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    © All Rights Reserved
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    9 views7 pages

    UTLAPPG2 Boiler Water Treatment

    Uploaded by

    Aleem Qureshi

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    SPECIAL REPORT ey = ‘rnopnospnate eoncantatien, pam PhosphatelpHl coordinated contol ‘maintains xd ratio of sodlum to phosphate in boiler to avoid tee alkalinity (ower tegion, ratio Below 3.0), by controled adaiton of mono, di, and tvsodiam [hoophate. Tinted arca fo regimen mast S2ppteabie to low and madera proses Boller. Highor pregaure systema ar hinted to rales betwoen 26 and 2 and 16 ppm phosphate concentrations 18. Chomistry monitoring is the key to ieatment-systom pertormance. Skotch shows princpal dosing and sampling points, parameters for moderate-pressura systom of condensers—inleaking cooling. water, Excess hardness or other mineral iempuri- ties in makeup may be the result of inefi= cient operation (or absence) of preteatmeat equipment; chemical teatment added to & boiler to condition these impurities often ‘ill contribute to boiler deposition, Solids dissolved and suspended (TDS and TSS) in boiler feedwater can accu malate within the boiler under tie con- centrating effect of steam generation. As steam (pore ater) exits the boiler, these Impurities remain behind. Higher temper- atures within the boiler cause some dis- solved impurities t precipitate out of solu- tion. Suspended solids, ten too heavy to remain in normal flow patterns, stat to accumulate in low spots or in areas of low flow: ‘When deposits occur ina boil, the elfect iso Torm an insulating. layer on Moke and reserve focouater esing oh the metal heat-transfer surfaces. the boiler then loses efficiency in converting fue! ‘enetzy to steam. The insulating effect of ‘deposits also may elevate local tempera- tures at points where inefficient heat trans- fer is occurring. Temperatures can easily exceed the design limits of boiler metallur- ay. and a point of metal stress is created. Beneath deposits. chemical environments can create highly corrosive conditions — Uinder-deposit corrosion, n modern botlers \deshuned for very high rates of heat tras fer, hotspots eaused by waterside deposits Bos can quickly lead to boiler faiures. Deposit control and inhibition are ac- complished by: mechanical and. chemical means. Mechanical control is exercised ‘through boiler blowdown to limit impurity {concentrations inthe water. Limits may be ‘based on solids content, alkalinity. silica, etc, which are keyed to operating pressure For hoilers operating at 30-300 pig, for example, the American Boiler Manufactur- ffs Assn recommends 4 maximum of 100- S300 TDS in boiler waver: the time range ‘drops with rising pressure, with 100 ppm the suggested limit for pressures exceeding 1000 psig (Table 2). Alkalinity varies s ilerly, going from a maximum of 700 pom at very low pressures to 25 ppm at 1000 ie Gontinuous lowdown of boiler wa- tera impurity concentration fy ‘Shot, ening the sae to be Red automatically within desired al iS Crem for contin lowdown is taken from that part ofthe boler ci ulation containing fhe most concealed rater In roder nit, ra ofthe sls tren solution anda ox taken om the steam drum at one pont below water devel. Wh this Kind of systny, nt socal pet tem Dlowoff valves need only be opened ‘occasionally on a regula schedule to discharge sludge fom the mud drum or lower header But lowdown alone is not sufficient to inhibit deposit foewation. Mt must be accompanied by chemical treatment. Two tasic forms of chemical treatment are sed. “The oldest is controled preciplaton and sludge conditioning, in. which impur are precipiated aod held in a. suspend fd, nonadherent form, The oer approach involves a solubilizing program tat maine ‘tains imports in salon "The former includes the carbonate eycl, various phosphate teatments, and some of the polymer tetments resem into- duced, Soldbilizing treatment sited to Ghelantype programs that make use Of helans, phosphonaes, and some pol)- inet, Treatment of both types may also be done concurently. Precipitation programs Carbonate treatment, the proach, involves intentional precipitation Of calcium hardness as calcium carbonate. (The method! requires concurrent adit ‘of a chemical to condition the resulting sludge sufficiently to enable its removal from the boiler. This practice is an out- growth of the practice of adding natural Substances, such as potato peels, followed by boiler operators in the early part of this century.) If silica is present with sui- ficient magnesium, it can be precipitated from boiler water as serpentine—a low- adherance solid that can be removed by ‘lowdown. Both sludges ae then removed ‘by baxtom lowdown. The carbonate-cycle method is applica- ble to operating pressures up to 250 psig— higher pressures if softened water is used. One advantage comes into play when oil for organic contaminants are present in the eedwater, since the sludge produced does rot react with organic matter. That reaction