Basic Guide to Boiler Water Treatment

7/30/2019 Basic Guide to Boiler Water Treatment

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BASIC WATER TREATMENT OF STEAM BOILERSSteve Kenny and D ave PopeChem co W ater Technology

Vancouver, W AThis is a brief discussion on low-pressure steam boiler chemistry. It provides drykiln boiler operators the tools to maintain an efficient and effective boiler chemistryprogram. The main goal of this discussion is to provide these tools to operators so that

they will be able to detect and prevent problems with their boilers and kilns preferablybefore they happen.In order to fully understand what a given boiler needs for treatment, a basic study

of its supply water m ust be d one first. Three types o f impurities exist in all supplies andcan cause a wide range of problems in boilers and kilns. These impurities are suspendedsolids, dissolved solids, and dissolved gasses. Water picks up the impurities from theground it contacts and the air through which it falls. The type of impurity depends oncontact time, and stream velocity. The amount of rainfall and where the rain occurs onthe watershed can and does result in change s in the character of the water throughout theyear. Water supplies typically come from one of two sources, ground water or surfacewater. Gene rally, ground water contains mo re dissolved solids and less suspended solidsand dissolved gases. Generally, surface water contains more suspended solids anddissolved gases an d less dissolved solids.

Mo st problems due to impurities present in the water can be so lved chem ically,one w ay or another. It is usually most econom ical, how ever, to address the impurities byphysical or mechanical mea ns, using chemical treatme nt only to clean up the remainingtraces left after physical treatment. Not only will this pre-treatment minimize chemicalcosts, it also has the difficult to measure benefit of improving a plant's reliability whilesimplifying operators' jobs. Operating kiln boiler plants without adequate pre-treatmentcan be c om pared to a high wire act without a net...one slip and its curtains.

Comm on Pre-treatment Methods Found in Dry Kiln OperationsSuspended S olids Dissolved Solids Dissolved GasesFiltration Ion Exchange S oftening DeaerationClarification Demineralization DegasificationReverse Osmosis DealkalizationThe optimum pre-treatment scheme for each plant must be worked out on anindividual basis taking the entire system into account. Costs, maintenance requirements,environmental impact, and many other factors come into p lay.

In the Northwest it is not all that common to have a suspended solids problemwith dry kiln boilers. However, the problem does exist. Suspended solids can causecorrosion and deposition problems in boilers and in kilns. Simple multimedia filters area com mon way to rem ove suspen ded solids. A pressure vessel, fi lter bed of various sizesof gravel, sand, and anthracite coal is usually sufficient to reduce suspended solids toacceptable levels. Improveme nts to filter performance can be achieved through chem icalmeans. Another way to remove suspended solids involves a settling basin or clarifier.Still water promotes particulate settling. The addition of coagulant and flocculent

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chem icals speeds up an d improve s this settling process. The result is cleaner wa ter forboiler makeup or other applications.In an effort to address a d issolved solids problem, ma ny dry kiln plants use water

softeners to pre-treat boiler makeup prior to system entry. Many advantages to its usebecome apparent when the softeners function is understood. The main types of boilerscale are composed of calcium or magnesium, w hich can be readily removed in makeupwater by softeners. Their removal dramatically reduces the possibility of boiler scaleformation. Water softening can be performed by ion exchange, whereby favorablesodium ions are exchange d for unfavorable calcium and m agnesium hardne ss ions by theion exchange resin beads. Eventually, the softener resin bed exhausts (fills up withunfavorable ions), and must be regenerated, rinsing the unfavorable hardness ions to thedrain and replacing them with sodium ions. The so ftener bed is again ready for service.

Similarly, if better dissolved solids control is required, another form of ionexchange m ay be em ployed. Dem ineralization is a me thod of choice for removal of nearlyall dissolved solids for higher-pressure boilers that have tighter restrictions on boilerchemistry. Positively charged ions (cations) such as sodium, calcium, magnesium, andiron are exchanged for hydrogen ions, and negatively charged ions (anions) such aschloride, sulfate, carbonate, and silica are exchang ed b y hydroxide ions . Instead of salt,Demineralizers are regenerated with sulfuric or hydrochloric acid for cation beds, andsodium hydroxide for anion beds.

