yr Part2 Mitigate Corrosion in Condensate-Return Systems Understanding the chemistry behind corrosion in condensate-return systems can aid in selecting and properly employing the best mitigation technique ‘SK. Mukherjee Consuitant IN BRIEF ‘CORROSION COMBATING 12 Importance of steam-condensate return systems to boiersin the chem- ical process industries (CP?) cannot be overemphasized, especially with regard to enhancing operating efficiency, Tis also enables water conservation by re- ducing waste. However, condensate-retum ‘systoms are prone to severe corrosion due lo the presence of non-condensable gases, like carbon dioxide (CO,) and oxygen (0,), which are associated with steam generation. This often renders a condensate-retun sys tem ineffective, and can result in additional energy costs, as well as the extra cost of re- placing lost bole feedwater. Table 1 provides ‘an example of the costly effects of corrosion (inthis case, two 2-mm holes that developed in @ condensate line due to corrosion that caused water loss). The cost impact of lost ‘condensate and makeup water can be sub: stantial i several leaks develop in the entire Ccondensate-retum system. This article pro- vides an overview of some current technolo- {gles used to combat the underlying corrosion issuesin condensate-return systems, andthe ways to deploy these corrosion-mitgation techniques effectively, Corrosion mechanisms AAs a first step to combat condensate-sys- tem comosion, the ingress of gases into the condensate system should be mint mized. Ingress of gases can occur In the following ways: * Non-condensable gases (CO, or O,) absorbed trom the ar can dissolve in boiler makeup water: in this case, the non-condensable gas flashes over the steam and eventually nds its way into the condensate ra Peeters Canons header pressure ar 5 Canes tepertne, °C 199 Nakeup water empeatue °C = Baier tice, % = Fila ent, imion 22 eee uel ast St 7,300 atonal makeup wate, metic ions mtyyy_ 5900, ‘Absorption of non-condensable gases in ‘equipment that is inal fl of ar (steam- ing operation during startup) or air leak ‘age in equipment that is handing steam at Sub-aimospheric pressures +00; produced’ in the boll by the” decomposition of boiler feedwa tor alalinty that has dssolved into the condensate Te folowing section oulines some spe cite chemical-reaction mechanisms. that can cause corrosion in steam-condensate retum systers. Condensate system corrosion in the pres- ‘ence of oxygen. The following reaction rep- resents the Corrosion of on (Fe in water [7 Fe + 2H.0 5% FelOH)2 + Hp This reaction continues to equilibrium if no Opis present (2. Also, the formation of fo "us hydroxide (Fe(OH), increases the con- Gensalo pH and retards the reaction rate When O2is present in the condensate, the following reaction occurs, forming hydrated femic oxide (Fe03+H,0) 4Fe(OH), + Op 5 2Fez03H,0 + 2H,Oleads to debris that can deposit in small parts, causing blockage, as seen in Figure 2 Combatting corrosion As stated previously, the ingress of (0, 6r CO, into the condensate is the ‘main cause of corrosion in conden sate systems. Hence, any effort tore. duce corrosion to acceptable levels ‘must deal with expeling these gases from boiler water and neutralizing their corrasive effect with the addi- tion of chemicals [7,3]. The main pro- cesses for fighting condensate-sys- tem corrosion are summarized in the following sections. Deaeration. Tho boler feedwater is mainly comprised of makeup water and return condensate. Dissolved 0» is primarly present in boiler makeup ¥ / water, while cissoved CO, can be FIGURE 1. Inte presence of oxgen,erc-xdecomasion ccs and can weakhavec on anéensete- present in the return condensate. ‘stem ecpment Both gases introduce corrosion po- tential for the boiler and the conden Faric oxide, also called hema- 2NsHCO, + heat 5 Na,GO, + sale system. Deaeration effectively tite oF red rust, isa loosely adhering CO + Hz reduces dissolved non-condensable oxide layer, and can travel with the gases trom feedwater. In the de- condensate flow through the con Na,CO, + HO + heat + 2NeOH aeration process, the makeup water donsate