Chapter 6. Operating Procedures Having described a number of physical and chemical methods for pre paring water to be transformed into steam, i is important to now examine aspects of opera 6.1 ‘TYPES OF BOILERS ‘The quality and con large extent by the type of b the operating pressure, Acco possible apy a, Stationary Field-Erected Boilers Central power stations at from large generators assembled at the building site. Typie: {ube boilerswith 1wo to four drums, fred by coal, fuel ol water tubes shielding, . refractory. Asa rule, utility steam generators hav surface that includes the superheater, and a relatively sm face. In order to improve efficiency. boilers in power plants are equipped Tue gas to the feed water just be heater is inst tion air. Before being introduced into forced by a fan through the heater, where it is wa 120 from flue gas. Heated makes combust suitfur t and raises 1 temperature of the furnace. ate elevtricity, ated by 1 perc The ‘minimum of stee demands 8 hi soot-blower, draft fan, piping and wiring, tog gauges, safely valves, and contr bust weight of “ y ft wide, 15 11 high, and 25-30 0 is extremely rapid from a cold stan on secount of the sn flux is ip to 250,000 xs designed 30-40 years ago. Oper 1n 250 psi to 900 psi; a few packaged at 2000 psi. Because of the intense heat flux in these unit in fora field erected by Feed water ler operated erator the density of steam eal pressure, 3203.6 ps phase separ sition fromone while that of water de rly a small change in temperature.) on process at the evitieal pressure ‘out the heat absoare fied with fvel oil. On large tankers, au he shell and tube type are sor OPERATING PROCEDURES 123 50 pai. The advent of the Muid catalytic stacking process 25 years ago lead co the introdu which carbon monoxide ftom the catalyst regenerator is mixed with sup. el and burned in a furnace to produce 800-psi process stearn is a recovery OF otherwise wasted heal: the carbon mon orat about 1000 F 62 WATER TREATMENT PROGRAM: In pee application of individual chemicals and their functions in treating water were discussed. Combinations of chemicals and sequences of treatments used to prepare water for the generation of st re now considered. ns are marketed under 2 multitude 'ere ave only a few fundamental methods of nmary of chemical treatments that have 5 at particular pressures. In Preparing this table care hos been taken to ensure that the recommended treatments are chemical to char above S00 F, above 600 psi. On the other hand, polyaerylates and polymethacrylates begin to char at ~ 700 F. so there is no limitation on their use becouse of {hetmal considerations. Chelant-treaiments have been secommended for boilers operating hetweea-150 and_1500_psi, but heze 600 t0 900 pai is let 600 psi the appropriate methods of softening often do total hardness of the make up water enough to make s chelant treatment economically feasible. Also, at 900 psi EDTA is ther. i Same pressure NTA loses mucit of its che ‘© Polyoxyalkylene glycols f ie ids in boiler water is < 2000 ppm, whereas lerant of high concentrations of suspended Consequently, the latter are limited to a maximum of 750 psi and ler are suggested hetween 750 simi iderations were taken into account At pressures below 500 pai itis usually unnecessary to make special noval of silica, for in plants where lime-soda soften: 's used the concentration of silica is significantly reduced in the soften treating water for boi{ (Gace (aan (aac (teed (cea (rea (teas Geese (eae (ana (eae (eaan( eee | 124 THE CHEMICAL TREATMENT OF BOILER WATER = OPERATING PROCEDURES isl g 213,01 form os é eee ti sludges of magnesia éj3— = 5 ieate is added : a8 increases the HE i : rescaled caustic reserve meh Ns | Seaceeaecneaaet oldest, least expensive, and still most widely used 2 £3 . ing boiler water. Filtered, sof | a is aded i nd catalyzed su elalle 8 supp foam and by Ah is Tan added to disperse Judge. Fiee alkalis formed in the S/glé ¢——- #2— 9-21 es and bicarbonates, producing a pil of 3| || é as 3 § 117, Advantages of the caustic reserve method of tceatment are i i 3 eo A it i. a i: i ne cost Is . Jer than expensive S 2] tele 3. a proprietary - settee (ste) Ae caeseeseeeeeceee sg seca ne eal lz ae ab € es z ¥ | Rl eeg ge z 2 B) gggge 2 7a see eee | Scene emma neg aa “|za55 # gis : E fe Free-and easy way itis Eri i— [er i Sod nae soften added fan ac pressures (900-1500 psi) There are in : : service, however, a large numberof low pessure boilers with ap riveted or a/gee 8g 88 888 8 butt-and Teak steam and water, é Baa a leading to the loce yrdroxide and the possiblity126 THE CHEMICAL TREATMENT OF BOILER WATER of cau these steam generators (generally operated at < 200 pal) should be treated with sodium nitrate. At higher pressures and temperaiuees nitrate is successively reduced by magnetite to nitrite, hypo ly decomposes to nitrite ond oxygen. NOs" 2Fe304 = NO,’ + 3Fe:03 6 2NO;"+ FesQx = NiO," + 6Fe205 (62) 4H,0 +N,0,7 + 4Fe 0, = 2NH,ON + 6Fe20; + 20H” (63) 4NH,OH = N,O+ 2NHy +3H,0 (64) I is essential when using nitrate in boilers ranging in pressure from 900- 1500 psi to be aware that each mole of nitrate produces one mole of hy Groxyl ion and one-half mole of ammonia while oxidizing six moles of ‘magnetite, as shown by the net results of the above four equat SH,O + 4NO,"+ 24Fe 0, = N20 + 2NH, + 36Fe:03 + 40H 65) ion of ammonia Jn addition to the generation of free alkali, the concen in the steam is greatiy increased. Curcently, there is much interest and promotion of chelants as an sealants for the internal treatment of boilers. It is alleged that the b operator can expect cleaner boilers and higher rates of heat chelant programs than are obtained with conventional phosphate treat ments; under ideal conditions this is probably true. One shoul realize, however, that overstreatment with chelants inexeases ec rates while lunder-treatment produces troublesome scales. Deposits formed as ares ‘of insufficient treatment, eg., pump failures, neglecting to prepare chela mixes, improper quantities in the mix, erroneous test results, are much hhatder, more insoluble, and more adherent than those formed under phos phate treatment. For this reason, it is advocated by some that phosphate be used with chelant to serve asa reserve of antiscalant in case of softener leakage or the enforced use of hard water in emergencies. The work of Walker and Stephens,” however, shows that if boiler water contains phos phate, hydroxyapatite, Cas(OH\(POx)s, preferentially precipitates in the presence of an excess of either or both EDTA or NTA, on account of the exceedingly small solubility product (Kyp = 3X 10°) ofthis base sal OPERATING PROCEDURES. i? Using chelants stall in the presence of phosphate ica is present at con- which suggests that a chelant treatment is not appropriate for boi ing at < 500 psi. The solubility product of serpentine, Ms(OH),(SiO,)2, was empirically determined by Walker and ens a ted the formation constants (ofien called stabi logarithms of several chelonates of sodium (ethylene: )Metraacetate (EDTA) and sodium ni n constant isa ‘al ion and a chelant together. Thus, he lager the format nore firmly bound the met TABLE 6.2 Formation Constants of Selected Chelonates Chetanate PKp CaEDTA 10.7 MgeEDTA 8 Fe EDTA (ous) 144 Fe EDTA (ic) 25.1 Co EDTA to caNTA a2 MaNTA 70 Fe NTA (ous) ax FeNTA (ic) Is. 3 in boilers, it is ob. chelonates of EDTA and ydronide (Ky = 6 X 10),f ( ( f ( ( ( ( ( ( ( ( ( ¢ ( G ( c 128 THE