Reverse osm osis is yet another method for reducing dissolved solids from watersupplies. It too reduces both positively and negatively charged ions but in a d ifferent way.Since RO is a process that requires much attention and usually has pretreatment of itsow n, it is rare in low-pressure dry kiln boiler operations.To reduce corrosive dissolved gases from makeup water most plants use somevariation of a deaerator. Deaerators exploit the physical properties of temperature andpressure to drive off dissolved gases. The wa rmer wa ter gets the less carbon dioxide andoxygen ca n be dissolved. On ce the gasses a re forced out of solution they are vented offwith a steady flow of steam. To improve a d eaerator's performance a plant may need toincrease the temperature and/or steam flow. Depending on the DA design, some othermechanical improvements may b e required.One way o f reducing the corrosive gas, carbon dioxide in steam a nd condensa teinvolves the use of a deal kal izer. Dealkalizers are yet an other form of ion exchan ge. Like

softeners they are regenerated with salt and often a combination of salt and sodiumhydroxide. Dealkalizers exchange unde sirable nega tively charged ions m ostly carbona tesfor desirable ions m ostly chloride and so me hydroxide. Carbonates break dow n in boilersto form carbon dioxide, which carries off with the steam. Carbon dioxide becomes verycorrosive when it dissolves in condensate. Pitting is often evident in kiln piping wherecondensa tion occurs in systems where carbon dioxide is a problem. Ke ep in mind that thesource of most carbon dioxide is not a dissolved gas in makeup water removable bydeaeration. It comes as a dissolved solid associated with sodium and calcium ascarbonates or bicarbonates in ma keup w ater, which then transforms into carbon dioxideinside boilers. Deaeration can remove ca rbon dioxide in return condensate, but damag eis already do ne in kiln and return conde nsate piping.

Specifically, there are a number of advantages to a properly managed boilerchemistry program. Boiler chemistry programs include not only chemical addition, butalso pre-treatment equipment. Maximized equipment life, reduced maintenance costs,minimized dow n time, ma ximized safety, optimized chem ical costs, minimized fuel costs,



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ASM E G uidelines for Water Tube BoilersDrum Pressure Iron Copper Total Silica Total Conductivity0-300 0.100 0.050 0.300 150 *700 7000301-450 0.050 0.025 0.300 90 *600 6000451-600 0.03 0.020 0.200 40 *500 5000* Total Alkalinity must not be allowed to exce ed 10% of the Cond uctivity.(psig) Hardness Alkalinity

minimized water consumption, and minimized waste water are the main benefits.Equipm ent that is properly protected w ill last longest an d w ill require the least am ount ofmaintenance and down time. The same equipment is less likely to have catastrophicfailures leading to safety conce rns. Properly treated systems w ill also reduce chem ical,fuel, and water consumption to a minimum. Reduced water consumption directlytranslates into further reduced fuel consum ption since every ga llon of w ater that entersthe system req uires energy to raise its temperature to turn it to steam .

As sentinels of the heart of dry kiln plants, boiler operators have control over twobasic aspects of the chemical program; blow down and chemical feed. Blow downrequirements are determined by the type and amount of impurities that exist in thema keup w ater. Blow d own rates of course directly affect chemical feed rates. Therefore,a complete analysis of the raw and makeup water is the first step in establishing thecorrect program. From this analysis a qualified firm can determine the right operatingparameters for the program.

The imp urities found in the ma keup w ater will build up in the boiler as the waterturns to steam leaving most impurities behind. There are know n m aximum limits for theseimpurities, which can and will be surpassed without proper blow down. The maximumconcentration allowable by the limits can be expressed as the maximum cycles for thatwa ter supply. Usua lly on e imp urity w ill reach its ceil ing first, making it the limiting factorfor that water supp ly and thus establishing a bo iler's maximum cycles. When a ma terialsurpasses its solubility limit, it begins to form deposits or precipitate. The actual limits arenot exact numbers for al l plants and b oilers but are best expressed by ASM E or A BMEguidelines (see chart below). Some of the impurities (calcium salts, etc.) begin toprecipitate as a result of the higher temperature and pressure of a boiler environment.They either form dep osits or react with treatment chem icals to form harm less materialsthat are removed through blow dow n. Calcium, for instance, reacts with phosphate at theproper pH to form hydroxyapatite, a harmless precipitate sludge (when dispersed) thatfalls to the bottom of the boiler where it can be removed through bottom blow down.When boiler water pH is not within the proper range, calcium reacts with phosphate toform harmful calcium phosphate scale. Other impurities such as silica and iron can bet ied up by d ispersants and chelants and remain suspende d in the boiler water where theycan be removed by continuous surface or bottom blow down. Left improperly treatedsilica and iron both can form ha rmful deposits.