piping. An example of iron- + COy and return condensate are heated ‘oxide corsion is shown in Figure in @ deaerator vessel with low- 1. The ingress of dissolved O> in As the steam from the boller pressure steam to a temperature the condensate prevents equilbium transfers its latent heat and con- that is sufficient to reduce the par from being reached, and ferrous hy- danses, the COp dissolves in the tial pressure of the dissolved gases dfoxde is removed continuously condensate, depressing the pH. over the water surface. This results fom the inner wals of the piping The following reversible reactions in almost all of the dissolved gases ‘and ftings (2) take place: coming out of the liquid phase, The The following are the two types dissolved gases are vented from the fof comasion that cocur when Op H,0-+ CO, %H,003 deaerator vessel along with a small is present [3 ‘amount of low-pressure steam to aid * Generalized corrosion on the metal HyCOs H* + HOO venting. This process is known as surlace, which causes a loss of mecharical deacration ‘metal from the entre surtace HCO 5 Ht + CO; Chemical oxygen scavenging. * Oxygen pitting, which causes a ‘Some residual Op remains ater me- highly localized loss of metal that The corrosion of iron by carbonic chenical deasration, as. the partial can result in a catastrophic falure in acid (H;CO,) is promoted by hy- pressure of O, cannat be reduced a shor time. Pittng begins at weak drogen ions (Hi) from the above to zero, This is @ potential source for points in the oxide fim and at lo- dissociation reactions. The overall Oz corrosion. Chemicals are added Cations where the fm is damaged. reaction forming ferrous bicarbonate to react with’ the leftover O. The The corrasion penetrates into the (FeHCO})) is chemical is usualy added below the surlace, effectively drling @ hole water level in the water-storage sec- into the metal 2H + 2HOOs + Fe $s FAHOO3)2+Hp tion of the deaerator. The most com- Condensate system corrosion in mon Oz scavenger is catalyzed so- the presence of CO Carbonates _A low pH causes generalized loss _ dium suifte (2NaSO4), which has the ‘and bicarbonates, such as sodium of metal, rather than the localized following reaction: bicarbonate (NaHiCO;) or sodium pitting caused by O>. Corrosion is Carbonate (NajCO,), are commonly characterized by the general thinning 2NaSO, + Op $ 2NaSO, present in Doler makeup water, and of the pipe wall or groaving along the these anions are generally caled bottom of the pipe (2), This thinning _ Another O» soavenger is cethyhhy “water alkalinity” With the appiiation often leads to failures, particularly at droxlamine (DEHA: 4(C-HaloNOH) cofheat, these carbonates undergo the threaded joints. In adaition, coro- TheoverallreactionofO with DEHAis folowing reactions in the boler [7, 3]: sion that causes decay of pipe walls as folows:FGURE 2. Corio pipe wal can bad to widespread ists, nto the formation of depts and ockages in sal ping components 41CgHg)sNOH +902 8CH{COOH 4 2N; + 6H,O ‘The addition of DEHA also has a passivating action on metal surfaces. ‘When hydroxide alkalinity is present in the boller water, the acetic acid Is neutralized and removed in blow- down as sodium acetate, Controlling corrosion ‘The objective of chemical control in the condensate is to elevate the conde H so that the ingress of carbonic acid is neutralized. Neu: tralzing amines (R-NH,) are used to neutralize the aciaic H* that is gener- ated by the dissociation of carbonic ‘acid. Neutralizing amines also serve to increase the pH of the conden: sate, The amines hydrolyze when added to water, and generate the hydroxide ions that are necessary for neutralization. The chemical reaction for a neutralizing amine in water is, folows: ANH, + H,0 5 RANHg? + OH- The overall neutralization reaction is shown below: FLNHS + OH + HCOs" + HO HCO. 5 R-NH3* 62 By regulating the dosing rate of the neutralizing amine, the pH of the condensate can be elevated to the desired level. Many amines are used for condensate-acid. neutralization and pH elevation. Morpholine and yclohexylamine are common neu: tralizing amines. Often, a blend of