CHEMICAL TREATMENT OF BOILER WATER OPERATING PROCEDURES fe ould not be added to the feed ng. amines should be injected ine for sulfite to reduce ony: !s should never be he same reason they water near the deaerat ods of nuclear magn nposes 10 iminodiacetate and N-hydroxyethy ede, composition being accelerated by oxygen. Both of products are chel he sske of mechanical expedi 66) TABLE 6.3 Chelant Demand of Feed Water Hardness $n tt ced ater Hardness Regardless of the chelants used and the claims s for par eee caeel soul ions of product a poly. 372 mer be F the program.) A polymer is 37 Needed to disperse insoluble sats thet for ions in 93 the hardness of feed water pump, or Iss erroneous analyses. Su: ange of 600- —_T 900 psi include sodium polyacrylate. sod e, and care boxymethylcellulose, The laiter enars at about 600 F, so should not be ‘Doble 6 3the sto of chelants to hardness are shown, used above 1500 psi. principle, chelant is continuously proportioned to the total hard ness in the feed water by means of 8 chemical injection pump. For example. if the average concentration of hardness in a feed water is 0.5 rpm CaCO, {about the maximum pe: relant program to be econ Feasible), it would be necessary to maintain 1.9 Instances of severe corrosion havebeen noted in steam drum concentrated chelant had been injected form of thinning at the waterline, ted in areas of the drum where the velocity of flow is high. Wastage is also enhanced at hot spots and in the upper sections of the risers; usu sion is uniformly dark and s the eye. To avoid this hazard, cl ld be fed continuously ‘hrough a Type 304 stainless stel injection nozzle to the Feed water. Ti Point of injection should be as far as possible downstream from the ceaera. tor if catalyzed sodium suifite is used as an oxygen scavenger. Under no isbe mixed together, tants imac: vate the cobalt catalyst (see Table 6.2), preventing the rapid reduction oxygen. The latter enliances eontosive attack by NTA, haste degradation of EDTA, and causes pi economizers. If make up water is sof able to add neutralizing amines to the feed water to neutealize carbonic acid in the condensate le, should Dut at 900 psi 20 ppm of EDTA, oF 30 ppm of NTA ace reasonably jximwum concentrations of chelant, Pract at should be appreciated before attemp ‘chelant program. One of these able 'n a boiler plant to measure accurately concentrations of total hardness be. 1 proper rate of ad chelant depends upon values that lie in this range. Suppose, that a boiler operator detem conservato Table 63 EDTA. If perator's idaess ($ 0.1 ppri CaCOy ned EDTA is 0.1 X 3.7. 20,0r 74 Pm, and the residual EDTA in the boiler water is (38 — 7.4) = 30.6 ppm, es ipplement ation of i scale on boiler 1 900 psi) the free alk NaOH. Equivatent alk Bereading = 3.6-7.2 Lorenc and Bermer‘!2? have disclosed 9 methed for co 1 combinat process centration of nited to 8-10 py the phosphonate (at about |.5 ppm) is evidently depended up the formation of scales, as discussed by Ralston.'2) Obviously, Jant Is over- or underfed, corrosion or scaling ine an. and hydrazine are also ine ‘method of treatment. Walker and Steph ‘0 form more stable complexes than NTA that also are therm more stable than free EDTA, Wi is advantageousin that NTA can be determined more precisely Suggested operating conditions for an 800-psi boiler under chelant treat ‘meni are listed in Table 6.4. Once again itis important to emphasize that a chelant based on phos chelant progra salines and less disturbance oy h phosphate treatments, [At pressures above 900 psi caustic gouging becomes a serious consider chemical treatment of boiler water: above 1200 psi it isa de (OPERATING PROCEDURES BL TABLE 64 CChelant Treatment in 800-psi Boilers boiler water Si ble concentrations ppm CxCOs) 75-150 20 max 30 max Total Chelant with Phosphonaze (ppm NTA} 10" Polymer (pam) 35 803°") 15-20 (ppm NaH) 0.10-0.20 Silica (pam Si03) 25 max * Assuming les than O.$ ppm Css total Mardnes in feed wate. te hazard, In the range of 850 to 1200 pst in boilers provided with a make up of superior qu: incralized or evaporated), caustic wate-pH teat- sure range sodim Js 10 decompose to some extent, celeasing sulfur dioxide, an acidic gas al can cause severe corrosion in the condensate system. At pressures higher than those now being considered, the decomposition bevornes more rapid. Thus, inboiler water containing 20 ppm Na;SO; there is = 0.2 ppm of SO; in steam at 1550 psi and 0.5 ppm of SO, in steam at 2000 psi. As us acid is much stronger (Ky = 1.72 X 10°) than carbonic acid (K, = 4.2 X 10°7}, the pH of condensed high-pressure steam could be < 2. Furthermore, the decomposition of sulfite increases the free alkali in the boi $05"" + H,0 = 20H" + So; 7) For psi Because the coordinated phosphate-pH system is especially appropriate for marine boilers, whi ively small volume of make up pre Pared by the evaporation of seawater, this application will be used for The dist ished by heating it with 10-pst seam, then introducing the hot saline water into one or more flash cham: 1es€ reasons, hydtazine is the oxygen scavenger of choice above 900132 bers where it vaporizes The di trated brine remai o seawater, are fabricated of 90/10 ly made of cast iton Leakage in the m through alumin tor, can intiaduce seawater and damage to the turbine, When operat 4 two-stage, fash-type evaporator con solids with pechaps0.08-0.07 ppm of silica In applying the coordinated phosphate-pH program a moderate rs Wor phosphate (15-25 ppm) is maintained inthe always available 10 react with caleium and magnesium conta the feed water. The pH of the boiler water fm n Fig. 6.1 shows the ranges in which pl ‘This can be ac 1d by adding disodi ate andor o- dium hydroxide. As can be seen by examining the arrows in the figure, adding disodium phosphate increases the phosphate resi ual wi ing the pH, whereas adding sodium hydroxide raises the pH, affect the phosphate residual. The objective is to keep the pH and the concentration of phosphate within the normal operating region in Fig, 6. but in any case, always beneath the curve Seawater contains dissolved air, the greater part of wl ferred into the distillate in the evaporators. In addition, air can leak into portions Of the condenser circuit that are under va al joins are not tight. As the main condenser on a ship is one of the larger pieces of equipment, and is of bolted construction, itis a primary source of air con- ‘Asin any steam plant, most of any dissolved gases are removed from the feed wate: by mechanical deaeration, Residual oxygen (< 10 ppb if the deaerator is functioning properly) is reduced by injecting a sotution of hydrazine between the high-pressure and low-pressure stages of the bine when at sea,or into the storage section of the deaerator when in port. ‘The turbine cross-over is the preferred point of injection when steaming, rather than the boiler feed water. If hydrazine were added to the feed it “OPERATING PROCEDURES ge § : t Poe Be | 8 \ | 3, T ae | 8 dl al 1 78 L | lg | : 2 i Litt ES ane 3 3 Foose ay ana wd unre PPM POg 133 Fig 6.1 Coordinated Phosphate ptt Convely destroyed in the superheuter. steam to reduce oxygen in U ed Corrosion by carbonic avid «: to the storage section and condensate systems. Deck steam lines - 3f€ particularly susceptible to ¢orrosion. ese lines lay idle rusting occurs, then when steam is turned the lines loose rust is swept back throu condenser the drains tank the deaerator operates effectively