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A PROPOSED DOJ PROJECT FOR FTA ON CHEMICAL CLEANING OF BOILER

CARRIED OUT BY:MRINAL KANTI GHOSH

(Employee no. 103085)

RITWICK GOSWAMI
(Employee no. 103086)

Under the guidance of

Mr. B L SHARMA
DEPUTY MANAGER (CHEMISTRY) VINDHYACHAL SUPER THERMAL POWER STATION

CERTIFICATE
this is to certify that the project entitled chemical cleaning of boiler submitted by Mrinal Kanti Ghosh (Emp. No: 103085) and Ritwick Goswami (Emp. No:103085)in partial fulfillment for the final term appraisal (fta), as a part of doj is record of trainees own work and it was carried out under my supervision.

(B L SHARMA)

DEPUTY MANAGER (CHEMISTRY) VSTPP, NTPC LIMITED VINDHYANAGAR

OUR VISION
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OUR CORE VALUES BE COMMITTED

B BUSINESS ETHICS E ENVIRONMENTALLY & ECONOMICALLY SUSTAINABLE C CUSTOMER FOCUS O ORGANIZATIONAL & PROFESSIONAL PRIDE M MUTUAL RESPECT AND TRUST M MOTIVATING SELF & OTHERS I INNOVATION & SPEED T TOTAL QUALITY FOR EXCELLENCE T TRANSPARENT & RESPECTED ORGANISATION E ENTERPRISING D DEVOTED

HR VISION
TO ENABLE OUR PEOPLE TO BE A FAMILY OF COMMITTED WORLD CLASS PROFESSIONALS, MAKING NTPC A LEARNING ORGANIZATION

ABSTRACT
Chemical Cleaning of Boiler

The purpose of preoperational cleaning is to remove construction contaminants which could cause operating problems or even failure during initial operation. Preoperational contaminants include mill scale, weld slag, corrosion products, oil, grease, debris and dirt, temporary protective coatings, and other contaminants remaining after fabrication and erection of the unit. Mill scale, a dense magnetite layer produced on steel surfaces during fabrication, is subject to fracture and erosion during system operation. Because the exposed metal is anodic to the mill scale, these surface cracks are potential corrosion sites. In addition, mill scale and weld scale can become deposit accumulation sites and may cause damage if they break loose. Removal of metallic scale and corrosion products generally requires chemical cleaning. So it is necessary to clean and passivate the internal surfaces of the steam generating portions (water touched surfaces) and heating surface (Economizer). This will render these surfaces free from mill scale and other deposits and form a uniform and smooth protective layer of magnetite. With this protective layer, the generating surfaces become passive to generate adequate negative potential under the operating pH to resist corrosion.

Outline of chemical cleaning Chemical cleaning of boiler is carried out in several steps which are as follows I. DM water flushing: To remove loose dirt, sand, water soluble ingredients those are present in the circuit. This is actually done by mere filling and dumping method. Boiler drum is filled with water through economizer and superheaters by using circulating pump. A recirculation flow is established through boiler water-steam circuit. Circulation is continued till the conductivity of inlet and outlet water become same. Water is then dumped. Boiler refilling and dumping is continued till the conductivity of washing water levels with that of fresh filtered water. Alkali Boil Out: Alkali flushing is carried out to remove oil and grease, if any, present in the boiler drum, waterwalls, downcomers, and economizer. Requisite quantities of Tri-sodium phosphate (400 kg.) and Disodium hydrogen phosphate are added to the mixing tank along with DM water and solution is thoroughly mixed by recirculation so that final solution in the boiler contains 0.1% TSP and 0.05% DSP. Boiler is lit up as per O&M instructions and temperature is gradually raised

II.

III.

IV.