could result in formation of an adherent scale on boiler surfaces (asin some pho ‘hate-based programs, described below). ‘On the other hand, carbonate treatment generally dictates fewer eyeles of concen- ‘ation (higher blowdown rate) than do fther programs, leading. to greater con- sumption of fuel, water, and chemicals. Because of this and the greater dificulty BOILER WATER TREATMENT in handling resulting sludges, carbonate lweatment was largely displaced by phos- ‘hate treatment-—particulaly for medium- pressure boilers-in the 1930s (Table 3). Phosphate treatment has been the most common approach for several decades. In water containing sufficient hy- drate alkalinity, phosphates combine with calcium hardness salis to yield a sludge knovnas hydroxyapatite. In systems work- Ing at 800 psig of below, the sludge Is Withdrawn by bottom blowdown. Simulta- rcously inthe presence of adequate silica, serpentine is formed. The orthophosphate residual at Jow pressures is typically 30-60, ‘ppm as POs, with hydrate alkalinity levels ‘of 200-400 ppm. ‘The process converts hardness salts 10 1 readily controlled and removable form Tn lower-presse boilers, suspended solids removable by blowdown can accrue to ‘very high levels—far higher than those acceptable with other programs. But there are some disadvantages to phosphate teat- ‘ment, It adds to the total suspended-solids Content, which becomes increasingly unde~ Sirable as boiler pressures approach and ‘pass 1000 psig: AS pressures rise, required SPECIAL REPORT ETHYLENE DIAWINE-TETRARCETC ACID (EDTA) 16, Chelants such as EDTA (diagrammea at let) combine wit hardness salts to preclude precipitation in boilers. Effectiveness derives {tom cisplacement of H~ lon from carboxy! groups by Cal" of Mg * ons to frm stable rings (tinted, right) makeup purity also must rise (Table 2). fol ar other organic contaminant is pre- sent in condensate returning from plant process, moreover, it may combine with Suspended solids to form a product that adheres to heat-transfer surfaces, Overheat- ng and te fature can result ‘Coordinated control. The wisely accepted approach © control of caustic orosion is based on adjustmeat of beil Ceewater chemistry 1 provide 1 balance ‘perween its pH and the phosphate con: centration. Known as coordinated control, it is designed to prevent the existence of free hydrate alkalinity (exoess caustic), by maintaining boiler-water pH below the curve representing the relation between pH and isodium phosphate, NasPO. (Fig 14) All points on the curve have a sodium to-phosphate ratio of 3.0. Free hydrate alkalinity is present in the region above the curve, and the poten til for caustic corrosion exists. Below the jourve, the phosphate isin both trisodium and disodium (NasHPO.) form, the sodi- lum-to:phosphate ratio is less than 3.0, and all alkalinity i ted up by phosphate, In general, controlling. phosphate add tion (both form and amount) to keep the ‘water in the rezime denoted by the shaded area provides sulficient buffering (safety ‘margin t preclude corrosive action (Note that high-pressure boilers—above about 1200 psig—are more sensitive tothe possibility of caustic heing sequestered in ‘small crevices or beneath boiler deposi Because ofthis, the broken eurve (Na-to- PO.=2.6) was offered as a better upper ‘bound 10 ensure adequate buffering —the “eongruent-control” philosophy. As a rule, today's high-pressure. systoms maintain boiler water in the range between 2.6 and 2.8. with phosphate concentrations between 1 and 6 ppm.) Organic conditioning agents. Nat- ‘ural organic materials have long’ been used to condition boiler scale and sludge ‘The firs organic conditioners were derived from plants, and included potato. skins (starch) and coffee provnds (tannins) (Table 4). In boilers so treated, organics are adsorbed on crystals formed from pre- cipitated calcium and magnesium, distor ing the crystal structures. Thus, precipi- {ated salts are readily dispersed, Facilitating blowdows ‘Modification of these natural products resulted in greater solubility, improved performance, ete. Most often used. were Sulfonated lignins, tannins reacted with sulfites, and chemically modified cellulose (CarboxynetiytetTulowe). A anajor advane tage war their low cont, since most were based on ante matter” For some, thelr ‘brownish tint made visual control relatively easy on the basis of boiler-water color. OF ‘cours, fairly high dosages (100-500 ppm active ingredient) were needed for effec- tive performance. These products are still in use in some plants, particularly those with lower-pressure systems (125 psig. or less), They are best for conditioning cal- lum carbonate scale, but not too effective ‘on calcium andor magnesium phosphates. ‘Thus, as phosphates found increasing use in treating feedwater hardness, improved deposit conditioners became necessary, Perhaps one of the major breakthroughs in scale and sludge control was the discov ery that a new series of synthetic chem feds, polyacrylic acids — nore specfieal~ Jy, polymethacryte acids (and tele neural