ASM E P hosphate Treatment Guidel ines (boilers below 6 00 PS IG)OH-Alkalinity 100-600ppmPhosphate 30-50ppmSilica 200 - (0.25x Boiler Pressure)Total Dissolved Solids 2000-3000ppmWestern Dry Kiln Association 3 May 2000


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It is difficult to determine the true conce ntrations of ma ny im purities in the boilerwater because of their interactions with treatment chemicals and other impurities.Chlorides, however, are relatively unaffected by other materials in the boiler. Whencomp ared to the m akeup water chloride concentration, boiler water chloride con centrationwill most accurately show the cycles of concentration of a boiler. Consequently, chloridesshould be used to control boiler blow down. If ten cycles of concentration are permissiblefor a given boiler, then the con centration of chlorides should ne ver exceed ten times thatof the makeup water. For example, the makeup water chloride concentration is 10ppmso the b oiler chloride concentration m ust never exceed 100ppm .

The on ly way to control the cycles of conce ntration in boilers is to rem ove (blowdown) som e of the highly concentrated boiler water. Makeup water replaces blow downand dilutes the remaining boiler water. Blow down is performed two ways; bottom blowdown and surface blow dow n. Ideally, blow down shou ld be done in proportion with steamproduction. If the entire blow down is being done manually, as with bottom blow down,it is important that operators monitor cycles closely and adjust frequency and length oftime of blow down accordingly. This process can be very difficult to control cycles ofconcentration. A surface blow do wn d oes a m uch better job of keeping cycles leveled out,since a constant flow of blow dow n can b e adjusted via a m etering valve. In any case, theboiler water chloride level should be mo nitored to ensure the blow do wn rate is correct.If the chloride level is higher than the recommended maximum, more blow down isneede d. If it is low, exces s blow dow n is occurring, resulting in wasted che micals, water,and heat ene rgy. In som e cases the chloride level never approaches the recommende dmaxim um, even if litt le or no blow dow n is being done . Conseque ntly, the boiler may havea vessel leak or a leak through its bottom blow dow n valve(s).

If a plant's steam production fluctuates like dry kiln operations do, the surfaceblow dow n stream can easily be set up to automa tical ly com pensate for the changes inrequired blow dow n rates. A steam grade solenoid valve or motor operated valve can beinstalled in the surface blow dow n line. The feed water pum p circuit actuates the valve.As the s team load increases, the w ater level in the boiler falls more qu ickly and activatesthe feed water pumps more often and/or for a longer period of time. Consequently, thechem ical addition pum p(s) adjust feed rate(s) automatically. To fine-tune the blow dow nrate, a metering valve on the surface blow dow n line must be adjusted initially. Once themetering valve is adjusted prope rly, the system will remain quite stable. This configurationis known as proportionate blow down. Manual blow down then becomes primarily asludge remo val function an d does n ot need to be va ried to control cycles. A variation ofthis blow dow n control method includes the actuation of the blow down valve by a ma keupwa ter meter or make up wa ter valve. Since the steam production rate directly affects themakeup water requirements, the required blow down rate is also proportionate to themakeup water needed. As the amount of makeup increases, the water meter or valveactuates the chem ical pumps more often. To visualize how much blow down is actuallyrequired, ten cycles of concentration means that one pound o f blow dow n is required forevery nine pounds of makeup w ater used, or 10% blow down rate. Twenty cycles wouldbe one pound of blow dow n for every nineteen pounds of ma keup wa ter used, or a 5%blow d own rate. Monitoring actual cycles is critical in m inimizing w ater, chemical and fueluse. If cycles get too high, even proper levels of the best chemicals cannot guaranteedeposits will not form. In this situation carryover may also occur, contaminating the steamand p ossibly dam aging system comp onents. Chloride testing is the only way to monitorcycles accurately.