at full steam load, it suffers 4 sharp drop in eft lord, oF dh leads as, for instance, when the ship is maneuvering. Significant concentrations of oxy= gen enter the boiler under jons, as itis not feasible to change the dosage of hydrazine continually. As # consequence, b nonferrous surfaces are coFroded to some extent 1g finely divided oxides of iron and copper © condensate system, These oxides, if id at rough spots such as butt-welded ng and gouging. For be an integral part of water treatment ‘To remove the oxides of imn and larger than S ly. the nuld be located in the main condensate stream just feam of the deaerator, but as approximately 90 percent of the total oxides can be removed by ent t0 instal pamp. On many total flow of condensate, 0 suffices. The filter should have the capacity to contain at least 100 Ib of to perm ige changes to be made at 6-9 month OPERATING PROCEDURES 135 \ge canbe changed in about one-half hour, it is unnecessary the single filter ean simply be bypassed w' idge. An AMF CUNO Type SL. ‘The Following conte are Lypical 1200 psi TABLE 6S Feed Water and Condensate for Coordinated Program pH (Condens Suspended Solids (Condensate) No pat than $ microns Hydrazine (ppm NaH) 0,01-0.05" Iron (ppm Fe) 0.02 max Copper (ppm C 0.02 max ‘Oxygen (Deaerstor Outtet), (pnb O2) tO max Amoionia (Condensate), (ppm NH) 0.5 max st * Measured in the feed waterline afer the last Feed water heater, Hyarazine 3 thould be at the lowest level detectable, but an acta res menurabie, For reaso ‘method of caus ing 1200 psi of 8.5.9.3. Fig, 6.2 represents the rel ins of phosphate in a mixture containing 60 percent of NasPOs of NazHPO,., in which the ratio of sodium to phosphate is 2.6 L operating cegion shown in Fig. 6.2 (2-4 ppm PO,, pH 8.5-9.3} 's suitable for boilers operating in the range of 1500-2000 psi: fram 1200 ip of pH to various conanion exchanger. TABLE 66 Boiler Operation with Coordinated Program Components in boiler water Suitable concehtrations 98-102 12-22 25-45 300 max! Chloride (ppm CU} 30 max® a (ppm Si0:) 4 max! ;osphate (ppm POs”) 5-28 Hydrazine (ppm NH) 0.01-0.1 evaporated make up. Higher values are allowable ir (ee Table 6.12), but an a ship woud indicate ecndenses leak oF Uupit in dhe evaporator ators that operate in excess ef 1200 psi ere rather than process steamn. The make up tate in perhaps 1 or 2 peteent—so raw water is Virtually all steam gei used to produce elec these plants is, therefore, smal purified either by evaporation concentration of total dissolved solids in the raw wat dem ion is used; above 500 pp, evaporation OPERATING PROCEDURES. y \ REGION SY NSS PPM Og norwat OPERATING Fie 6.2. Congenonteomtnal save le 9.0}-—— ee} L 96 oa 2.9] eaessary e of a strongcacid cation exchange resin in the hydrogen form, followed by a bose anion exchange resin, el this way at the rate of 2-5 gal ional type of demines Section 4.3b, it isunly necessery to add (0 be demineralized is grea while to install a dogasifier between reduces 1 the cation exchanger to al fon the anion exchange resin and low roxide—now an expensive, er fesin. As the opera: er is deseribed TABLE 6.7 + Operation with Congruent Program boiler water 85-03 85-93 5 2 Hydeazine 9.05-0.19, 0.08-0.10 Siliea (ppm $10) 3 max OPERATING PROCEDURES 139 Wee of a typical sequence of ion exchange resins fed river water having a conductivity of 200 the flow rate in this particular train i650 gal/min, The weak boc anion exchange tesin used for the second siage of demineralization hee a iah exchange capa an be regenerated much more efficiently than a strong.base resin, ler is required too, however, to remove silicate TABLE 6.8. Performance of a Four Stage Demineralizer or Volume of resin Type of resin «ey mn Exchange, Strong Acid 150 Anion Exchange, Strong Base 70 Anion Exchange, Weak Base 80 Mixed Bed, Strong Acid Strong 50 Bose chemicals can be used for wa hydrazine alone is added to the feed water a centrat reatment above 2500 psi, 150-200 percent of the con. In some plants hamge of the condensate extraction of oxygen, which should be less than 3 ppb hydrazine so ump, and sometimes aqueous ammor boiler feed pump. TABLE 6.9 Boiler Operation with Volatile Treatment Suiteble concenteations 2000-3000 pst 1s in boller water 45-95 20-30 2 max 05 max Serres ees aef eee ee eee eee (eee 140 THE CHEMICAL TREATMENT OF BOILER WATER t pressure of 3203.6 psi, virtua tolerated in boiler feed water, as al that passes throug! value the cor 10:8 uso found that a large propo: s smaller than 0.45 micron be removed by deminerelizat the high-pressure stage Duff and Leven first and second reheat deposits donot form in rates in sy al boilers, even a few parts per billion of copper oxides he steam ean soon drastically reduce the efficiency of a turbine. As these deposits cannot be washed off with wate mechanically, eg., by blasting with made to prevent metallic oxides from entering done by raising the pH of the condensate to prev ty brass in condensers, by ng") the condensate, By inst with Mow rates of 20,000 gp | sate aysiem, part of oxides and colloidal hydroxides can be climinsted. The total concentration af iton can be reduced to 3-8 pod, and that of copper to 1-2 ppb, with the cond than 0.1 umbos. This process also protects t nd turbine in the event of a condenser-leak. In dei ing condensate accor taken of the exhaustion of the cation exchange resin by ina singh ‘exhausted resin is discarded and fresh resin. This pur nates deposits of tively, and TABLE S.10 BeOUS. IF not essent ose filteraid downstrea idensate demineralizer, Condensers ly Fabricated of copper slloys rather than steel on account uf the sistance of the '0 aerated cooling water. Stainless steel ean be used if the coolant is fiesh water, but is inappl brackish water or seawater is used, because of Austenitic alloys to stress corrosion cracking by 7) recommend that feed water (0 avoid deposits of copper oxides in 103) Sodium (ppb Nad ids (ppb) fron steam (ppb Fe) Copper-steam (ppb C\ * Tradomark of the Graver Water Division, tcodyne Co don, New Jersey 07083,TABLE GIT —— Recommended Fei Water Quality a Maximum (ppm) 900 1000 1500 2000 2500 3200+ Sitica range (ppm) ‘Total hardness ‘Oxyeen Ton Copper 78,00 - - 7 20.00 = - 2.00 ~ - -8 2.00 0.030 : - 0.20 0.030 - 2 0.10 0.030 a.0so 0.020 9.05 0.007 0.020 o.ois 0.05 2.007 0.020 ols 0.00 0.005 0.000 0.010 0.00 0.005 oot 0.010 9,00 0.003 0.003 0.002 0.02 max 0.00 0.002 0.002 0.001 * tn modern industrial boilers, which have extremely high ates of heat tansfer, these concentrations shoul be essentially 2670 simaaiy, should 8s total hardness should noi exceed 0.3 ppm CaCOy, even at the lower pressures; suspended solids in the feed water 220, f poste wi YALA MATION JO ANIWLVAUL TONS aL a | TABLE 6.12 Recommended Concentrations of Boiler Salines Maximum (ppm) ‘Ronee inp) Frame — Sawason Dissolved Suspended Tou ier me “estea) Rewdesl Resist sd" tempernme|F) subs asia" alkainty"* Sua Natural Syhetio™phoophate alle tydreine 100) 'so0a0 soo 3003800 180s Nr 90100 NR 200 sooa00 380, soo 20000 1s) 1S, gassed 300 380900300 7m 17500 0) 1S 5020 NR 500 300000 “60 soo 400030 “560 NR 600, x0000 50 503300710 gos NR a — 200090 __4 300__3000_N@__1a. 30 Ne 300) ooo 00 30 3002000 NR ‘PoTo.0IS 1000 5000010 so ogo, NR. NR OIDOS 1500, too 3 0 hte: NR WR SR 00-010 2000 soo 0 “TW NR NR wR OoS-010 3500 100 8 Tn ey MR zoo 00:8 Dom NR NR NR Gants (or pratt (0950p apy cone bonl etree bob wth nore aes ha at, 50.000 BA AT ie unre of chap bars