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~ VGO TECHNISCHE VEREINIGUNG

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DER GROSSKRAFTWERKSBETREIBER 6.V.

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VGB Guidelines
for Boiler Feedwater, Boiler Water
".,
'-....
"I
and Steam of Steam Generators
With a Permissible Operating Pressure
IIl . > 68 bar
- VGI3.R 450 Lo-
c., ,
ri
I'
i Published by
VGS TECHNISCHE VEREINIGUNG
I: DER GROSSKRAFTWERKSBETREIBER E.V.
lj

Firsl Edilion 1988

(printod In 10051
•••••

• • j •

Atlunliun is drawn 10 the f<lelthal thu eonlcnls aro legally proleeled by copyright
Reproduction is pormilled only wilh the prioI approval altho publisher.
,

Obluinuhlo tram:
VGB-J(RAFTWERKSTECHNiK GmbH
Vorioglochnlsch<wisslJn::;challJiehor Schritton _
Puslloeh 10 Jtl 32, 0.4503U E$son

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The VGB hereby presents a revised version of its Guideline on Boiler Feedwater,
Boiler Waterand Steam "ofStea:mGeneralors With a ~'1rmi\;'sible Operating Pres-
suro > 68 bar. This new edition replaces the "VGB Guidelines for Boiler Feed-
water, Boller Water and Steam for Water Tube Boilers with a Pressure of 64 Bar
and Higher, Ocfober 1980 Edition". The pressure range up to 68 bar is covered
by the "VdTOV Guidelines for Feedwater, BoilerWater and Steam In Steam Gener-
ators with a Working Pressure up to 68 ba(' which appeared as a VdTOV-Code
of Practice in Chemical Engineering 1453 (VdTOV-Merkblatl Technische Chemie
1453, TOV Rheinland Verlag, Cologne).
Tho present Guideline is Ihe work of the VGB technical committee on "Waler
chemistry in thermal power plants" and has been discussed and agreed by the
Association of Steam Boller, Pressure Vessel and Piping Manufaclurms (Fach-
vcrband Dampfkessel., Behiilter- und Rohrleitungsbau e.V.. FDBR), Dusseldorl,
and the Association of German Technical Inspection Agencies (Vereinigung der
Tochnischen Oborwachungs-Vereine e.V., VdTOV). Esson.
The fundamental changes over the October 1980 edition ara that relative to the
scope of this Guideline only the overwhelmingly used mode of operation with de-
mineralized water has been thoroughly considered and Ihal combined feedwater
conditioning with alkalizing and oxidizing agents. which is now widely used, has
been incorporated in the Guideline. Furthermore, several specified values have
changed slightly "normal operating values" in addition 10 specified values are also
I

quoted for fcodwater and steam and the theoretical relationships between pro-
tective layer formation and the effects of chemical conditioning in particular are
described in greater detail.

Essen. March 1995

VGB TECHNISCHE VEREINIGUNG

DER GROSSKRAFTWERKSBETREtBER E,V.
 ,

Contents

Pogo

1 Introduction, scope 7

2 General , ;., f c . 8
1_~l:! 2.1
.. / .~
Protective layer formation -.:~ ~' ,:..•-:.-.•1_;".J.i:-:.•.•; :. _ ..f...
2.2 Corrosion producl transport and deposits
'" ,/ .-- -'.-'.,.' 9
10
2.3 Impurities in stoam 10

3 Chemical condilloning or water/steam cycles . 11

3.1 Feedwater conditioning with alkalizing agents
(all volatile trealment) 12
3.2 Fecdwater conditioning with oxidizing agents (neutral conditioning) . 14
3,3 Foodwator conditioning with alkalizing and oxidizing agents
(combined conditioning) 15
3.4 Conditioning lho boiier water of drum-type boilers 1S

4 Explanallons concerning the slgnlllcance

01 the parameters associated with specified values
and their analyllcal monitoring 1G
4.1 Conductivity , , , , , ,. 16
4.2 17
4.3 Oxygen 18
4,4 Tolal iron, tolal copper " . 18
4.5 Sodium 18
4,6 Silica , . 19
4.7 Phosphate 19
4.3 Organic substances " ,.., . 20

References 21

Appendix 25
 ,,-
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1nJ; tJ d11C 1; Lv 0 • .w:':;'

gcop
0 (I

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-.J ;)~Q!2'"
drjvc<JrdloYl' ;~eY'-' rr-:- 0;'
Jedl J • I /~ /,/
~
/ ~ " cJ. i J d b L,o
1/(J _<I::. C '-;-' c,::r I - ~::' ) cJ l~
,. ~,fl" _
.;;, - U!f t..:..~.,) y'", "'-,./ erfccr ./1 ~ J: _ I-P~~ ,-
(f?1{1i(e. yl')f' ~-;r- c ,/ r
rJ--- b../r L:: LJ/()J _.!:\" ry
" Il! 1,11.
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d'f"c{PI'O{l ;/ G~~"\. I"'J'~ ---.Y~
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Jy...... - ck, I_x' ..::.v Is, y~;;I- - 1 Introductlo~. ~1fope l",; G,