With the right blow down rate established, chemical feed can be fine tuned byrecipe changes or do sing pump setting changes to bring residual chemical concentrationsinto the proper ranges. Standard boiler chemical programs include sodium hydroxide



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(caustic soda) for alkalinity, sodium sulfite for oxygen scavenging, some form ofphosphate for scale prevention, phosphonates and synthetic dispersants for depositcontrol and/or removal. Also, Various amines are employed for return condensatetreatment, which prevent condensate line corrosion and ultimately corrosion productdepo sition in the b oiler.

A variety of parameters should be tested to maintain good boiler chemistrycontrol. Con ductivity testing is used to m onitor the am ount of ma terial dissolved in wa terby m easuring its ability to conduct electricity. The mo re ma terial dissolved in the wa ter,the higher its conductivity w ill be. As a b oiler approaches its maxim um allowable cycles,it will also approach its maximum allowable conductivity. If a boiler water's conductivitygets too high, indicating excessive d issolved m aterial is presen t, steam w ill start to hav etrouble escaping the water's surface. This phenom enon is due to increased water surfacetension from higher dissolved solids con centrations. The b oiler at this point will begin toprime, or foam and bounce, resulting in tiny d roplets of boiler water carrying ove r with thesteam. Good quality steam is essentially distilled water. Carryover reduces the BTUcontent of the steam resulting in excess fuel consumption and reduced kiln efficiency.Measuring condensate and boiler water conductivities are important for ensuring goodsteam q uality and can e xpose m echanical problems w ith boiler and kiln operation.

Sodium hydroxide provides a highly alkaline environment in the boiler. This isabout the only environment where water and steel get along well. Heat magnifies thenormally corrosive effect water has on steel, since it speeds up chemical reactions.Maintaining the correct alkalinity range minimizes this highly corrosive effect of water.Alkalinity also plays a critical part in various chem ical reactions in the bo iler. Frequently,most of boiler water alkalinity comes from the addition of sodium hydroxide in thechem ical program. Som e of the alkalinity com es from n aturally occurring alkalinity foundin raw water supplies. If it is present naturally, it contributes to the required alkalinity inthe boiler and de creases the amount of sodium hydroxide needed.

Alkalinity is typically measured as either P-Alkalinity (Phenylthalein Alkalinity)M-Alkalinity (Methyl Orange Alkalinity) or OH-Alkalinity (Hydroxide Alkalinity). P-Alkalinityis determined by a relatively simple titration procedure. OH-Alkalinity is determined byeither using a modified version of the P-Alkalinity test, or by calculation using P andM-Alkalinity (2xP-M=OH). OH-Alkalinity is primarily the most important. However,P-Alkalinity is more convenient to test. If P-Alkalinity is in range, the OH-Alkalinity will bealso. Boiler alkalinity is directly related to b oiler pH so if the alkalinities a re in range , thepH w ill be also.

Chloride, as discussed earlier, is used to mo nitor cycles of concen tration and tocontrol blow down rates. Makeup water and boiler water should both be tested todetermine the cycles of concentration. Makeup water quality can change with time. Forexample, failing water softener has the potential to increase the chloride concentration inthe makeup water. Along the coast seawater encroachment has the potential ofdramatically changing makeup water chloride concentrations also. The procedure fortesting both boiler and makeup water samples is the same except for one thing. Theboiler water sample m ust be pH neutralized. The chloride test is most conveniently doneon the same sample as the P-Alkalinity test for boiler water. This sample has alreadybeen neutralized w ith an acid titrant. The chloride test will not work p roperly on a high pHsamp le. (Note: OH -Alkalinity sam ples cannot be used for chloride testing. This test usesbarium chloride, resulting in an incorrect high chloride reading.) The recommendedchloride range for a boiler depends greatly on the m akeup w ater chemistry.