lune in st mele mate cant ne mag’ carne 9 éaperen pera sesbe rcs (UP"No, The caver ame tiny proces by mrmona hygeine Serpe oe ba SANGIN ONILVNAIO ert144 THE CHEMICAL TREATMENT OF ROILER WATER For convenience, the man} values qu water treatments appropriate For boilers at specific operat narized in Table 6.11 and Tabie 6.12, These tables were prepared 2s guidelines only, Values shown reflect the assun : at low pressure can use poorer feed w: pressures. Thus, feed water sofiened 6) hardness of 15-20 ppm CaCO; older boiler generating process steam at 200 ps re for 8 modern packaged boiler, inv ions of suspended solids are intolerable, Similarly, modern at 850-1200 psi have very applications the values in Table 6.12 aze too a. The Water-Treating Plant is apparent from the preceding dis the way of chemical treatment of feed water for extremely high boilers: make up is evaporated or demineralized raw water £0 wl dustrial steam plants, on the other hand, generate process ste: n at moderate pressures that do not require exceptionally pure feed water. Because t jon of steam plants is a matier of considerable impor tance in the manufacturing industries, itis important to consider a typical waterreating plant suitable for preparing make up for 8S0-psi boilers, Proper operating conditions for such boilers, using ‘method of treatment (see pp. 125-126) are shown in Table TABLE 6.13 Operating Conditions for 850-psi Boilers Components in boiler water Suitable concentrations ‘Total dissolved solids (ppm) 1500 max Silica (npm SiO) 25 max M-Alkalinity (ppm CaCOs) 250 max Phosphate (ppm PO.) Lo-15 Sulfite (ppm $05) 15-20 ‘OPERATING PROCEDURES 14s is proposed to treat raw water having the compos 6.14, 10 make it suitable for make up for six B50-psi ng 175 000 Ib of steam per hous. TABLE 6.14 Analysis of Raw Water Abbreviation Concentra Compon: 790 470 320 sat der to conserve water not more than 5 percent blowdown, To achieve this a reduce the concentrations of silica ard total dissolved solids, both of whi can be accomplished by coldime softening in a Spa apter 4, pp. 57-58 ,it is best when usi he chemical treatment for max and sequence of oper wake up for bei ig sulfuric acid, he sodium form, whi146 z Ar21800)3 THE CHEMICAL TREATMENT OF BOILER WATER (S98: sTeaw pases! ra FEED WATER soner ‘CoAT Pre ‘conveNsare STORAGE RETURNED CONDENSATE SToRace Neg805 DEAERATOR seauiome PaecniTaTen cio » SOFTENER TANK FireR Fig. 6.3, Water treatment plant for moderate pressure boiler feed water ‘ORERATING PROCEDURES 147 places calciuin and magnesium fons with sodium Returned condensate ic passed through @ Milter precoated rnum hydroxide get to remove any oil intioduced by machinery or process deaks. ied condensate is then combined with the filtered, softened raw water and deaerated, Catalyzed sodi le is added to the storage section of the deaerator to scavenge the last traces of oxygen, after which ready for use. Chapter 3 and 4 contin com: jons, but it is worth while here 40 ator more closely, as these properly managed. Fluctuations ‘aw water also upsets these units. (0 calculate the proper dosage of tee: sory tohavea way of measuring the flow of wate slumi- ancous reading recorded on a 244 circular chatt and a n 0 to 100; an integrating fa {or is required to convert the chart reading to gallons per minute. TI integrating Factor is, eg., 15, and the chart reading happens to be 5: then the instantaneous rate of flow is 15 X $2.0 780 gpm. If. for ex ple, the totalizer at a ime reads 2,748,403, and & h later reads 2,748,915, the number of gallons processed in 8 his the difference in read ings, $12, multiplied by 900, ie., 15 X 60. or 460,800 gal In order to reduce the concentration of silica, the proper amount of slaked 1 softening together with magng ee times the concentration of slice in the raw water. Rel to Table 6.12 it is seen that M > CaH, therefore the proper dosage 0 Ca(OH) is 0.742(M + Malt), or 0.742(65 +32) = 72 ppm Ca(OH) [see Chapter 4, pp. 41-43]. The concentration of silica in the raw water is 12 ppm, so 3X 12, oF 36 ppm of MgO should also be added. These two chemicals can be mixed togct fe ny (a0) joned to the flow of To vontain the mixed slurry a cylindrical to achieve the desired concentrations of Ca(OH), and MgO must now be determined. Also, itis convenient to use entire bags rather than odd bers of pounds in making the mix: lime is available in 100.b bags, magne: sium oxide in 60-1b bags.148 THE CHEMICAL TREATMENT OF BOILER WATER ne of the vxer is An? or 3X mX 16 = 150.8 f ‘equivalent ‘with water, ing an average flow of 460 800 gal, 8 1 Ht is necessary to add 72 X 3 840 000/108, or 277 Ib of Ca(OH). con- wously over an 8h period. This can be done by adju ner 19 Feed 277 X 36/500. oF 20:n. of slurry over an Bh per . to obtain 36 ppm of MgO it i necessary to add 36 X 3,840,000/108, oo 138 Ib of MgO in 8 h. AS this is (0 be fed in the same 20 in. of slury, 138 X 36/20, or 248 Ib of MgO must be added to the lime mixer also Note that four bags of MgO we whieh is ease enough for this operation. Next the alkalinity differential, (2P ~ M), of te eff ‘ent from the precipitator must be adjusted so that it falls in the range of 12-18 ppm CaCO, ion offers sulfate fed froma separate mixer wi ner: 200 Ib of feree sulfate in 36 in of water is satisfactory. The usual dosage is around 7 ppm of Fen(SOs)s— about 5 in, of solution in 8 b sf using 2 36.in. mixer The heat of solution of anhydrous ferric sulfate is such that about 50,000 Buu's ate liberated when 8 200: portion ofthe satis dissolved water. The corcesponding tise in temperature of the water increases the @ of solution of the salt, but the final temperature should not exceed 100 F, or fuming occurs. IF the temperature of the water is too low, or it the proportion of water to salt is too great, undissolved ferric sulfate is likely to foul the mixer and feeding equipment. Its, therefore, important to take into account the temperature of the dilution water and its volume when preparing an aqueous solution of ferric sulfate. The folowing table lists volumes of water at various temperatures to use for dissolving 200 Ib of ferric su 20m completely disolved, dilute to the working volume of the mixer (36 in in this example) ‘Once the propottioners on the lime and ferric sulfate mixers are prop: erly set for a particular flow of water, they automa amounts of the slurries as the water flow changes bec steam demand or luctvations in the amount of returned cond + emulsion® is used t0 co must be added cor carryover in ,eailable from American Cyanamnid Company, Industrial Chem 3. Wayne, N.J.07470, is suitable OPERATING PROCEDURES 149 TABLE 6.15 Preparation of Ferric Sulfate Solutions Temperature of water (F) Volume af water (eal) Percent salt (wt/wt) 45 10 2» 60 95 20 70 20 u 80 240 9 90 360 6 ously from its own mixer to the inner cone of the precipitator. Approx iately 3 gal of the emulsion can be mixed fe inner cone by mes ty the drum in 24h, The ‘55gal drum and adjusted surface of the water Nowing into the col trough. Sodium aluminate is often added es 18, but the polymer recommended here is more efficient use when the aim is to remove si used it must be added from a separate mise Vide make up for six 850-psi b ing 175,000 tb of steam er hour. This amounts to 175,000 X 6 X 24, 0% 25,200,000 Ib of steam per day, which is equivalent to about 3,000,000 gal of water. Because of ing these boilers at § perce I be 1/0.05 = 20. From Eq, (1-6) 3,009,000/19, or