.....c ( I This VGB Guidelinel1ea'is' with the quality require';ents for boiler feedwater, boil-
i(cu/)'c -) I _ 9' r- /'
l....-)J~/
U )IJ};I -C)lJ'-J.~) or water and SJ.~cyn~~our
~!~3~nl state of knowledge, c~~liance with the Guide-
lina will guaranlce'tro~e-froo continuous operation of t,igh pressure steam genera-
P'! e. cr~y e. )yP" ..'N"') /;---'-J (-./'1
/
,,) . (.p' , J '/ ..J/
")
/ f

.•..-
tors, ':l~QQ...4M9..t?Yihe Steam Boiler Directive (Dampfkesselverordnung). as well
as sfoam lurbines. Tho water and steam quality requirements are set out as specj~
V ') U/ ' fied values which are supported by reference to links and i~£tiQ@ within a
itfTci(efC,t;on D\~\J';- d~cY wa lorIs loam cyclo and oxpla nations concerning the importanS? ~artjcular param-
eters, The s~W,ed valljes given in the tables are recomlTlendlltl'Oosand should
C /' f ( '/? ?
')
/~ particularly be taken int8'~era1iQn wheo_constructfng~ and commissioning new
') rl '-- V"--: -l )';'\ P -:J/ _
I,rl,
v P'-".M-."
,~, plant. W!Lill,commend Ihe application of the specified values to existing plants to
£,ffCiftpJ o,~¥/"':" <~~ /, o ~~)-,,.\.Il'---:-e~gh availability. H?~eysr~t~~ntswilh legs'~rigenlwater quality require-
"I 1 •
,/ ~ " .7 ments havo been operatln,j'$allSfaclarl1y for many years, then - based on tllis
Re(
1
D ,>1 nO e 11 c rx-7;" fl t"",......<" ~ _ J;'>.) ~ operating history and the piscretion of oxperts - these specified values may be
disregarded; but the requirements laid down in TRD 611 11J must be adhered to
'!'r: -, v-/' in all cases, ",'-'.:;/....;',
ern S I ouq {O n ~.(70~" J<:,--'./ . ,.p f
Tho spocified values apply to continuous operation. This term is meant to describe
Co,, s7;ruc1!(Jj cP Lv'" '(),J-L- / the operating condition, which will be found at virtually constant load, During com-
missioning of new plants and under varying op~raling co~s - i.e. during slart-
()U)!~f
up and shutdown and load changes -, a degradation of water and steam as operat-
IJ V I{ i I(j b d) •..
.> \y;:""{e.-:~l~-.c~ ~ . " Ing agent is unavoidable, which makes it impossible to meet the specified values,
The effect is only brief after load changes. When restarting a plant, which has
"r
:;/vi.'lgjcol '-, .-'- _ J-.JU:"4l
=.t-'-G~' o~.-' r I ,_
~~<:.>';;j) been temporarily shut down, the continuous operating conditions should be achiev-
od wlt11ina short tlrne - generally aftar 2 to 6 hours. Special technical equipment
5c/i'?J((Jc1o(,/. "."/C,~LP/ or operational measures should bo used in plants with frequent start-ups and shut-
' (,j \../ ,
downs 10help reestablish continuous operating conditions as soon as possible,
op.p~ -OJ--:,'" ~" ----:1- 1
-OYUI-V _
e.g. filtration or draining of contaminated start-up condensate.
I ;',i,'.,
VI(llfcJ/j V!h),! - ~ t J;9~'~-:</yj 7 I"'"
"d~~ t'.:"VJ
Cr"S!C II}1 IJv ~~ &
"Z't,t;1
/ .~-~.- 1 ",1.:,.,',:
! .~\\fi~:.
10powor plonls oporollng wllh condensale normal operating values will be achlov- The Guideline reflects lhe current slate of knowledge which Is based On practical
od, Wllicll mo cloarty holow lho spoclflod valuos (for dellnilions of Ihd'torms, seo oxperionco and scientific findings. Its aim is to prevent corrosive damage to the
12J). This Guideline is Ihe lirsl documenl 10 quole such normal operating values components in a water/steam cycle, minimize corrosion product take-up by water,
lor leedwaler and sleam in order to give an impression of the ratios, by which minimize Ihe formation of deposits In systems In contacl with water and steam
"Jlociliorl vollJoa 11",1 no,,"ul operollng values are Inlorllllked given an approprlale and facilitate tile production of purified steam for turbine operation.
oporallno mode and n propor slolc as woll as an undisrupted working condition
01 compononts and syslorns.
/
tl is customary for Ihe make-up feedwater for boilers with a rated pressure of 2.1 ProlecUve fayer 10rmaUon > <" _ I
..3 /('-'" '/
(.
?
V-
> 6R har 10 ho lroaled by means 01 complete demineralization and for Ihe boilers
