operation, gradual break-ing and opacity were observed in cation and anion resins, even though, the resin was guaranteed by the manufacturer, at least 10 years of operation without any problem (F i g u r e 3 ). Therefore the resin sample was sent to the manufacturer for analysis. Afterwards it was reported that, total exchange capacity of the cations de-creased to 0.94 from the reference value of 1.3. The 30 % chemical degradation was reported as the consequence of the pres-ence of high free chlorine. The reason of the high free chlorine was found as the sodium hypochlorite solution

which has been dosed into sea water intake lines in order to prevent macro fouling. The sodium hypochlorite solution directly comes to desalination unit, and passes through evaporator effects and reaches to ion exchange resins. The contractor com-panies of the electro chlorination, desali-nation and demineralisation units were different. Therefore, this simple but at the same time very important detail was un-derestimated. After the incident, as a rem-edy, the mix bed resins were completely changed. And as a preventive action sodi-um meta bisulphate was started to be dosed at the upstream of the evaporators to remove free chlorine in order to protect the new resin.

Na2S2O5 +H2O 2NaHSO3

NaHSO3 + HOCl HCl + NaHSO4

Case 3: Frequent tube leaks in feed water pre-heatersThe steam-water cycle has been treated with the oxygenated treatment (OT). Therefore oxygen has been dosed into the condensate and the feed water system to maintain the desired oxygen level and am-monia will be dosed into the condensate system in order to establish the required pH value. Oxygen in pure water promotes the formation of very stable Hematite pro-tective layers.OT will be applied during undisturbed op-eration. Normally, all the values have been under control and in accordance with the VGB guidelines and OEM’s recommenda-tions (Ta b l e 1 ).Since 2003, the first commercial operation year, until 2013 there haven’t been any problems and leakages in the High Pres-sure (HP) feed water heaters named A6 and A7. However the first leakage was no-ticed in August 2013 at the A6 pre-heater of unit 20 and time by time tube leakages are ongoing up to now. When the tubes are ruptured the HP heat exchangers have to be by-passed and after cooling down, then the vacuum test can be performed and ruptured tubes are blocked. This is a difficult and time consuming job. Moreover by-passing the heat exchangers are decreasing the efficiency of the power plant (F i g u r e 4 ).Fig. 2. Blockage of the NaOCl dosing line.

Fig. 3. The microscopic view of the resins: Magnification 12.5x.

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Chemistry for coal-fired power plants: Experiences and challenges VGB PowerTech 3 l 2017

Therefore some experts were consulted and as per their recommendations, the dis-solved oxygen (DO) values were checked. Because, lower DO levels could propagate the corrosion and consequently results in tube leakages. Normally DO levels of the extracted steam and feed water had been measured only at the upstream of the A6 preheater and they were all within the ac-ceptable range and more or less same as the set values which were in between 80 to 120 ppb. Afterwards, it was decided to check the DO in the condensate lines of the pre-heaters and new sampling lines were installed and, it was found out that the DO values at the condensate lines of the A6 and A7 pre-heaters were far below the set value. After some field investigation, it was seen that the vent valves on the shell side of heat ex-changers were kept open since from the commissioning period, which normally had to be kept  in a closed position. Then the vent valves were closed and the O2 set value was increased to 200 ppb in order to saturate the system and form the Hema-tite  layers in  the missing places. After a

couple of weeks the dissolved O2 value has started to  increase and after 6 weeks the value became same as the set O2 value at the condensate lines of the A6 and A7 pre-heaters.

Both units of the PP have been working un-der the same conditions and the same re-medial actions were repeated. However the DO values in the condensate line of the HP pre-heater – A7 of U20 couldn’t be in-creased to the desired levels (F i g u r e 5 ). Although the O2 levels have already be-come the normal values, there are still some tube leakages in the heat exchangers. Which could be because of the reduced thickness of tubes, which has been a conse-quence of erosion/corrosion (F i g u r e 6 ). These are important heat exchangers in or-der to keep the efficiency of the PP at the desired levels. Therefore the A6 pre-heat-ers will be renewed, albeit earlier than the expectations. That will be an expensive and difficult remedial action because of the huge dimensions of the heat exchangers and the lack of space to manoeuvre and re-place the new ones. However, in order to protect the new ones following preventive actions will be carried on;Additional O2 make-up lines will be in-stalled in the shell side of the heaters so that in case of facing with low levels of DO make-up O2 can be supplied to the heaters to form or keep the Hematite layersThe H2 levels will be measured frequently, which is an early warning for corrosion as per the Schikorr reaction.