about 138,000 gal/day, and from Eq, ( feed water flow is (3,000,000 + 158,000). or 3,158,000 galjday. This vol ume of water passes throug treated with 1-2 py water. Catalyzed s0« way as lime and ferric sulfate. To add | ppm of SO,” to the water, n of NisSOs, i 16 X 3.158.000 x 8.410% = 42 of Na;S0) every 24 h. This assumes that the deaerator is working properly and producing water containing less than 10 ppb of dissolved oxygen The removal of oil from condensate using precoated filters is described jomed fron a mix taISO THE CHEMICAL TREATMENT OF BOILER WATER OPERATING PROCEDURES, Ist in general, ae easier to apply and have fewer dis nes, The dosage used depends upon a number except to note 1 pt the degree of corrasion pi eee inp be Win es yh a pH as adequate to Pcs 0 fan hte dawoge fed otro eps St iron was achined st pi of 93.95 Incosne al a any dosoge Methods for es ropes dosage are given in Chapter tem through 4 ndensate extraction pumps, a 5. pages 108-109, densers, or in undeaerated quench water. These gases are not corrosive as Proceeding 10a discussion of the internal calment of when dispersed in dry stean ate (© examine nd copper in condensate. Bonafede and Sandell,®2) in a study of corrosion in a Feed water system ing cupro-nickel high pressure heat Dreporderance of suspeniled over dissolve fn the presence of morph of water form (particularly at bends where sharply) and corrosion procesds, Brindisi@®> reports that found a ‘They also observed that, 8 of buth suspended and feed, whereas the concentration of dissolved copper wasincreased, Suspended copper wasnot significantly affected. Table 6 16 ‘summarizes a few of these results ide corrosion is indicated by a charact face, whereas the ravages of oxygen a ing amines are often recommended for prolection against oxygen. Added as an emulsion to the feed water, they are said to be effective ai 5 up {0 2200 psi and superheater temperatures to 1005 F, The in which condensate contains < 10 ppm range of 4-8, Slow flow rates, pH values F corrosion products, ond hyd rocar: formation of films TABLE 6.16 Effect of Morpholine on Iron and Copper in Condensate ee cen ey een ETE Jron (ppb) Copper (wpb) Diss Total Susp. Diss. Total Condensate source ny industri 7 nO Turbine A 1996 120 09 on is widely used, however, it is 2 4 2 1s that should be observed 7 1 9 10 320 42 i amines are injected contin ProvessNo.1 A 27028-29002 1 1 deaerator, oF alternative Bo 42 047 S902 to emulsion ProcessNo.2 A 250 36 290 03 09 12 en increased by 0.5 ppm B45 17 6202 eee nee ee mm dosage (based on steaming rate) of 2 ppm t¢ condensate becomes heavily cont water should be discarded unti f ‘ f ( ( i ( 15? THE CHEMICAL TREATMENT OF BO} is the rate of depletion of & To answer the first two questions reated make up, condensate, and feed watec must be referred to: suppose these are as shown in Table 6.17, TABLE 6.17 Analyses of Water Streams Component {ppm CaCOy? a0 1a Lo iy (Ppm CaCO,) The volume of plos comiprise the tote! boiler feed water, By accursiely ion of silica in each of these streams. itis possible to calculate the per centage of feed water, The volumes of ‘make up, condensate. a ated as Vn, Mey and Yj and of condensate in feed water are desi of silica in dhe 10.2 ppm, and in the feed woter 09K, = 18K y + 02% ome From whieh = 0.7% 100/16 = 44 per valent, To answer the154 THE CHEMICAL TREATMENT OF BOILER WATER TABLE 618 Blowdown Limits in Table 6.23 ‘Total dissolved solids (ppm) 1500 max 35.0 (ppmCaCO;) 250 max 4.0 Siliea (ppm SiOz) mx 0.9 To restrict the concentration of silica to a may blowdo dissolved solids is ~ 970 ppm and M-alks b lors requires b ler water, imitations in 850 psi Boilers Feed Ble of 3.6 percent. At thi iy is = 110 ppm CaCO, in th Before addressing the third question it is necessary to corvect the pre- liminary values of f and 6 obtained on page 149 by assuming a blowdown rate of 5 percent. Presuming that the steaming rate, s, renains constant at 175,000 Ibjh in each of the six boil 3,000,000 . It isnow possible to caleuiate the into the steam drums of the six bo logete/ea) Setting aside for a moment the mechanics of injec be simply assumed that each of the six b phosphate, which will be called cy. As is the total blowdown, V1 the combined volume of the six bi (see page 9). Time, ¢, is in days, therefor at the end of one day 24 b its concentration, Togee — loge] ogee bis calculated from Eq. (1-6). wR 1) (6) 281) 100 gpd 1 of depletion of phosphate injected ‘To do this Eq. (1-10) is used: b(t 0) 1g phosphate, it can ly 15 ppm of 0,000 hosphate is added for Ibe =111,900)150.900 2708-0740 OPERATING PROCEDURES 155 = 1968 © = 7.1 ppm PO, oe of phosphate a 15 pp 3 equlent of 79 ppm uf phasphate even, 34 IPO, is : : necessary to In pounds of | 7.9 X 150000 X 8.34/10* x 0.669 = 15 1b the steam drum of each bei ving an adjustable stroke. Becau lium polyacrylate and 3 i can easily be calculated, ‘again using Eq. (1-10), thet 2.6 ppm of polyacrylate and 1.6 ppm of foam must be added every 24 h, ‘These concentrations are equivalent 3.2 lb and 2.0 Ib, respectively Jn contrast 10 steam generators in central power sta ‘on industrial steam creased by a rapid rise water le is advisable to use an ani which have extremely (Beading > 8), sho ‘Two types ate available: the solu ble polyamides. Ti ler sludge. but they do tend to form s and transfer lines. Neither type is effect tamination, but under noxmal operating slyeols ace more efficient and convenient to use, An exeelient «an be prepaced by diluting S gal of UCON $0 HB $1004 to 50 gal with156 THE CHEMICAL TREATMENT OF BOILER WATER OPERATING 2ROCEDURES 187 he polyacrylates are more stabl+ “han casboxymethylee! Is advisable to i perature and alkali ose at high because “ne polymer is heid together by ca foam, Femmin an 850.psi boiler. ‘hat happens t The major 10-25 pereen that i also present in the feed water walls of brown algse (kelp) isa poly ur var 2 some concentration, ¢y, The eonsstration of the salt inthe bol water in, norgine, and alginic acid. Mannuronie acid isthe poly. tease or decrease depending >on the rate of blowdown, If ama. merizing unit of alginic acid, polymers such as sodium carboxymeth ylee are also used Ie, Synthetic is found that the change in total in the feed water) in Ws ve — be + Sey 68) volume of water in be: =2- (gal) 2 water (Ib/gal) (eal/h) feed rate (gal/h) of change of concentratiar. of creased by entering feed wia:z7 and decreased by blovidown defdt = p2¥ ~ bev 69) Assurning of opera which under any particular set the varies are first separated de = Wop — be/Vyar eat (610) ing imgesis form of the expression on the left at is found in a table of f dxfla + bx) = ibylog a+ bx) Sodium polyacrylateif f t f f ¢ ( t 158 THE CHEMICAL TREATMENT OF BOILER WATER and thus, de = oe Hence, Yoga EE = -b0-1yY (612) or fey — be = (feg~ bee ™'~"2 Eq. (6-13) for some purposes is more convenient to use if solved c= fold + (Co ~feylb)e TOMY (6-14) [As 1 becomes large the exponential term becomes vanishingly small ané Eq, (6-14) reduces to Eq. (1-3) dey = fb = (3) As an example of the use of Eq. (6-12), suppose itis necessary to calculate thelengthof time ‘the concentration of silica to reach 25 ppm in one of the 850-psi boilers, assuming it is just being started up, with the concentration of silica in the boiler water equal to that in the feed water, i2.,09 ppm. The values to be substituted are 000/24 X 6 = 21,600 gph b= 111,000/24% 6 = 771 gph ¥ = 25,000 gal ¢ = 25 ppm SiO, Go = ¢y = 09 ppmSiO: Therefore 1,600 X 0.9 — 771 X 25] — = 7714/2500 [21,600 x 09-771 X09] loge é fee (ea fi ( ( ‘ OPERATING PROCEDURES 159 Jog. (0.0088) = ~0.0308" -4.73 = —0.0308/ 1 153h fone wants on of silica Eq. (6-14) would be used eo 771188 28 000 4s = (21,600 ¥ 09/771) + (09 ~ 21,600 0.9/7 Ye = 252+ (09-252) 14 = 252~(243¥ 0.227) = 19.7 ppm 12) suppose r in one of the 850-8 Sia. How long will it take fo return the concentration to 25 ppm Sis. if the Blowdown rate is increased to 1000 gph? (Note that when B isin creased fincteases by the same amount, je.,= 21 829 gph.) (21,829 X 0.9 ~ 1000 x 25] [21.829% 08 — 100033] t loge 10001/25,000 (0.433) = -0.0400 -0.837 = -0.0407 1 = 209h ‘The foregoing examples show matical analysis to the operation of ab we information; a number of similar an appendix. In Section 5.5 the volatility of silica was discussed and it was noted that the extent of volatilization depends upon the pressure, steaming and the concentration of silica in the boiler water, Barker?) s ited @ curve showing the relationship between the concentra ler water and the pressure of the boil steam at of below the m Using the methods of analytic ge idy problems ate included in160 P = —774108 o(ppm SiO,) + 1948, (6-15) bpm of SiO, woteris Tog,o(ppm Si0;) (1500-1948) (774) = 058 | ppm SiO, = 38 et al.24) have presented data relating the ratio of sitica in steam boiler water to the alkalinity of the boiler water. The following their data reasonably wel logioR = 0.01067 F—0.17( 16) where: R = ppm SiO; in steam) boiler water 1F = satucation temperature of steam epm OH” = equivalents per mi ydroxyl ion Suppose: P= 850 psi; 1 F = 525; ppm SiO; (in boiler water) = 25; Paalkalinity = 140; M-alkalinity = 201; pH = 11.2, Epm OH” can be eal: ‘culated from pH or from (2P ~ M) as follows: pH = 112 POH = 140-112 = 2. (OW) = 10-28 = 1.58% 107 ep! 158X107 X 10? = 1.58 epm OH” (2P—M)x 0.02 = epm on (2X 140 ~201) x 0.02 = 1.58 epm OH Then, 10g oR 0.0106 x 525 ~0.17/1.58~8.27 = -292 2 OPERATING PROCEDURES 161 = i 0.0012 0.0012 X 25 = 0.03 ppm SiQ; in the ste dete of doiler water and titrating to the end point of phenol standard acid. P- and M-alkal ppm CaCOs, but B values are in the unusual terms of parts of carhonate pet 100,000, The B value is converted t ppm CaCO, by multiplying by 16.6; the resul (2P ~M), In the above example B value is (2X 140~201)/16.6 = 47 The normal range of B values for 850-psi boilers is 6-8. Ata B value of 8 '¢ seam would contain 0.018 ppm SiOz and the pH of the boiler water would be about 11.8. TABLE 6.19 ppm CaCOs pom eac Os (GPM) 080 = ppm NOH In Table 6.19 the pH, P., M water from 850-psi boilers are listed, (QP ~M) is a measure of hydroxyl fon and 2(M — P) is a measure of car Donate ion. be noted that ppm NaOH calculated from (2P ~ M corresponds fuisly closely to that obtained from B value: this provales 3 cheek on theaccuracy of the P-and M-alkalinities. Both the P and B values samples in this table the ¥162 THE CHEMICAL TREATMENT OF BOILER WATER the make up (see Fig. 6.3) . Chemical Analysis and Control Routine analysis in stean-generating plants serves three purposes: it makes possible the correct operation of water treating process units; it detects eontamination in components of boiler feed water; it ensures ade. ate protection fort ‘establish a testing obtained wi um number of tests. As the fi proper frequency of testing of bol is useful he concentration of an added chemical al value, supposing none is added 1, ya» is caleulated from Eq, step in determi ate = =bi/V = by loge? WV 0693 ov i ( ( ti Hee ‘ ( ( OPERATING PROCEDURES 163 = 0.693/0.0308 = 25h ‘This means concentrat during that p is desirable to keep the concen he range of 10-15 ppm. There ‘onder to detect an injection pump failure or a plugged phosphate line before ige of concent. ion, itis obviously necessary to test for phosphate mote afte per day. Using Eq. (1-10) hosphate suld decrease from 15 t0 11.7 ppm, siould the supply would be advisable to enneentration of phosphate once every 8 times at various blowdown ratios in the 850-psi boilers being used as an example TABLE 6.20 Half-Depletion Times R Percent aye ha to 100) 0.0926 8 67 0.0595 5.0 0.0439 ie 40 0.0347 20 33 0.0287 M4 Raw water must be dete removal is a consider ish the proper dosage of magnesi water is variable. recked occasionally for M proper dosages for jea concentra16a THE CHEMICAL TREATMENT OF BOILER WATER 16s B . = ers. The instument sh ree 9, when It alas eee kegs by the versenate ee absence of a continuous analyzer, each softener sho Feet hardness every 2h. Continous analyzers that monitor Hy all ae mandatory on deminer boilers. In normal operation ee unit is indicated. Asa deminer é : the eMuent and its pH Pls bru a] gi cet Neutralizing amines ar us g) 2p 2] 8 cient 10 aie its pH to 8-9, so the rep Sees densote is necessary 0 apulate the dosage of amines. Most contamina 5a al é Be li canbe detected by continuous conductivity monito seas vena | dee Of combined condensate rises, indivdual returned seams. should. be z e| 2|"*" ‘| Faa8 checked—usually for hardness and silica. On boacd ships, however, iis Sale ties he eoncentation of sodium chloride inthe vonden 5 sof gt Reeve lenaresue aide sate Frequently to detect condenser leaks and c mn by seawater Bl) glenegeeess | 8888 Feed water for boilers being tested with ch cked 3 ae a lady for hardoess so thatthe feed rate of chelant can be adjusted to te Rl issaBeges proper value. Sulfite (or hydrazine) residl shou alto be determined | 2| the feed water once per shit. The concentrations of slic and chlonde in cee feed water when compared to those In bolle water ean he used to appro 5 ot percent blowdown, Se tests sted Table 6.21 ean be peformed reasonably wel by oer | Eleheeauihe and glassware~burets, vol S)steeiase: Simplified. boratory procedures eescacasé ‘More difficult for boiler operators.los THE CHEMICAL TREATMENT OF BOILER WATER unbuffered sampies st ineralizer effluent often lowers the pil of wecks for fe water by 4. Continuous Analyzers fs used to drive tur ity or the concentea y is affected by certain opei Jit is best to sample precatutions are IF it contains It is advisable to monitor bines, by measuring, jn a condensed sample, As steam pui variables (load swings, water level, soot-blowing, ete and monitor continuously, bearing in mind 1 necessary to ob ta sampling be ing nozzle must equal steam in the pipe being simpled. For measuring carryove 1g nozzle should be installed in one of the superheater supply tubes between the steam drum and the superheater. When sampling 2 pipel o the Mow of steam. Sam ust entering the samy single varying to some degree the pressure of the boiler. Below 400 psi. steam may c ‘of solids: at 600 psi.0.3-0.4 ated steam for high-pressure turbines, exceed 30 ppb. As a get tral cule, steam at pressures of 900-1200 psi is of adequate purity if it con URES” le? 7 carbon dioxide, dissolved solids (* 0.1 ppayum werge. T yydrazine is used as an oxygen scavenger because so a is produced by fiest NaitCOs 870 oa? Na,SOq 1300 130 NaC 1330 13s Na,CO; 1600 160 N01 4500 430 Her 7800 730 Steam purity cam also be assessed by measuring the concen *Manufsctured by Beckman Instruments, 89 Commerce Road, Cedar G Jersey 07008.‘ fi ( ( Ca ee ( ( 168 THE CHEMICAL TREATMENT OF BOILER WATER OPERATING PROCEDURES 169 a reference electrode. the concentration of s ppb; there is no interference by Analyzers are available that conden jous analyzer takes advantage of of hydrogen to monitor 8 generated in the internal corrosion of boilers. 