The corrosive attack of waler or steam on steel I~ing to"the formation of iron
10 bo oporaled willl deminoralizod leedwator (conduclivity after a slrongly acidic
oxides Is naturally limited if a prolective layer, i.e. a dens{and uniform oxide lay- , , I '
calton exchanger < 0.2 pS/em). The specified values are based on lhis assump-
er lorms on the surface of Ihe steel. The only iron oxide, which can e~~Lln direcL" [J"'YJ.-J
lion. Recycling 01 condensale inlo Ihe water/steam cycle is only permitted inso-
lar as 1110condilions lisled in Tab I e s 1 to 3 (see pp. 20 to 22) lor boiler feed.
conlact wilh the metal is magnetite. on which oxides of !!:ixalsQJ)ron can grow, »-tJ: ;j;....
depending on the redox conditions. Such prolective layers restricl the transport .
walcH, hoi lor wlIlm nnd slomn nro not nogalivoly affocted. This must bo monilor-
01 corrosion products to P?rs diffusion and reduce Ihe area a~Jilable for reaction
ud LInd <lssurot.llJy condonsato polishing, II necessary.
belwoen steel and water 7r, steam, theJ~by minimizing, the miteriallossc_~at~ _~surM
I hll 11:10Ilf rnlllorl1ll1luko.up wutor lor boilors up 10 07 bnr mInd prossure Is on lace layer passivity)., •. u :'-'P
p
, .'
••• / f ('yhl.;,~~
-J-:./ (I' / •.....
~,// - L/) /L',;J'-7 j. 11..J
uxc"pllon In viuw 01allnan 1 ollhls Introductlon and Is not donlt with In dotallin
The basic chemical reaction between iron (carbon steel) and waler Involves iron
Illis Guideline( 1).
dissolution through several reaction stages - a redox stage Fe(/I) -> Fe(I/I) and
condensation slages (Schikorr reaction) - 10 Ihe Ihermodynamically stable end
rroducl, magnotito_ The k\noJ$s of tho Schikorr reaclion stlOW marked tomperaM
tum dependency which is characterized by inhibition of the redox stage, Oxida.
lion of Ihe divalent iron by water needs particular configurations and conditions,
2 General ,. "\ \: which onlY-Qccur in exceptional cases at low temperalures (Section 3). On Iho
(~(.J7' '1~-t)) ()--mr~d, magnetite Ts spontaneously formed at temperatures, when conden-
Fondwilluf lor ollcc-throuqh bollors,locdwntcr and boiler water of drum-type boil-
(.. ')
.-(~ \.... ( salion 01 iron(/I) hydroxide iJpossible. The sleel is covered by a prolective layer,
I
ers as well as spray wnler for sloam temporature conlrol must meet specific quali-
ty requirements both to ensure a safe, economical operation of the steam genemM ..3 Based on these interactions, water/steam cycles in power planls can be divided
tor!"; :lnd 10 ensuro tho necessary steam purity for superheaters and condonsing into two areas: ir lJ,,)
/ r , :/'.
l.~)..p
llJrllIIlO~;, Ir Iho moclhuTl Is e1rclIlnlnti In n closod cyclo, tho qunlily of clrculallng - tile lemperalure range up 10 arOUnd 200 "C, where an inhibited Schikorr reac-
wnlor IHH.lulonm rntJ~1 1101Just bo sufluble lor Individual plont components but for lion ass!JI.CS that the steel surface in contact with water remains active in re.
all 1110cOfllponollls illtllo complelo waler/steam cyclo, This can lead to more strin-
yenl loquircrnenls ttlUn the individual plant components would demand.
......
/")~
1~ ~pect 0", iro-n dissolutio~ (V:r ~ 0.Y --- -
- :- the hot waler area Irom around 200 .,c, where the magnellle prolective layer
forms spontaneously,

I If tlnUll-Ivpu bolh,"~ willloul spruy dusupOItlcl.lling ore operated wilh lully domlnerallzed milko-up wllior
Iron dissolution is at maximum at around 150 "C. ,\~_;. J J 'l.
I

IHI(j !inll contninlng IlIlJdwnlor, orllV nll.votnlilo treolmenl ollho leedwulor Is pO!l~dblowilli a ~irntJlInflo- In the condensate/teedwater line, Le. near the LP prehealers at low and me~ ~~ f"-:' .,
nils i1tlta1ilifl{l of tile boilm waler wilh solid 8IkRII1:ln{logenls tn accordance wilh 'f Hllles 1 and 2. In COli. WOller tomperatures, the Iron dlssolullon In pure water Is normnlly dlffusion'con. !
hl1s110 T ablos 1 ilnd 2, lhe conductivity or the teedwater will not be spocified; instead n direclly mellS-
trolled, It can change into erosion-corrosion Under Unl?Vo.u[~~le local /low condi- !