morpholine and cyciohexylamine is a better choice than using either alone. The choice of neutralizing amine depends upon the distnibu- tion ratio and the numiber of con: donsation sites (3 ‘Another option for controling con densate-system corrosion is the use of filming amines. Octadecylamine is a common filming amine. Film: ing amines are introduced into the team header, and form a very thin ‘amine-fim bafrier on the metal sur- face by replacing the loose oxide scale, This bartier layer prevents O, land carbonic acid from reaching the bbase metalin the condensate-return lines. During the initial dosing pe: Tiod, loosely adhered oxide depos: its are ited off of the metal surface and repiaced by an amine film. This, is due to the surfactant properties of the amine, In the case of old or untreated condensate lines, excessive dosage of filming amines can dislodge pre- existing deposits and the sludge can foul the condensale-retum system, This sludge can potentially reach the boiler, causing tube failures. How: ‘ver, for uniform and effective cov: erage of a large condensate return system, a biend of a straight flming amine with a neutralizing amine and emulsifiers provides a superior film bond, reciuces deposit problems and provides better and more economical system coverage [3] ‘Yel anather option for abating cot- rosion in condensate systems is the use of DEHA as a matal passivator and Op scavenger. DEHA converts loose, ‘unprotective iron oxide (red hematite) deposits on the conden: sate pipe's inner surfaces to a black magnetite protective fm, ferrous oxide magnetite (Feg0q). The follow. ing is the chemical reaction for this conversion [1] A(OpHsJ2NOH + 6Fe,03 5 4Fe:0, + 4CH;COOH + 3H;0 The magnetite layer on the metal surfaces reduces corrosion rates from Oy and carbonic acid. DEHA ly dosed along with a nou: ralizing amine, as itis most effective ata pH higher than 8. DEHA has a high distribution ratio due to its high volatilly, and hence provides effec: ive protection by directly dosing it Into the baller feedwater instead of into the steam header. Due to the high distribution ratio, DEHA also spreads more effectively to the en- tire steam and condensate system tn, Boiler makeup water that is low in alkalinity helps in reducing car- boric acid corrosion in condensate systems. Also, less amine adcition is required. Dealkalizers and reverse ‘osmosis can be considered for the reatment of boller makeup water to reouce alkalinity When condensate in the piping is near its saturation temperature, car- bonic acid formation is minimized, as the solubility of CO, in the conden: sato is low. However, if the tempera: turo of the condensate is below the saturation temperature, likely due to improper insulation of the conden: sate lines, more CO goes into solu: tion, causing potential carbonic-acic Corrosion. Therefore, itis important that condensate return lines are properly insulated and that the in-tegrity ofthe insulation is maintained of iron which was sitting upstream Similarly, Op scavenger concen- during the lifespan of the steam- of the closed valve, There are three tralion must be precise within the condensate system. Giferent tests that can be run, for system. If DEHA 's used, a residual which proprietary methods of testing of 100-150 ppb should be targeted Monitoring corrosion are avaiable. [o). Ths residual quantity will take Monitoring corrosion in condensate-* Thesuspended:iron test measures some time to appear, as the DEHA return systems allows for early detec- insoluble suspended iron by pass- il ntialy be consumed in passivat- tion of problems — when the prob- ing the sample through a mem ing the system. A cooling coll should lems are stilrinor these problems —branefiter Suspendediron, mostly be used for colecting the sample {0 unnoiices, they can very soon fericiron|Fe030rFej0,, whichis to avoid loss of volatile chemicals if Become maior problems, leading to Fe,03+FeO)ietheresutotan ox there is steam flashing. leaks, plugging of condensate Ines dizing.conaiton nthe condensate, Corrosion coupons. Pre-veighed ‘or catastrophic boiler-tube failure. The point of this test