3 Fe + 4 H2O Fe3O4 + 4 H2

As a summary; even though the recom-mended parameters had been all in accord-ance with the VGB guidelines and the rec-ommendations of the OEM, a simple vent valve which might have been forgotten in open position have affected the chemical conditioning adversely and ended up in an expensive and difficult remedial action. Therefore the operators of the PPs should follow the developments in the area of PP chemistry and continue questioning them-selves whether the PP chemistry in their power plant is acceptable and adequate.

Tab. 1. Water steam cycle target values (VGB-R 450 Le. Guidelines for Feedwater, Boiler water and Steam Quality for Power Plants / Industrial Plants).

ParameterFeedwater Steam

OT AT OT & AT

Cation conductivity at 25 °Cdownstream of a strongacidic cation exchanger,continuously measured atthe sampling rack (CC) (μS/cm)

<0.2 <0.2 <0.2

pH at 25 °C 8.0 to 9.0(Target: 8.5)

9.0 to 9.3

Total iron μg/l <20 <20 <20

Silica μg/l <20 <20 <20

Oxygen μg/l 30 to 150(Target: 50 to 80) <20*

* When the CC increases then the oxygen concentration in the feedwater should be less than 10 µg/l

Fig. 4. Screen shot of the water-steam cycle of the DCS system.

Time

Diss

olve

d O

2 in

ppb

UNIT 10 and U20 DO Levels250

200

150

100

50

0Start 1st 2nd 3rd 4th 5th 6th 7th 8th week week week week week week week week

Set Value

U10_A6

U10_A7

U20_A6

U20_A7

Fig. 5. The increase of dissolved oxygen levels at the downstream of HP preheaters.

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VGB PowerTech 3 l 2017 Chemistry for coal-fired power plants: Experiences and challenges

Case 4: Optimisation of Wastewater Treatment (WWT) of the Flue Gas Desulfurisation (FGD) unitThe power plant has a limestone slurry, forced oxidation and wet (seawater) FGD unit. In order to treat the waste water com-ing from the dewatering process of gyp-sum, a typical chemical treatment plant was built (F i g u r e 7 ). Firstly the pH of the waste water is arranged by caustic soda. Then FeCl3 is dosed for the settling of met-als as metal oxide. Afterwards, pH is ar-ranged again and organasulfide dosing was planned for settling of the heavy metals. Finally polyelectrolyte is dosed and waste-water is directed to the clarifier for settling of the sludge. The clarified water is over-flowing at the clarifier and the sludge is ac-cumulated at the bottom of the clarifier. Sludge is filter pressed and stored as haz-ardous waste in the licensed landfilling area, where there is impermeable layers isolating the sludge and its eluate from the nature.

After the commissioning period, the opera-tion had been continued as it was designed and recommended by the OEM. At that time, it was decided to check whether the chemicals are suitable and good enough for the treatment. The most expensive chemical was the organosulfide, which is

mainly necessary to settle down the oxi-dised mercury and lead. In a typical power plant the oxidation of the elemental mer-cury, which is coming with the coal, is tak-ing place in the catalyst of the Selective Catalyst Reaction (SCR) DeNOx units. However, there is not a DeNOx system in the Isken PP and, probably, during the de-sign of the WWTP, this issue had not been taken into consideration and organo-sulfid had been dosed, albeit it was not nec-essary.

Moreover, there was no regulation for lim-iting mercury emission in the discharge water of the power plants (Ta b l e 2 ). However, in order to be on the safe side, German regulations were accepted as the limits for the PP, and accordingly heavy metal concentrations in discharge water were measured. As per the German regula-tions, which were valid at that time, the Hg content must be lower than 50 μg/L and the lead content must be lower than 100 μg/L in the effluent of the FGD WWT plants. Lastly, the chemical dosing had been decreased step by step and finally it was stopped. As it can be seen in Ta b l e 3 ; the outlet parameters haven’t changed so much and the results were all below the limits, even in the inlet water. Seemingly NaOH and FeCl3 dosing were enough to re-duce the concentrations of the heavy met-als as well. It is also known that, organosulfide is not only necessary for the quality of the dis-charge water but also important for the el-uate analysis of the sludge. Accordingly the eluate of the sludge has been periodically tested, by the third party independent lab-oratories and found out that there is not a difference in the heavy metal content be-tween dosing and not dosing the organo-sulfide. Finally, it was decided to stop organophos-phate dosage, which has resulted in a con-siderable saving for the PP and eliminates the risk of an unnecessary chemical either from environmental or work safety point of views. However, it is known that when the PP will be retrofitted with the SCR DeNOx unit, then the elemental mercury will be oxidised and it will be removed in the FGD processes. Therefore the dosing station and storage tank is still remaining in case of lowering the legal limits, coal/limestone type change or any other disturbance which can affect the outlet water (like De-NOx installation). Cancelling the unneces-sary organosulfide dosing was the remedi-al action, however the root cause was lack  of information exchange during the design phase. Because FGD WWTP was de-

Fig. 6. The corrosion indication of the tubes and the shots of the tube rupture.