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SulfiteSulfite is used to consum e dissolved oxygen in steam b oiler systems. If dissolvedoxygen is permitted to exist in the boiler, it attacks the steel in the boiler forming oxyge n

pits. This pitting causes serious damage and eventually tube failure. This is the mostcommon form of corrosive attack in steam boilers. Dissolved oxygen can also flash outwith the steam and cause corrosion throughout the condensate return system. Sulfitereacts with dissolved oxygen to form sulfate, thus making the oxygen unavailable todam age system me tals. Sulfite is best fed into the feed wa ter system as far upstream aspossible. The optimum feed location is at the storage portion of a DA. A long distancein the feed water stream increases the reaction time of the sulfite with the oxygendecreasing the possibility of oxygen getting into the boiler. Consequently, much of thefeed water system also gets protected.Phosphates

Phosphates are used to react with calcium and m agnesium ha rdness to producecontrollable materials (hydroxyapatite and serpentine) removable by blow down.Phosphates should be added to low pressure boilers to maintain a residual of 30 to60ppm as ortho-phosphate. Testing for phosphate in a bo iler sample requires filtering outthe phosphate precipitates already formed. Any calcium or magnesium present willconsume the ortho-phosphate. The consum ed phospha te can sti ll show up on the testsgiving false high readings. The benefit of softening boiler feed wa ter becomes very evidentonce basic boiler water chemistry if fully understood. Hard makeup water requiresenough phosphate to maintain the 30 to 60ppm residual in addition to that needed toneutralize all of the calcium and magnesium hardness in the boiler water. Soft makeupwater only requires enough phosphate to maintain the same 30 to 60ppm residual. Aboiler on soft makeup c an be o perated at higher cycles of concentration, thus requiringless blow down and less chem ical treatment in general.

DispersantsPhosphate precipitates (sludge) must be dispersed thoroughly to prevent themfrom baking o n to the heat transfer surfaces of boilers. A variety of dispersants are used

for this purpose and must be fed in a proper ratio to the phosphate treatment. Sodiumlignosulfate, a brown organic substance, has been used in lumber mill boilers for manyyears. How ever, it has m any limitations that the more m odern synthetic dispersants andscale inhibitors do not have. The newe r treatment chem icals available today have m uchgreater capabilities but tend to be more expensive. The lignosulfate and some of themodern dispersants should not be used together since they can react, making bothuseless and possibly making an undesirable material. In most cases older treatmentprograms using lignosulfate should be converted to more modern programs usingphosphonates and other dispersants and scale inhibitors.Amines

Return condensate is naturally corrosive because of its purity. The pH of purewater is easily decreased in the presence of carbon dioxide. Carbon dioxide dissolves inthe water to form carbonic acid. Oxygen readily dissolves in pure water also. Both lowpH and dissolved oxygen lead to corrosion in any water system especially in the presenceof heat. The amount of carbon dioxide in a dry kiln depends primarily on the amount ofcarbonates present in the makeup water. Various amines are used to neutralize theresulting carbonic acid in condensa te causing the p H to stabilize at higher less corrosiveWestern Dry Kiln Association 6 May 2000


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levels. The return condensate system is then protected from carbonic acid corrosion.Reducing corrosion decreases the amount of corrosion products that would normallyreturn to boiler and form deposits. These deposits can be the most difficult to remove.An amine or blend of amines must be selected to meet the needs of each system. Thechoice of am ines depen ds upon the length of the steam lines and their configurations (T'setc.). Am ines are rated through d istribution ratios (DR 's). The higher the D R the furtherthe am ine travels. A high DR a mine ha s a great affinity for being in the steam pha se. Alow D R am ine has som e affinity for staying behind in the water phase (in the boiler). Thelower the DR the more it recycles in the system. In a smaller dry kiln operation a lowerDR amine is usually most economical as a result. Special amines known as filmingamines are used to coat the inside of the return condensate system further protectingthem from corrosion.

Neutralizing amines should be fed at a rate sufficient to produce a returncondensate pH of 8 to 9 for best results. The exact feed rate depends on the percent ofcondensate return since higher return rates mean less makeup, the primary source ofcarbon dioxide. A higher return rate also m eans be tter recycling of the am ine already fedinto the system. As a result, less am ine has to be fed to replace w hat is lost. Amines ma ybe fed in several locations depending on the configuration of the system. They may befed directly into the boiler, the steam header, or into various strategic steam line locations.Som e recycled amine will be lost in a DA since some steam is vented from D A's. Addingthe amine to the steam header downstream of steam l ine to the DA makes e conomicalsense.