V.

to 130 - 140C. Boiler is then tripped. Fans and one CC pump is kept running. Boiler is tripped when the temperature comes down to 95C, CC pump is stopped and boiler water is drained to the plant water disposal system. Effluent is diluted with plenty of service water. Hot Water Rinse: After complete draining, Boiler is refilled with DM water. Then boiler is lit up and temperature is raise to 130-140 C After reaching the desired temperature boiler is tripped and fans are kept running with CC Pumps are operated on rotation. Running CC Pump is stopped after 30 minutes and boiler is drained in HOT condition. The effluent is diluted with service water so as to bring pH and PO4 in the effluent below 7.5 and 10 ppm respectively. Cold Water Rinse: Cold water rinsing is done by fill and dump method. pH is monitored during draining of cold water rinse stage. The rinsing operation is continued until the pH of drained water and the inlet water for rinsing become equal. During this step all the CC pumps are run one by one for proper rinsing. All sampling and blow down lines are flushed. Acid cleaning &Passivation: Acid cleaning of boiler steam and water circuit covering economizer, water walls, boiler drum and excluding superheaters, reheaters and associated piping will be

carried out to remove iron oxides, mill scales and silicates from the system. Acid cleaning will be followed by passivation, so that the uniform protective coating of magnetite is formed on the metal surface so that further corrosion or oxidation damage to metal surface is prevented. Acid cleaning process will be carried out in following stages Stage 1: Acid washing Stage 2: DM water rinsing after acid washing Stage 3: Citric acid rinsing Stage 4: DM water rinsing Stage 5: Neutralizing with Sodium Carbonate Stage 6: Passivation 1st stage Stage 7: Inspection Stage 8: Passivation 2nd stage According to the conventional method we generally use 4-5% HCl solution in the 1st step of acid cleaning. But now a days HCl is replaced by EDTA as it is more advantageous to use EDTA instead of HCl. In the commissioning of unit 11 in VSTPP we also use EDTA instead of HCl for acid cleaning purpose.

EDTA and Its Application in Chemical Cleaning

EDTA or Ethylene Diamine Tetra acetic Acid is a hexadentate strong chelating agent which has an extensive potential to form highly stable water soluble chelate complexes with transition metal ions present in boiler such as of Iron and Copper etc. This special property of EDTA is used in the chemical cleaning of boiler.

EDTA

Iron EDTA complex

By forming this type of highly stable water soluble complexes with metal and metal oxide scales EDTA removes them from boiler.

EDTA Pickling & its Reaction

After EDTA cleaning there is no need of citric acid rinsing of boiler. So by following EDTA method of acid cleaning we can save both our time and chemical also. After EDTA cleaning of boiler during Passivation stage a protective layer of magnetite is formed in the water touched metal surface of steam generator. Magnetite layer which is a combination of FeO and Fe2O3acts as a coherent media that stops further corrosion of the base metal. The detailed procedure, service requirements and safety precautions of EDTA cleaning, followed during commissioning of unit 11 at VSTPP is discussed below.

Service Requirements for EDTA Cleaning 1. 3200 m3 of DM water is expected to be consumed for the entire chemical cleaning process. Prior to the commencement of chemical cleaning all the DM water storage tank should be kept full and DM plant should be ready to meet additional requirement of DM water, if any. At any time during acid cleaning, a minimum of two boiler volumes of DM water should be available in ready stock to facilitate rapid flushing of the system in the event of chemistry upset. 2. Availability of required quantity of chemicals:

Name of Chemicals:
Ammoniated EDTA (40 % wt./wt. as active EDTA, (ammoniated soln. pH = 9.0 - 9.8, Density : 1.18 ) Ammonia solution (20 % Min as NH3, Sp. Gr: 0.91) Hydrazine hydrate [80 % Min Conc.]

Quantity
40tons 1800 Lits. 1800 Lits.

BHELMAX 690Kg BHELSOL 690 Liters 3. A temporary drum water level gauge glass is made available. 4. Availability of temporary pump sets for boiler filling. 5. Availability of HT/LT power supply and control supply.

6. 7. 8. 9.

Availability of instrument and service air. Availability of Chemist & Express Lab for testing during the process. Availability of flood lights, telephone and walkie-talkie. Availability of compressed air facility and suitable perforated Carbon steel/polythene tubing arrangement for neutralizing pit.

