CHEMICAL CLEANING OF BOILER

I 1. 2. 3. 4. NEED FOR PRECOMMISSIONING CLEANING: High purity of steam depends on the cleanliness of the water side of the boiler. During erection at site components undergo both physical changes i.e. rust due to atmospheric corrosion and formation of oxides of iron. The other common impurities found are lubricants, greases silica in the form of silicates etc. Non uniform surface is susceptible to severe pitting corrosion.

II NEED FOR OPERATIONAL CHEMICAL CLEANING: 1. Some percentage of insoluble can be expected to deposit on boiler inside surface. 2. Pre boiler corrosion due to oxygen, ammonia deposits on boiler surface. 3. Deposits of calcium and magnesium may be present in unit that experience condenser leakage. 4. Internal boiler tube deposits are a principal factor controlling tube metal temperature resulting overheating and corrosion based tube failures. III CRITERIA : Principal criterion for determining the need to clean boilers is specific deposit weight limits and its relationship with unit cleanliness is given below for high pressure boilers. Internal Deposit Weight Unit Cleanliness Less than 15 mg/cm2 Clean surface 15 to 40 mg/cm2 Moderately dirty More than 40 mg/cm2 Very dirty surface All values are as measured on the furnace side of tube samples and include soft and hard deposits. Note : For all practical purpose 1 mg/cm2 = 1 g/ft2 This limit has proven effective in avoiding overheating and corrosion problems in a large number of utility boilers. 1. Clean boiler - It does not require chemical cleaning and can be safely operated until the next scheduled inspection. 2. Moderately dirty boiler - A chemical cleaning should be planned as part of the next scheduled outage. 3. Very dirty boiler - Vulnerable to corrosion and overheating and continued operation will quickly produce tube failure. IV TIME INTERVAL: Industry experience indicate that a four year interval between chemical cleaning for high pressure boilers has been recommended as the frequency needed to assure long term boiler integrity even though boiler has operated without excursion in cycle water Chemistry. V SOLVENT SELECTION: A strong solvent formulation may be desired depending on the variability of deposition in past tube sampling. The four primary criteria for selection of a solvent system are the 4 ES.
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a) b) c) d)

Effective - Complete removal of deposits. Efficient - Protection of base mental. Economical - Cleaning operation cost effective. Environmental - safe and enviro-friendly.

There are about five types of solvents which has been commonly used by domestic utilities for removing operational deposits from boilers. 1) Hydrochloric acid 2) Hydrofluoric acid 3) Ammoniated citric acid 4) Hydroxy acetic - formic acid 5) Ammonium Bromate 6) Ammoniated EDTA 7) Sulphamic Acid. The solvents generally recommended for removal of mill scale are inhibited Hydrochloric acid and Hydrofluoric acid. VI a) b) c) BASIC TECHNIQUE : Chemical cleaning of the boiler will be carried out by a picking solution of 3% - 5% inhibited Hydrochloric acid. To intensify the action of HCL and to dissolve siliceous impurities, Ammonium Bi Flouoride is added to the cleaning solution. In the final phase of cleaning the freshly pickled surfaces are protected from corrosion bya passivated layer of magnetite formed chemically by the addition of Hydrazine and Ammonia.

The above layer is reinforced further by the process of second stage passivation the later stage at a drum pressure of 40 kg/cm2. VII INHIBITORS : To prevent or retard this reaction without of course affecting the attack on the deposits, 0.2% by volume of inhibitors are added with the acid. Most commercial inhibitors break down or loss their effectiveness above 700C. It is therefore, recommended that the temperature be limited to 600C. STEPWISE ACTIVITIES OF CHEMICAL CLEANING OF BOILER. I PRESSERVATION OF SUPERHEATER : Superheater flushing is done with D.M. Water and back filling done with DM Water, Ammonia and Hydrazine concentration more than 200 mg/l. PH is raised to 10 with ammonia. The connecting tubes are plugged with temporary accessories. The superheater is kept under pressure (say 8 kg/cm2) throughout the cleaning process. II i) BOILER RINSE : Cold Water Circulation: The boiler is filled through economizers, taking care that the water does not enter the superheater. After filling the water is drained from the system.

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Hot Water Circulation: Again boiler is filled with steam injection, circulation started, temperature is raised to 500C to 600C then system is drained. III ALKALI FLUSHING : This step is also called as degreasing. In this step chemicals like tri-sodium phosphate, Sodium hydroxide, Surfactant i.e. Teepol are added and temperature of the system is maintained at 700C for four hours. This step is carried out to remove any grease or oil from the surface. After 4 hours or as per the analysis report, this step is stopped by complete draining the system and again the system is filled with DM water and system is rinsed thoroughly. IV COPPER REMOVAL STAGE-I: When copper content in the deposit is known to be higher than 5 percent, this step is carried out before acid cleaning. In this process, 1% citric acid, 1% Sodium nitrate is used at 500C and at a PH value of 10.0 is attained with the addition of ammonia. This process needs about 4 hrs. V D.M. WATER RINSE : Two/Three rinse with DM water is done after copper removal.

i)