Fig. 7. The screen shot of the wastewater system of the wet FGD unit.

Tab. 2. The Hg and Pb concentrations at varying amounts of organosulfide dosage.

Sample point Organosulfide dosage Hg (μg/L) Pb (μg/L)

FGD WWTP – Inlet -- 39 70

FGD WWTP – Outlet

Full 0,4 <10

3/4 1,1 <10

1/2 0,9 <10

1/4 1,0 <10

No dosage 3,4 <10

Tab. 3. FGD WWTP Sludge – Eluate analysis to determine the heavy metal content.

Sample point Organosulfide dosage Eluate analysis

Hg (µg/L) Pb (µg/L)

FGD WWTP – SludgeFull <3 <10

<3 <10

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Chemistry for coal-fired power plants: Experiences and challenges VGB PowerTech 3 l 2017

signedand constructed properly by a repu-table subcontractor however, seemingly they didn’t have detailed information about the systems downstream of the FGD WWTP and made a standard design necessary to cope with oxidised mercury as well, which hasn’t been an issue for the Isken PP yet.

The challenges aheadIsken PP is obliged to meet the new emis-sion limits introduced by the Regulation concerning the Control of Air Pollution

arising from Industrial Activities and thus complete construction and integration of the DeNOx investments until 08.06.2019 (Ta b l e 4 )The designed NOX emission of the PP has been 650 mg/nm3 and with the help of low NOX the average NOX emission is around 560 to 600 mg/nm3. After the detailed in-vestigation and comparing the different technologies, High Dust SCR was selected as the technology of the DeNOx unit. The main motivation was, it is a well proven and

reliable technology for our size of PP. More-over the fly ash coming out of the PP is a by-product and very low ammonia slip re-quired and/or accepted by the customers. The most challenging task will be the lim-ited time to retrofit the unit because the DeNOx should be ready by the 08.06.2019 and up to that time only the yearly planned outages will be given to the contractor to dismantle the ducts and install the SCR catalyst reactor (F i g u r e 8 ).

Summary and ResultsAll major units of the power plant are de-signed and built by different companies like a giant Lego toy. The technology pro-viders are mostly reputable and experi-enced ones and often supply the state of the art technologies. However, they are mostly lacking the overall view and the processes that are placed on the upstream and/or downstream may affect theirs ad-versely. These issues may not be seen im-mediately during the commissioning and/or warranty period. However, in the mid–long term, power plant operators are fac-ing with different kind of problems and developing their own remedies. Therefore a close cooperation is recommended be-tween the operators and the technology providers. Additionally, the power production from coal is fading out in Europe. However, there is still great interest of the investors to build and operate Coal Fired PP’s in Tur-key, South Eastern Europe and MENA re-gion. Moreover there will be numerous retrofit projects soon, especially in the area environmental areas, in order to cope with the new and stricter e(i)missions regula-tions. These will be the new challenges for the power plants to overcome and opportu-nities for the experts and the technology providers to support them.

ReferencesKemmer, F. N. (1987). The Nalco Water Hand-

book. U.S.: R.R Donnelley & Sons Co. l

Tab. 4. New Turkish emission limits as per the regulation Concerning the Control of Air Pollution Arising from Industrial Activities.

EmissionLarge Combustion Plant Regulation

Before After

NOx ≥50 MWth 800 mg/Nm3

Plants already in operation* New plants

50 – 500 MWth

600 mg/Nm3

50 – 100 MWth

400 mg/Nm3

>500 MWth

200 mg/Nm3

>100 MWth

200 mg/Nm3

* There is a transition period for the power plants already in operation. The new limits will be valid from the 08.06.2019 as noticed in the Large Combustion Plant Regulation.

Secondarystructures

Inlet Gas Ducts(Equipment)

SCR DeNOxReactors

(Equipment)

Secondarystructures

Secondarystructures

Outlet Gas Ducts(Equipment)

Outlet Gas Ducts(Equipment)

Trussed planeframe

Trussedbeam

Central trusstower

Trussed planeframe

Trussedbeam

Fig. 8. The Schematic view of the High Dust SCR DeNOX unit.

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