Safety Precautions
1. Sufficient number of following Personal Protective Equipment should be available. i. Gum Boots (various sizes) ii. Rubber made hand gloves iii. Rubber or polythene aprons iv. Helmets v. Safety goggles of plain glass vi. Face mask (transparent plastic) 2. First aid box (containing dilute NH4OH, 50% Na2CO3, eye lotion, bandages, Tincher of iodine, cotton, Burnol etc.) 3. Ample supply of water for flushing and washing should be available at all possible points of discharge, spillage or escape of chemicals.

4. Adequate provisions of eye wash bottles, located conventionally at places where discharge, spillage or escape of chemicals can occur, should be made for emergency treatment of eye. 5. Arrangement of Safety shower should be done near chemical handling area. 6. Protecting clothing and apparatus required for emergency use should be available near chemical cleaning area. 7. Near the chemical handling area there should be a suitable first aid room with outside telephone facility. FIRST AID MEASURES: 1. If chemical splashes on eye it should be immediately washed with plenty of water. To make the washing effective the eyelids must be kept open. If an eye wash bottle is used, the jet should not be directed to the front of the eye, instead it should be directed from the side so that flow is over the surface of the eye. Washing should be done for 5-10 minutes after which the affected person should be taken to the first aid room. Irrigation should be continued in the first aid room. After thorough irrigation the eye should be covered with a pad. Then the victim should be referred for medical opinion. 2. In case chemical splashes on skin the affected area should be washed thoroughly avoiding spread of chemicals on the face and eyes.

GENERAL PLANT SAFETY MEASURES: 1. The temporary connection to boiler should be of good quality and are hydraulically tested at 12 kg/sq. cm. 2. Test area should be cordoned off and entry of unauthorized person should be prohibited and whenever any inspection is made during the cleaning process the location should be adequately ventilated. 3. If the light up after completion of chemical cleaning could not be done within 4 weeks then the system should be suitably preserved. 4. Temperature limitation specified for various steps should not be exceeded.

Other necessary arrangements: Provision is made for measurement of temperature. Total 6 nos. of thermocouples are used for the measurement of water wall tube metal temperature and 2 nos. of thermocouples for economizer tube metal temperature. Sampling during the process: To get representative samples of the process solution sampling points with sample coolers are provided at the following locations: CC pump suction (with temporary cooler), the sampling line from cooler outlet is extended to zero meter. Another sampling point is provided from bottom ring header through temporary cooler, the sampling line from cooler outlet is extended to zero meters. Boiler waterwalls test tube coupons are securely placed at two ends inside the drum and in the bottom ring drum to see the effectiveness of the cleaning. Proper effluent treatment arrangement is made available. Inhibitor efficiency test should be done before the start of chemical cleaning. Acceptable corrosion rate should be less than0.1 mg/sq.cm/hr.

Minimum Operational Requirements 1. Readiness of the following including their protections, interlocks, measurements, alarms and annunciations: One ID Fan One FD Fan One secondary air pre-heater with Soot Blower All the CC pumps Light oil firing system FSSS SADC Scanner Air System Boiler Fill System Measurements, alarms, annunciations, pertaining to secondary air, flue gas, feed water, steam and boiler metal temperature CC pumps purge line with continuous water supply at 15 kg/cm2 for purging of CC pumps. One fill pump on emergency supply to continue

2. Free expansions of the furnace and duct and provision of expansion marker. 3. Blow down system of boiler. 4. Proper drainage system of boiler area. 5. Mechanical readiness with air in leak test of at least two passes of ESP. 6. Adequate quantity of light oil & readiness of light oil handling system. 7. Temporary sampling system along with the cooling arrangement for collecting samples from bottom ring header and CC pump casing during chemical cleaning. 8. Water and steam systems. 9. Air and flue gas system. 10.Effluent treatment pit to hold approximately 800 m3 of effluent. 11.Drainage line to effluent treatment and bypass for direct draining of mass flushing water. 12.DG set, DG switchgear, emergency switch gear and availability of emergency supplies for scanner air fan and emergency lighting. 13.UPS 14.Firefighting system of concerned equipments 15.Equipment cooling water system. 16.Adequate quantity of DM water. 17.Adequate capacity of instrument air and service air system.