2°) Ae: of atomic weights in the reaction 3Fe + 4110 = FeO. + ally (17) al the evolution of I Ib of hydrogen gas corresponds to the oxida of 21 1b of steel by hot water. Thus, 3b Hs X steaming rat, Ibfday X 2 me ia My etay Feioss, Ibfday = concentrations of hydrogen, normally less than 1 ppb, are also *d in the thermal decomposition of a:ganic materials such as poly. mers, lignins, tannins, chelants, hydrazine, and amines. hydrogen, attibutable to general corrosioy be taken of tion of boi stress increase corrosion and the rate of eval A deaer: at con: sloading, surges in feed water demand, intemal me Fes, or interruption of the steam supply can drastically reduce the efficiency of deaes For this easot it is worthwhile installing @ dissolved oxygen analyzer on the denes * Milton Roy Company, 5000 Ps (Orion Industrial, 380 Putnam Ave., Cambridge, Massachusets 02139. 271+ 40, + H,0 = 271" + 20H 19) chemical, its k In cases of poiso 2Ag + Cl + KO, + HO = 2AgCI + 208 sve, New Jersey 07 "8.0 : CHEMICAL TREATMENT OF BOILER WATER. 1s (1500+ psi), but moalerate pressures ‘An instrument a 2 increases; the change water, A standard measuring eorrosiveness by electrical me in a 600-psi boiler is 0.2-0.7 mpy: at 850 psi less When considering the application se that depend upon electrical s Fe amines can quickly inactivate them by forming ‘conducting surfaces, ¢. Interpretation of Water Analyses As there are @ number of sources of error in analyzing boiler water, s for selfeconsistency be sions from water 3 aw any prac to do this, it i assumed that samples from five 850:psi boi with their Teed water are silica, and catalyzed phate and supplern se analyses are displayed in Table 6.23 In scanning the results in Table 6.23, the kes the eye. As sa t ¢ ( ( ‘ (eee (Heer OPERATING PROCEDURES . 14 TABLE 6.23 Boiler Water Analyses fn Boilers Sats waer “7228S solids (ppm) $2.0 tppmCaCO3} 9.0 102) 09 ppm Nac 40 ‘pm NazSOq), 220 Phosphate (ppm POs”) = (ppm $0," os compared water in each boi is done by dividing the concentration of each salt by the corresponding concentration of each sal icant of these ratios are those of total dissolved are routinely measured by conductivity, and those of total which are skewed by the neutralizing amine added to the feed jute to the alkalinity of the feed water, but not to + water. Table 6.24 contains the blowdown ratios of salts in the five boilers calculated from results recorded in Table 6.23. TABLE 6.24 Blowdown Ratios asa 2h a8 38.0 288OPERATING PROCEDURES ls AAs the total equivalents per million of anions equals that of the eations he analysis is correct as given and that nothing has, equivalents per million are identical on of cations and anions are quite different, It is possible bbe equal, but to find this in a natural water is highly unlikely id in Table 5.4. Factors are given in Table 6 18 PPM CaCOs to ppm ior and co ¢} TABLE 6.26 6.3 OPERATING GUIDELINES Conversion of Concentration Units ‘The chapter is concluded with some miscellaneous infon havi (TH CoH) X08 = x 0.082 = a Renee f 7 ui Sua easy 2 to do with practical operations of boiler plants: for convenience these eee Sonia ace classified as chemical and mechanical, Among t ies i Serpe eennasis! are procedures for laying-up boilers, proper methods of treatment to pre xX 0083 = pare 2 boiler for shutdowa, and costs of water and chemical trea xX oo = n quality, desuper x 002 = Procedures relevant to the operation of marine ppm sid; X 4.27 = ppmsiov” x 00% = Table 6.14 can be verifled by substitu s are summarized in Table 6.27 se analysis i javen there in Table 6.26. The res cst of chemieal treatment is easily de more than one souree of supply is available of minimum treating cost is more complicated, Suppo. is necessary to generate 100,000 Ib of process steam TABLE 6.27 vowever Verification of a Water Analysis n a 300+psi boiler, using 100 percent make up, the only ext ae ent being filtering and softening by cation exchange. Internal (eeu iors etapunt teenie to be accomplished with a single tion priced He ieee at $0,80/lb and applied at a dosage of 50 ppm. The daily cost of int TH 7 Mg 17 0.68 treatment depends upon the blowdown cate ofthe boiler and is calculated Creer de eect eee 0.96 by the following formula Na 1s Nat 150 06s P 4 HCOy CH Siday = $0 (ppm) X 0.80 (S/B) X 8.34 (ib water(gal) x M 65 8 cL 7 70 biowdown rate (gpd) x 107% $0.17 170 Si. 12 150 The blowdown rate,of course is governed by the quality of the feed water = To illustrate this. suppose two sources of water, and Il, ae available with ToS 160 33 saa compo: ins as shown in Table 6.28.176 THE CHEMICAL TREATMENT OF BOILER WATER TABLE 6.28 . Water Compositions ‘Source of water Limitations, 3008 Components tou oiler, maximum 2 1s 12s 700 70 170 3509 ‘The data in Table 6.28, when plotted as shown in Fig. 6.4, readily gives the proper mixture of waters f and II for minimum blowdown. The figure is constructed by plotting the percentages of I in II against the minimum blowdown necessary to maintain the limits specified in the last colurnn in Table 6.28 (also see Table 6.12). To plot the M-alkalinity line, for exam ple, itis noted that at ze:0 percent of I (100 percent of {1}, the blowdown ratio is 700/125 = 5.6, and percent blowdown is 100/5.6 = 17.9. At 100 percent of I the corresponding blowdown ratio is 700/25 = 28, and perce blowdown is 100/28 = 3.6. Silica and total dissolved solids lines are pl ted similarly. It is apparent from an inspection of Fig. 6.4 that the proper mixture for minimum blowdown is 83 percent I and 17 percent Il, At less than 83 percent of I more than 6 percent of blowdown is needed to keep the Malkalinity at a maximum of 700 ppm CaCOy. At mote than 83 pé cent I miore than 6 percent of blowdown is required to keep the concentra tion of silica at a maximum of 175 ppm SiOz. Total dissolved never be the limiting factor because of the re ‘curves, In operating any boiler limiting concentrations may vary from time to time, with blowdown being controlled by whichever component reaches its limiting value firs. as is often the case, water from one source costs more than that from another, the determination of minimum cost isa little more difficl For example, if T costs $0.45/1000 gal and II costs $0.28/1000 gal, i i necessiry 10 compare water costs of various combinations of the two soutees with the corresponding chemical costs, This is done in Table 6.29. where it Is seen that despite the highest cost of chemical treatment, the total cost using If by itself is less than any combination of the two sources. TABLE 6.29 (OPERATING PROCEDURES Water Treating Costs Total (Siday) Water (siday Chemicals Blowdown Feed tena Minimum lowdown (21 Water cost (iuayy apa 65/1000 at) ERESSsi ti ( ( ( ( ( 178 THE CHEMICAL TREATMENT OF BOILER WATER Fig. 64 15, water tubes are inserted in the drums and headers and then expanded to form a st the process js called rolling. Occasionally, oll leaks develop, notably after replacing a phosphate treatment ela Phosphate is leaks and, in fa ‘often seal leaks by hate feed to «Up to 123.€ (253 F Phosphate increases as temperature increases.