salts. "polymethacrylates) gave greally ‘Improved deposit control. This marked the advent of carboxylated polymers. They can be used at much lower concentrations than natural organics —usually 10-50 ppm active in boiler water. Offering good bonate- and phosphate-scale conditioning, ther higher thermal stability enables use at pressures 0 800 psig. While lack of color- Ing prevents easy field monitoring, boilers tusing them were found to be much cleaner ‘and could be operated longer with better Performance. Industrial plants have used both polyacrylates and polymethaerylates, cither with oF without some of the modified tural organics, ‘An important consideration in recent years has been the increasing recovery and tse of returning condensate, This intro- ‘duces significant amounts of iron oxide (product of corrosion) into boiler water. ‘Though generally rather effective, poly ‘crys are not the best chemicals for con- trolling iron oxide deposition. They can react with calcium hardness, leaving some calcium polyserylate deposits on the high heat-flux surfaces of modern boilers. This shortcoming led to development ‘of synthetic polymers and copolymers that fe extremely effective for metal-oxide control, as well as having greater ther ‘mal stability and excellent earbonate- and [Phosphate-deposit control. Polymers such 4s polymaleic acids, moditied polyacryhic acids, and polyacrylamides (ll earboxylat- cd) started to gain use with the polyacry- lates and some modified natural organs at rather low dosages—often 10-20 ppm (ac- tive) in boiler wate, The development snd use of sulfonated styrene/maleic anhydride copolymer (SSMA) during the late 1970s fad early 19808 ws 8 major advancement for phosphate- and carbonate-scale con trol. Is importance relative to the poly- [BOLE WATER TREATHENT » «spc not bis min sar rmethacrylates improved as dosage levels were reduced to 5-10 ppm aetive in some ceases, 2-3 ppm. Other copolymer developments include maleic-, acrylamide, and acrylate-based products containing carboxylate or sulfonic functional groups, or both (Table 5), They demonstrate great ability to control met ‘oxide deposits, Keeping materials in solu- tion long enough to ensure their trans- ‘port through the boiler. At dosages of 5- 10 ppm active or less, they have even ‘heen found ta increase the amount of oxide transported, indicating the ability to clean Up pre-exising deposits, The newest poly- mers and copolymers are often referred to as “allorganic” weatments, Includ= ing the aerylate/acrylamides and acrylate/- maleate, they rely upon excellent feedwa- ter quality less than 2 ppm hawdness Ta bles 3.5). (One shortcoming of these new materi- als, however, is the lack of testing tech- niques sensitive enough to control them reliably. (Typical dosing and monitoring locations ate shown in Fig 15.) Some test ‘methods have underestimated polymer eon- Cenirations by as much as several hundred pereent, causing considerable danger of fverfeeding. Thus, current deposit-contol techniques generally use blends of these specialty copolymers with the earlier syn- thetics. IC i still fairly common practice to inelude some lignin sulfonate or tan- nin to add color for contol. Because of their performance and low cost, polyacry- Jates and polymethacrylates are usually the owe June 18 BOILER WATER TREATMENT. 17, Amine combination uses uci-neuralzing capably of ess-vole amine close 0 bal that of more-volatle amine a further reaches of plant (colored major component of a blended treatment chemical Solubilize with chelants Internal boiler-water treatment using ‘chelants provides much cleaner (eposit= free) boiler surfaces. than precipitation treatment. This reduces. scale. formation and permits greater heat flux with less dan- ‘ger of tube failure, Chelants are organic ‘chemicals eapable of forming complex ‘molecules with calcium, magnesium, and ‘ther metal ions. The molecules are very Stable and remain in solution, ‘Thus, the inetals are unavailable for reactions that ‘could lead ta deposits of ealeiam carbonate and sulfate, magnesium hydroxide and sil- ieate, iron and copper oxides. etc ‘Chelant treatment requires low hardness feedwater—less thant 2 pp eual—t0 be economical, 50 its use is often limited to softened or demineralized makeup. Sodium salts of EDTA (ethylenediamine-tetaacetic acid) and NTA (nitrlotiacetic acid) are the two most common boiler-waterchelat- EDTA isthe more effective Available sites for bond ing with metal ions (Fig 16), while NTA has only four. However it stil requires 10 ppm EDTA and 5 ppm NTA to tie up each ‘ppm of hardness because ofthe large df= {erence in te sizes ofthe molecules. Com= parison of their stability constants shows that both have trong affinity for fei ton, Both chelants are susceptible to thermal degradation. EDTA breaks down gradual- ly, starting at about 300 psig: NTA is sta ‘ble to about 900 psig, but then decomposes rapidly. An advantage of EDTA is. that its decomposition products also have some chelating ability, and are effective to pres- sures as high as’ 1300 psig: those