18.Availability of test coupons and their fixing arrangements. 19.Emergency operating instructions viz. AC power failure, DC power failure, APH fire etc. 20.Adequate lighting in operating areas. 21.Public address system at all operating locations, including telephone & walkie-talkies at all working areas. 22.Readiness of staircases, hand railings and platforms at vulnerable areas. 23.Personal protective equipments. 24.Easy access and approaches to all the operating equipments. 25.SH temperature measurement for continuous monitoring in the control room. 26.Data logging printer at control room to record the boiler parameters periodically. 27.Proper isolation of Air Pre Heater not in service must be ensured. Alternatively, the same should be kept running. 28.Availability of APH soot blowers, Fire detection and fire protection system, rotor stoppage alarm.

EDTA CLEANING PROCESS: 40 Cu. m of DM water is drawn in mixing tank & Temp. Chemical fill pump is started and system is put into recirculation. Ammoniated EDTA (40% wt. /wt.) soln. is transferred to the mixing tank till the EDTA conc. reaches around 3 1 % by wt. Required quantity of Hydrazine hydrate and inhibitors are also added. Ammonia is added if required to adjust pH = 9.0 9.8 With this one batch of EDTA chemical soln. is ready for filling into the boiler. The quantities of various chemicals that are mixed per batch of 40 cu. m is given below: Ammoniated EDTA (40%) BHELMAX BHELSOL N2H4.H2O (80 %) : : : : 3-4 m3 60 kg. 60 lit. 60 lit.

Solution is filled into the boiler through low point drain header with the help of temporary chemical fill pump. The boiler is filled up to +200mm from

the normal working level of the drum. The middle CC pump is operated for 30 minutes to mix the chemical solutions thoroughly. Boiler water sample is then checked. The cleaning solution is quite harmless so there is no time limitation for filling the boiler and retaining the solution inside the boiler. The composition of the filling solution should be as follows: EDTA content Hydrazine BHEL MAX (inhibitor) BHEL SOL (inhibitor) pH : : : : : 3 1 % (w/v) 1000 ppm (min) 0.15-0.2% w/v 0.15-0.2% v/v4 9.0 9.8

The boiler is lit up with minimum firing rate and the time at which temperature is reached 110C is noted. Once the boiler water temperature reached 140 145 C, the firing rate is controlled in such a way that the boiler water temperature is maintained at 140145 C for a minimum period of 4 hours.
Boiler is then tripped but CC pump is continued in operation. ID and FD fans are allowed to run to bring down the boiler water temperature.
Boiler water temperature is allowed to come down slowly because minimum EDTA contact period of 6 hrs. with temperature above 110C is desirable.

Samples are taken every 30 minutes from the sampling points when the temperature in the system reaches 110 C and analysed for pH, EDTA concentration and iron content. When the temperature comes down to 95C, the running CC pump is stopped and the system is drained completely in hot condition in the designated effluent pit by opening all the drain valves. Process Completion: Cleaning process is to be continued till iron concentration in three consecutive samples show equilibrium states. When the iron in the cleaning solution is constant, it indicates that all the oxides have been dissolved. However a minimum EDTA contact period of 6 hours from the time of attaining the required temperature 110C preferably be allowed. Treated DM Water Rinsing: A solution of hydrazine (0.01-0.02%) and ammonia with DM water is prepared (pH 9.5 9.8) and the system is filled with this solution. Boiler is fired and temperature raised to 120C. Boiler is tripped and allowed to cool. When the temperature comes down to 95C, the solution is drained. Caution: If the iron concentration values do not level out and attain equilibrium status, regardless of analytical result, the EDTA contact period with temperature above 110C should not be exceed 8 hours.