is to indicate strips of metal (coupons) with very Without proper corresion-monitering procedures in place, steam systems can have undering issues that Without proper corrosion-monitoring procedures in place, persist for long periods of ime. De- s i aati Geese eShuing on tie toatmort method, Steam systems can have underlying issues that persist for Condensate monitoring can vary, but long periods of time. generally, the folowing tests are re- Quireds 1. pH testing at various locations inthe presence of O, in the system, similar composition to the metal- the condensate system either through improved deaera- lurgy of the condensate system can 2. Measurement of iron levels in tion ar the use of better O2 scav- be used to monitor the corrosion the condensate fenging in the boiler. Suspended rate. Corrosion coupon racks that 3. Measurement of residual amine iron levels in excess of 60 parts fold three coupons are generaly in the condensate peer billon (ppb) are indicative of used, One coupon is exposed for 30 4. Corrosion coupons serious corrosion days, one for 60 days and one for Evaluating pH. itis necessaryto test + The total ferrous and ferric iron 90 days. The coupons are removed the condensate's pH to determine if test measures both dissolved iron for each time interval, and the weight itighigh enough to prevent carbonic- (mostly ferrous) and suspended loss of the coupon is. determined. ‘acid corrosion from occurring. Con- iron (mostly fer). a membrane From the observed weight deterio- densate pH measurement should be iter is used to remove the sus- ration in the coupon, the corrosion cared aut at more than one loca- pended iron, the test will measure rate is calculated in mils (0.0001 in.) tion, to ensure that carbonic acid dissolved iron, For most industries, per year (mpy) / does not attack differently in sepa- a test result of 0.8 parts per mi- Edited by Mary Page Bailey rate sections of the system, This can lion (ppm) is considered a good happen when neutralizing amines test result References with ow distibuton ‘rates ike + The toll iron test allows for 1. sent A tw Suan Sn Cont morphojine) are used with multiple tracking total iron over time with- Su 9 Cl Coron tr condensation sites. ut regard for ‘oxidation state, D7#ltAonaon Men Protec Pog, Wiis sola Concerts erm Tis ea promos veuable Woe, aa post should Ge ensures tat po. back about the ofecivenose. ot > ayn Sul ces 1 cesta. ‘sure to air is minimized, and that the the amine treatment program of 3. Betz Latoraiorls in. “Betz Indus Water Candi PH test is run as quickly as possi- the condensate ‘toning, 9th ed, Sapt. 1991. bie, Ao, the sample shoud De wel Residual fming amine and Op 4 wus, ped Sok Osis wn cooled otherwise, CO, anciamine seavengers. Ia fining amine {8 wanes. eo Can both fasn off ofa fot sample, urzed the residual should be mea. ® rote feo) igen aiterng the pH.ApH of 8 orhgher sured. As stated cari, tho most gH Bikey ant Taha Shouts be argetod Soremon tring amine tr bodere masa irom measurement on, as a.coro-octadecyamine. I shoud be mea ‘sion byproduct, is an indirect indica- sured on a steam sample — not a Author torofetherlowoHorthepresencoct condensate sample, Dosayo cat be Os somewhere upstream of the con- controled to gue 0.2-0.6 ppm oola- densate sampiing point. If this areais decytamine in steam. Octadecylam- not bang checked for pH measute- ine fs most eflectne In condensato Tents, ron measurement should 69 with @ pH range of 610 8. Thus, the Gone. The sample shout! be om product ray requre supplemental anand wh mo tay ‘a continuously flowing stream to neutralizing amine to be added. A eae avoid slug of ron onde fom the cooling col is requited during sary Sto isco pes opening of a valve. A valve which is pling to prevent steam from flashing Si, operations, troublestonting, azar evaluation ened fron a closea poston (we Of which wit concentrate the amine va St i as poi eo taking a sample)can faeace a sug inthe sample, CHEMCALENGNEESNG WW/CHEMENGOALNE.COM MARCH 2008 af Sk Muinefge fn mse beset con) cute 2 pes Skt) epost on le thar MS AscSencesLis acter elmer a a Funcra Say Prsessre wth more tan 40