Chem ical feed is best done in proportion with water use. Like blow dow n control,makeup or feed water flow rates can be used to actuate chemical feed systems. Thischemical feed technique automatically compensates for changes in steam load givingstable chemical treatment control in the system. One of the simplest ways to employ thistechnique is to have the feed water pumps actuate the chemical pump(s). Once blowdown and chem ical feed rates are correct and stable, testing should be done regularly tomonitor any changes that may occur in the system. Any chemistry changes may beindicators of m echanical changes in the system. O nce the relationship of boiler chemistryis fully unde rstood, an attentive operator can diagnose p roblems to his plant by noticingchanges to boiler chemistry. For example, a system set up on proportional controlnormally operates at 75% condensate return with fairly stable chemistry. One day anoperator no tices his cycles of concentration increase, but the other chemistry stays in line.He makes sure the chloride tests are accurate on the boiler and makeup water. Henotices, however, his chemical usage h as increased. Finally, he determines that he mustbe losing more cond ensate (now only about 60 %) possibly through a new leak or througha change in lumber cond itioning procedure, because of the ma thematical relationship thatexists betwe en cycles of concentration and condensate return rate. Given the sam e blowdown rate, cycles of concentration will increase with a decrease in condensate return.Makeup water with dissolved solids must be added to replace lost (fairly pure)condensate. As m ore dissolved solids are added to the boiler the cycles of concentrationincrease. The operator may have a lso noticed a de crease in condensate pH . This wouldhave been due to the increase in carbonates added to the system through increasedmake up requirements and through a d ecrease of recycling amine. Ma ny other scenariosare likely to occur in dry kiln operations and can usually be traced through attentivechemistry monitoring. When these changes a re noticed when they first happen , operatorscan quickly prevent a variety of problem s and increasing chem ical costs.



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Mathematical Relationships for Boiler Chemistry ProgramsFeed Water = Makeup Water + Condensate Return

Makeup Water = Blow Down + Condensate Loss

Boiler Lay-up Procedure Wet StorageW et lay-up is used whe n the boiler will be ou t of service for shorter periods of time.The bo iler can be brou ght back into service quickly when laid up wet.1. Fill the boiler to its normal ope rating level, preferable with de aerated fee dwater.2. The w ater should be boiled with the unit vented to the atmosphe re to purgethe boiler of any excess air.3. Add e nough ca talyzed sodium sulfite to achieve a residua l of at least100ppm as S03. This will require the addition of approximately 1.0 to 1.5poun ds of sodium sulfite per 1000 gallons of water in the boiler.4. Fee d sufficient caustic soda (sodium hydroxide) to establish a pH of at least11.0 or a P-Alkalinity of 500 to 600ppm as calcium carbonate. The quantityof caustic will depend on the alkalinity of the fill water.5. Before the unit has cooled to the point where a vacuum has been drawn,comp letely fill the b oiler with deaerated feed w ater.6. Tightly close all connections a nd ap ply a sma ll positive pressure tocom pensa te for the vacuum that will deve lop as the unit cools to room

temperature. This can be achieved by using the feed water pump. As andalternative to app lying a b ackpressu re, it is possible to maintain a he ad orreservoir to serve the same purpose. Connecting a clean 55-gallon drum tothe vent l ine o r other ava ilable fitting atop the boiler will does this. As theboiler is filled, the drum collects the overflow. Then, as a vacuum developsbeca use of coo ling, the wa ter in the drum enters the bo iler and k eeps it full.Additional water ad ded to k eep the d rum filled should be treated with sulfite(1 oz per 50 gallons) and caustic (approximately 1.5 oz per 50 ga llons).7. The boiler should be tested weekly as long as the unit is in storage. Sulfiteand caustic should be fed as required to m aintain the recomm ended levels.W hen m ore chem ical is adde d, it is desirable to circulate the boiler water fora short t ime by me ans of an e xternal pump.8. For startup, drain the bo iler to the no rmal ope rating level. Initiate the feedof regular boiler wa ter treatme nt chem icals as soon as the boiler is placedin service.


Basic Guide to Boiler Water Treatment

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