Inspection Drum manhole is opened for removal of coupons. Lower Drum manholes are opened for inspection & Cleaned.
Chemical Cleaning Waste Treatment and Disposal

Treatment and disposal of the waste and effluents of the chemical cleaning process shall comply with the requirements/stipulations of state pollution control board. Hot DM water after flushing shall be drained into plant normal drain. The organic spent EDTA chemical solution after the cleaning process is drained into the neutralizing pit. The pH of the effluent will be in the range of 8.5-9.0 and hence no treatment for pH adjustment is required as it would meet the pH requirement for disposal. Compressed air is used to destroy the residual Hydrazine and organics. The effluent shall be disposed after aeration for 10 days, as per state pollution control board norms suitably. (The organic chemical is completely bio degradable)

EDTA cleaning results:

Advantages of EDTA cleaning in comparison with HCl cleaning:

HCl Cleaning Process: HCl cleaning the process is practiced as follows: Alkali Boil-out: The boiler (steam generating surfaces and economizer ) is filled with an alkaline solution containing 500 ppm of di-sodium phosphate dodecahydrate, and 1000 ppm of Tri sodium phosphate dodecahydrate and then fired to raise the pressure to 40 kg/ cm , following the specified operational procedures. Hot Water Flushing: After complete draining, Boiler is refilled with DM water. Then boiler is lit up and temperature is raise to 130-140 C. After reaching the desired temperature boiler is tripped and fans are kept running with CC Pumps are operated on rotation. Running CC Pump is stopped after 30 minutes and boiler is drained in HOT condition. The effluent is diluted with service water so as to bring pH and PO4 in the effluent below 7.5 and 10 ppm respectively. Cold Water Rinsing: Cold water rinsing is done by fill and dump method. pH is monitored during draining of cold water rinse stage. The rinsing operation is continued until the pH of drained water and the inlet water for rinsing become equal. During this step all the CC pumps are
2

run one by one for proper rinsing. All sampling and blow down lines are flushed. After completion of the above process boiler becomes ready for Acid Cleaning using HCl; the various steps of HCl cleaning are HCl Cleaning: Acid cleaning is carried out by adopting soaking technique, using hydrochloric acid of 5% + 1%, 0.2% V/V inhibitor Rodine 213 Special and 0.25% ammonium bi-fluoride. DM Water Rinsing: After draining the acid solution, boiler is filled with DM water heated to 60C 65C. the drum vent valves are Carefully operated to maintain 0.5 kg/ cm2 Nitrogen pressure in the drum. Water is filled up to the centre of the gauge glass. Further the level in the drum raised by 100 mm, by back flushing the super-heaters with treated water. Boiler circulating water pump is run till the uniform concentrations of acid and iron are attained in the system as indicated by analysis of the sample taken. Analysis of the sample done for pH. The pH of the DM rinse should not be allowed to go above 4.0. After getting satisfactory analytical results boiler is drained under nitrogen capping. Citric Acid Rinsing: a solution of ammoniated citric acid with concentration of 0.2% acid is filled into the boiler keeping the boiler water temperature at 60-65C. A uniform strength of 0.2% acid should be maintained in the water taken into the boiler. pH of the final solution entering the boiler should be kept between 3.5-4. The boiler

circulation pump is run for 5 minutes at an interval of every 30 minutes and sample from Boiler circulating pump discharge after stoppage of Boiler circulating pump is collected and Checked for acid % and iron concentration. When iron concentration attains a steady state value for 3 consecutive readings, citric acid rinsing is declared complete. . In any case it should not be declared complete in less than 4 hours or more than 5 hours. Boiler is drained under nitrogen capping. DM Water Rinsing: After draining the citric acid solution, boiler is filled with DM water heated to 60C 65C. Water is filled in drum up to + 100 mm mark. Boiler circulating water pump is operated for 5 minutes. Then pump Stopped and boiler is drained under nitrogen capping. Neutralization: This process is employed to neutralize any acid / acidic pocket remaining in the system and also to mildly passivate the acid pickled surface. This prepares the base for achieving an effective final passivation. The neutralizing solution is prepared by mixing required quantities of di-sodium phosphate dodeca hydrate and trisodium phosphate dodeca hydrate to get a concentration of 0.1% and 0.2% respectively. Boiler is filled with neutralizing soln. along with DM water, under the nitrogen capping and uniform concentration is maintained throughout the filling period. Boiler is fired and the pressure is gradually raised to 10 kg. / cm2. Pressure is hold at 10 kg/cm2 for 6 hours. After 6 hours boiler is tripped and is allowed to