of NTA. show almost no ability to chelate metal ions above 900 psig. But chelanvmetal ‘complexes of both are stable even at 1300 Dsig, provided they are formed at lower lemperatures. Thus, chelants are usually {ed into feedwater rather than boiler water, in systems operating above 300 psig in the ‘ease of EDTA and 900 pig in the case of NTA. Note that thermal degradation makes it impractical to monitor free chelant resid- uals in boiler water Because O: hastens chelant degrada tion, feedwater must be Oxree before the cchelant is aided. In addition, the presence ff both Op und chelane can beighten dhe ‘corrosion process: ‘The Former initiates it, the later perpetuates it by solubilizing the corroding: metal. In the presence of Os, cthelant prevents formation of a protective ‘magnetite layer on catbon stel surfaces. ‘Although chelants are capable of eaus- ing corrosion, they rarely do unless overted fora sustained period —a real possibilty in view of the dffieulty of monitoring resid- tals, The effect will appear first in local areas where chelants may concentrate, ust- ally at evaporation sites (along water Tines land. at points of departure from nucle= ‘ate boiling; steam-separation equipment is also sutceptible to chelant attack. Metal Surfaces attacked by chelant have a char- acteristic appearance. ‘Typically, they are SPECIAL REPORT Steam ig ae ‘ora ed Newratzng ame Sanday outraizng or hinng are] condensate 18. Filming amine adds to corrosion protection of condensate lines by applying surtace fn Primary and secondary appicaion pomts of fimers and noutralaere are shown here smooth and contoured in the direction of flow, CChielants are very aggressive wv copper alloys, and may induce contusion of Das fr broaze pump impellers if introduced head of a feedwater pump. Because pro- lective oxides on boiler steel are less tena ious below 400F, components located in low-temperature environments — feedwater Piping, economizers, blowdown piping — Aare more vulnerable to attack, Underfeed of chelants can permit for- ‘mation of scale, so their use is often sup plemented with Scale-contol polymers. An advantage of chelants, however, is that they gradually remove existing scale when formal feed rates are resumed. ‘Typica- ly, feed is adjusted to maintain a the- retical 1-2 ppm free residual in boiler water. Note that excess feed into a dirty boiler may cause rapid removal of deposits and deposit buildup in areas of high heat flux. Chelant feeding should be continuous and downstream from the point of deae tion, and thorough mixing should be com= pleted before its introduction. Its impor {ant thatthe chemical be injected into the bulk stream, never near a metal surface, and that chemical feed lines and injection ‘quills be made of stainless stl ‘Organic phosphonates are another ‘group of chelating chemicals, used in boil ets below 400 psig. AMP (aminomethy lene phosphonate) and HEDP (hydrox- yethylidene diphosphonate) are commonly ‘sed to inhibit calcium carbonate scale While these are the most familiar forms, other phosphonates and phosphino chemicals are seeing increased use because of superior stability and effectiveness. All solubilizing agents show behavior similar to EDTA and NTA in keeping calcium and inon in solution, but are not as strong. As such, they do n0t pose as great a potential for corrosion attack as the chelants. Unlike the latter, phosphonates are used in sub- Soichiometre dosages to keep calcium in solution. Thus, they can be used econom- ically at feedwater-hardness levels of 50 pm snd higher ‘Phosphonates may be fed into the boiler or the feedwater. Injection into feeawater following the feedwater pump is prefered, 2 this allows impurities to be complexed in the feedwater and transported in that form through the boiler. Free HEDP and AMP entering the boiler will gradually {decompose to orthophosphate, producing & phosphate-based treaiment program. AMP. Js much the less stable of the two, and will revert more completely under nor- ral boiler conditions. In fact, phospho nate-feed conttol is often keyed to ortho phosphate concentrations measured in the ier. Generally, up to 50% of the phos pPhonate is available to solubilize hard. ness entering the boiler. Boilers treated with phosphonate are much cleaner than those treated with phosphate or earbon- ate. though not quite as clean as with EDTAINTA. (See Table 6 for summary of ‘water-treatment chemicals.) Role of silica As indicated earlier, the presence of sil ica in low-pressure boilers can serve a vital function: In a precipitating-type program, ‘oven minimal amounts of silica will pref erential precipitate magnesium as serpen- tine. Two cautionary notes: (1) Too high a silica residual can produce an adherent sil- jeascale, and (2) above 600 psig it starts to ‘olatlize, passing over with the steam and potentially forming toublesome deposits ‘on turbine blading, ‘The extent of vaporous silica caryover pends on operating pressure and silica concentration. Pressure-related. guidelines

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