("2) Above the solubility decreases, reaching a F appre: ppm at of excess NayPO, seals leaks. In Chapter 5, pages 78-81, the chemistry of hydrazine as an oxygen Exeept in OPERATING PROCEDURES 199 scavenger was discussed, Table 6.30 contains re ship to compare the acti 5 of tests made on @ s of catalyzed and uncatalyzed hydrazine at ter temperatuces that prevail while a vessel is th slage healer establishes the temperature of feed ¥e economizer—the zone in which oxygen scavenging bbe complete, In power, 4 tem ales. As power is at around 225 psi er occurs and letdown steam, Tests were also done at perature of the extraction ste (390 F at the heater outlet), autom: is supplied in place of extrac TABLE 6.30 Qualitative Effectiveness of Hydrazine eee netaaattpeaeAeeaaa Hydrazine residual 4th Stage heater outlet (rpm) 410F 390F 375 Catalyzed 0.01 Type of hydrazine Uncatalyzed oat m m e 0.03 5 s s 0.03 : 5 es 008, 5 : 5 0.08 5 : m marginal; v* umstisfactony ta 0.03-ppm residual of hydrazine in the feed water gives ‘ory oxygen scavenging with either catalyzed or uncata lyzed hydrazine. and that the outlet temperature of the fourth-stage heater ‘much below 390 F if satisfactory seavenging lyzed hydrazine, When b nspection ar for major re be as clean as180 THE CHEMICAL TREATMENT OF BOILER WATER oral, Also, the boiler should not be drained on shutdown until itis coal Ifa boiler is to be placed on standby and is being kept filled, ready for to maintain a blanket of nitrogen in the to pre of the wet is placed on standby comes off is added to give an M-akkalinity of 500 ppm Fe is raised to 150-200 ppm. inder equipped with a 2-stage pressure reguiator is con- he nitrogen pressure at 10-15 psi, then open in a positive pressure of falls to 5-10 psi, and superheater. Ma ress the vahes to th LY warner suPpLy and thus be obtained from190 THE CHEMICAL TREATMENT OF BOILER WATER into evaporators, some portion of which can be expected to carry over into the feed water. As the tolerance of high-pressure boilers for low, operation in these areas should be avoided, if possible. Also, if the ‘evaporators are in operation as the ship moves into a shallow harbor, the hhighsalinity alarm may sound when, in fact, the salinity level is norm terials a dissolved gases, which frequently increase the conductivity enough to act vate the alarm, Foaming in evaporators is another source of contamination in the distil late, Usual causes are over-concentration of brine, operation at rates much higher than design, and contemination, especialy oil, entering with the seawater, To eliminate this nuisance most polymer Formulations for treat- ing evaporators contain antifoaming agents ‘The blowdown of marine bollers is managed differently from that of stationary boilers. Continuous blowdown is either to the bilges or to the shell of the evaporator, often through a conductivity monitor on the water in the steam dium, the rate of flow being controlled by a 1/164n. orifice in the line. Because of safety restrictions this rate is so low that celatively suspended solids do not move into the continuous blowdowa lire, ‘but instead concentrate in the boiler. For this reason, high-volume are made intermittently to the bilges ar overboard from the surface, bot- tom, and water wall blowdown valves on the boilers. This is done every 7-14 days, whether the vessel is in port or at sea, Thus, if a voyage is ex pected to last 10-14 days, blowdown should be done just before departure and then again in the middle of the voyage. Similarly, if the vessel is to remain in port longer than three days, the boilers should be blown down ‘upon arrival and again before departure, When boilers are under excep tionally good control, the period between high-volume blowdowns can be ‘extended to three weeks, in which event blowdown can usually be done in port, If itis done at sea, the following procedure is used: 1, Slow the engines and level off the plant for one boiler operation. Secure fies in the boiler to be blown down, and open the supes- beater vent. 2. Allow the pressure to fall to at least 15 psi below the normal boiler ‘pressure, at which level there is no danger of interrupting circula- tion. 3. Open blowdown valves wide, then close them in a single operation, taking 15-20 s to open and close the valves, Maintaining 2 visible a) Surface steam deur, 'b) Bottom blowdown on the mud drum. ce). Side water wall header 8) Rear water wall h 5. Secure the other boiler and repeat the foregoing procedure. 6. Treat the boiler with chemicals, te necessary 10 #@- esta ers. step 3a) is used to remove below the normal water lev and scums; its ou! steam drum192 a a 3) “ 6) © oO @) O) 0) an a3) aay as as) THE CHEMICAL TREATMENT OF BOILER WATER REFERENCES Klein, H. A., Kurper, J. .,and Schuetzenduebel, W.G. 1965, Cycle cleanup for supercitical-pressure units. Pre. Amer, Power Conf. 27:156. Shields, C.D, 1961. Boilers: tions, New York: McGraw HU Wangerin, D. D. 1964, Waste-heat bollers~principles and ap- plications. Proc. Amer. Power Conf, 26:682. Skrowki, B.G. A. Sept., 1958. Fuels: look ahead. Power 102.75 Denman, W. L. and Salutsky, M.C. Sept,, 1968, Boiler scale control. Power Metcalf, J.R, Jan Ind. Water Eng. 8 (1):16. Walker, J. L. and Stephens, J. R. 1973. A comparative study of chelating agents: their abuity to prevent deposits in indus- trial boilers. Proc, Intl, Water Conf, 34:134 Meites, L.,ed. Handbook of anelytical chemiztry. 1963, New York: McGraw-Hill. pp. 1-45 Venezxy, D.L. 1971, Thermal sta Proc, Intl. Water Conf, 32:37. Venezky, D. L. and Moniz, W. B, Thermal stability of nitrilo- iiacetic acid and its sales in aqueous tolutions, U.S, Clearing: house Fed, Sei, Tech, Inform. AD 1970, No, 715776, 13 pp. Swanson, D. A. Dee. 1967, Advances in boiler water trea ment. Ind Water Eng. 4(12)-22. Edward, J. C. and Merriman, W. R. 1963. Use of chelating agents for continuous internal treatment of high pressure boil- 15. Proc, Inel. Water Conf. 24:35. Lorene, W. F. and Bermer, R.A. May 30, 1972, Compositions and methods for controlling scale. U.S. Patent No. 3,666,664, Ralston, P. H. 1969. Scale control with aminomethylenephos- phonste, J. Petro, Techn. 21:1029 Klein, HA. Oct., 1962, Use of coordinated phosphate treat- ment to prevent caustic corrosion in high pressure boilers Combustion 34 (4):45. Noll, D. E. 1964. Factors that determine treatment for high- presture boilers. Prov, Amer. Power Conf. 26:783. Pocock, F. J. and Stewart, J. F. Jan., 1963. The solubility of copper and its oxides in supercritical steam. Trans. ASME. J. Engineering Power 85-A:33. Lypet, characteristics, and func Boller chelant reatment: an update ty of EDTA and its salts. oy (ay es) 6) Go fe res ( (eee fi ( t ( OPERATING PROCEDURES 193 Povock, F. 5., Lun, J. A., and Seibel, RW. 1966, Control af iron pickup in cycles utilizing earhon steel feedwater heat Amer. Power Conf. 28:758 Levendusky, J. A. Pros, Amer, Power Conf, 28:758. Bonafede, G. and Sandell, 1. W, Dee.. 1965. Copper, and nickel pickup in a power station feed water system. A tralasian Corrosion Eng, 9:19 Barker, PA. Mar.-Apr., 1973, Water treatmeat for steat generating systems. dnd. Wacer Eng. 1202) 5. Coulter, E.F., Pirseh, E.A.,and Wagner, E.J.Jr. 1986, Selee tive silica carry-over in steam. Trans, ASME 78:869, ‘Amer. Soe. Testing Materials. 1977 Annual Book of ASTM Part 31, D1066:69: 60. Standard methud of sai water sampling ang analysis E.S., ang Dravnicks, A. 1958, refinery equipment, Corros ‘Amer. Soe. Testing Materials. Philadelphia. Pa Book of ASTM Standards, Pert 31, D2776-72, i Jor conosivity of water fer (electrical method), 1c Power Conf. 32.729. b, F. C. and Grabowski, HA. 1945. Silica deposition in steam turbines. Trans, ASME 67°309, Herman, K. W. and Gelosa, L. R. May, 1973. Water