VI

IRON & COPPER REMOVAL STAGE-II : When boiler deposit contain copper upto 5%, the copper is also removed along with iron in a single step cleaning and stage-I is omitted. In this step followings activities are done:a) The system is filled with DM water and circulation established. The temperature of water is raised and maintained to 600C to 650C. b) Inhibitor (0.2% min.) added. c) Theo urea (0.25% min) added. d) Hydrochloric acid added slowly and % is maintained in between 4 to 5%. e) (0.5% min.) of ammonium bi-fluoride are added simultaneously. f) Once the acid percentage in between 4-5% is established, it is continued for 4 hrs. g) When acid strength, copper content and iron content reach more or less constant value, the acid circulation is stopped and system is drained under nitrogen cover. The spend acid is drained to neutralisation pit. VII NITROGEN CAPPING : N2 capping is applied to protect freshly prepared surface of steel from oxidation. Here after N2 capping is to be done during each dumping from and after acid pickling. Nitrogen capping to be stopped after first stage passivation. VIII D.M. WATER RINSE : After draining the system is again filled with DM Water heated to 45 - 500C and circulation continued for an hour. The discharge and return line samples are checked for acid strength and iron. When the value is almost constant, the system is drained under N2 covers. IX CITRIC ACID RINSE: The system is filled with DM Water 2% (w/v) citric acid. Circulation is established and temperature raised to 600C. Now ammonia is added slowly to increase the pH to 3.5 to 4.
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Circulation continued till the uniform concentration of citric acid and iron is obtained. Then the system is drained under N2 cover filled in with DM Water and circulation continued keeping 2 to 3 kg/cm2 drum pressure. It is drained under N2 cover when discharge and return line sample attains same iron. This is repeated till iron concentration falls below 35 ppm and acidity almost nil. X 1st STAGE PASSIVATION : The system is filled with DM Water and circulation established. Temperature is raised to 90-950C required quantity of hydrazine and ammonia are added to (200 ppm hydrazine, pH-10). Circulation continued. Hourly samples are collected and tested for pH and hydrazine. If required, chemicals are added to maintain the above concentration and pH. After 20 hours the system is drained hot. The effluents are neutralised with bleaching powder. The vents and drum holes are opened and the drum is inspected and sediments if any in drum or header are cleaned. XI 2nd STAGE PASSIVATION : The superheater plugs, safety valves, down comer orifice plates are removed. Drum internals are manually cleaned and refitted. All provisional equipments and pipings are dismantled and original fittings and mountings are installed back and boiler is made ready for normal operation. The boiler filled up to the normal operating level with 200 ppm hydrazine and ammonia to raise the pH to 10 by chemical dosing pump. The boiler is then lighted up. Pressure is raised to 40 kg/cm2 and maintained for 24 hours. Ammonia and hydrazine is injected into feed water to keep residual hydrazine of 25 ppm. After 24 hours, the boiler is boxed up and allowed to cool. At about 1 to 2 ata pressure the superheater vents are opened and at about 800C (Drum temperature) system is drained to neutralization pit. The 2nd stage passivation ends the chemical cleaning. IMPORTANT MEASURE TO BE TAKEN BEFORE & DURING CHEMICAL CLEANING. 1) All temporary pipe lines to be hydraulically tested and water circulated by the acid circulation pumps at maximum flow and pressure. Seepages/leakages to be thoroughly checked and eleminated. 2) All bands and tees etc where maximum turbulance occurs are more prone to leakages. These points should be wrapped with rubber sheets. This will restrict acid spillage over wide area in case of leakage at these points.

3) Though arrangement for venting hydrogen is made, there is every likely hood of accumulation of hydrogen gas at some place. Hence, no fire should be allowed in the area. No smoking boards to be displayed and welding work in the area to be suspended during the process.

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Provisions should be made for the following emergencies : Alternate arrangement for power and lighting should be made if one source of power supply fails, so that forcible draining of acid solution from the boiler in case of failure can be made. 5) Temporary pipings should be laid over ground to easy inspection for leakages and repair and should not be near or over equipment. DISPOSAL OF SPENT CHEMICALS: Nearly all the chemicals used for chemical cleaning of boiler and preboiler system are toxic, corrosive and potentially harmful to human beings and animals. The discharge to drains, sewage works to the river or to lake will cause damage to the flora and fauna of natural waters. The limits of pollution must be followed before these can be discharged to rivers, etc. The point of discharge of these effluents need also to be decided so that these do not get short circuited to the intake of CW or raw water. Generally in most cases, it may be possible to hold the chemical effluents into a holding tank. Here the effluents can be stored and then released at a slow rate of discharge so that when mixed with other waste water, no damage to sewers or drains occur and also pollution level is kept below the limit. Also effluents can be neutralised by the acid and alkali wash discharge. Hydrazine and ammonia may be stored there for natural oxidation. The tank should of course be of sufficient capacity to hold all the waste effluent and should be cordoned off by fencing with danger board display. However, only display of danger boards may not be enough as illiterate people due to ignorance and others not fully aware of the extent of danger, may ignore it. It is better to post personnel also to warn the people.

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