cool naturally and subsequently boiler is drained. While draining, super-heaters are back-flushed the with DM water conditioned with hydrazine and ammonia. System is allowed to aerate.

Passivation (1st and 2nd Stage): Passivation is done to form a protective magnetite coating on the steam generating and water touched surfaces that were exposed to the pickling process. For this a blended solution of hydrazine and ammonia with calculated quantities is mixed in order to finally achieve a minimum residual amount of 200 ppm hydrazine and a solution pH of 10.0, when filled in the boiler. Boiler is filled with passivating solution along with DM water and boiler water circulating pumps are started and boiler is fired at a slow rate. Drum pressure raised to 40 kg / cm2 and is held for 24 hrs. Residual hydrazine content of 25 ppm & a solution pH 10.0 is maintained in the feed water being fed into the boiler during the entire passivation operation. After 24 hours of operation, boiler is tripped and allows it to cool slowly. Boiler circulating water pumps are kept in service and pumps are shut down when the metal temperature drops to 950 C. Boiler is drained under atmospheric pressure and system is allowed to aerate.

Disadvantages of HCl Cleaning Process

More no. of chemicals required. Lot of temporary piping required. Auxiliary steam required in huge quantity. DM water and fuel consumption is very high. Nitrogen gas in huge volume & its piping system required. Process handling is difficult and hazardous due to corrosive nature of chemicals. Large cycle time (17 days). Effluent treatment & disposal requires huge investments.

Advantages of EDTA cleaning Process advantages:

Shorter cycle time (5 days). Less temporary piping required. Auxiliary steam is not required. Less number of chemicals required. DM water and fuel consumption is less. Use of Nitrogen & its system is eliminated. Ease of handling. Effluent treatment is much easy and also much less expensive.
Technological & Other advantages:

EDTA is a strong chelating agent with transition metal ions, so it is an efficient metal remover. Use of EDTA for acid cleaning process is economical in comparison to the use of HCl.

Conclusion
Efficient cleaning and passivation of boiler internal Surfaces both are done at single step by opting EDTA cleaning process. Assurance of good quality inhibitor (i.e. BHELSOL & BHELMAX) for EDTA cleaning as this is provided by OEM. EDTA cleaning has obvious advantages over conventional HCl cleaning with minimum effect on the base metal surface.

Comparison of EDTA Cleaning With HCl Cleaning

EDTA Cleaning 1. EDTA Cleaning Process: Alkali Boil-out Hot Water Flushing Cold Water Rinsing EDTA Cleaning DM Water Rinsing Passivation HCl Cleaning 1. HCl Cleaning Process : Alkali Boil-out Hot Water Flushing Cold Water Rinsing HCl Cleaning DM Water Rinsing Citric Acid Rinsing DM Water Rinsing Neutralization Passivation (1st and 2nd Stage) Shorter cycle time (5 days). 2. Large cycle time (17 days). Less temporary piping required. 3. Lot of temporary piping required. Auxiliary steam is not required. 4. Auxiliary steam required in huge Less number of chemicals quantity. required. 5. More no. of chemicals required. DM water and fuel consumption 6. DM water and fuel consumption is less. is very high. Use of Nitrogen & its system is 7. Nitrogen gas in huge volume & its eliminated. piping system required. Ease of handling. 8. Process handling is difficult and hazardous due to corrosive nature of chemicals. Effluent treatment is much easy. 9. Effluent treatment & disposal requires huge investments.

2. 3. 4. 5. 6. 7. 8.

9.