I,
wnd condlJf:IIVlly (:!~i"C) Ill.: ~lO(JpS/cm mUlll bll mnlnlalnlld In Iho boll or willor: in contrasl 10Tubla 1,
HilI luodwlllnr lI1u~11 comply wllh lllo tollowlng specified •••• alucs: oxygen < 0,020 mg/', 10101iron lions. Conditioning is needed to reduce corrosion ~~ corrosion product take,-up 1-'
'-,00:10 rllll!l. 101111 (;uppur .: 0,005 my/I Dnd 10101olkotlno earths (Co=" Bnd Mg" 'J < 0,005 mmolll.
by tile fee,'water (Section 3).. . ' i t'
r~ "(~r . L" -,J<f: " • )\,r " 9'~
8 \..>
J (-' --: --

',<.
'~\;.
,1
 ,
'ij'- !/
,"2.2 Corrosion producllronsport ond deposito (, ~r:;; '-.r! J)
/ where electrolyles are' invo"lved - cause corrosion in the presence of water or as
11011(11)hydroxidu us tho dl5so1vod corrosion product of iron, wllOse solubility /) a mollen maleriaL ~!lQr depositing on the turbine blades is unavoidable even if
uocrCLIses us Iho tomperaturo Increases, tends to form supersaturated solutions
J1,'Y1'-'V"
;...P the specified values in Table 2 are adhered to, minor corrosive attack in t~e w9t _
abovo 200 "C. At points 01 high turbulence, e.g. around boiler control devices, or
on 1"",lInO I,,,,,,,, "ubjuetor! 10 hiOh hont IIUXOB, mnonoilio procipl1ntoB out from
steam area of condensing
J\"-~41;(~V
turbines also cannot be excludef!., -"~J5Jc:':;U;')::;'CJ
-
~lJeh solutions In crystnllino form. This lends to reductions In cross-section or ham- ",,l "'" Inaaeguale water/steam separation In the drums of conventional boilers can
POlS 1110 hunllrnnslor in steorn generation lubes Gnd con cousc dam ago 10 mato- cause carry-over of boiler water droplets in the steam and even direct carry-over
rials duo 10 overhoating. of boiler water in Ihe event of a rapid pressure drop. Satisfactory water/steam
separation should be ensured by appropriate design measures, but this can be
Undissolvod, suspondod corrosion products, which are carried with the leedwater
adversely alfected by an increased tendency of the boiler water to loam. For exam-
il1to 1110bollor or oro produced in Iho boilor Iiself, can form deposits. especially on ple, suspended solids as well as dissolved or emulsified organic compounds in.
1l1Ormaily stressed tube walls and these normally have a detrimental effect. On crease Ihe foaming tendency of boiler water and thus increase the risk of steam
Iho ono hand, such deposits can elfoct the heat transfer, this causes tho lubo wall impurities.
lcmperalure to risc, leading to overheating and ruptures of the tubes as their ther-
mal "Iahility limit is oxcoodod. On 1110other hand, oloclrolytes dissolved io the In Ihis connection, particular reference must be made to 1I1ewaler for spray type
wolur "lin "Oll"olltrulo undor doposl1s, thoroby Inl1lating a chomical attack on the dosuperhoaters for sleam temperature control. it must be 01 the same quality as
lliho rJ1nlorilll or proloclivo Inyur. Tho concontrol1on of eloctrolytes de ponds on demineralized feedwater and must nol contain solid alkalizing agents, which would
soparate oulln the superheater or turbino.
1110 111lll1l111X (ovnpornllon Inlollnlly) nnd tho oloclrolyto conconlrotlon In tho wator.

2.3 Impurities In steam 3 Chemical conditioning of water/steam cycles

~-~ "='-<.,..;:J';
CHUSOcorrosIon and doponlls on suporheators,
11111'1111110:. ill :IIOllfll CUrl control Corrosion on plant c.Qmpbnet;ts in conlact with water and steam in a waler/steam
clcvicos nnd turbine blades and lead to salt formation In the superheater and ttlC cycle and as a cohS'~rfUence the absorption 01 corrosion products by water can
tlHbine. CJ,I( )~~-rJ.;~..:. be minimized by chemical measures. A commonAoature of ttlB standard condi.
Ci.lI bon dioxide is dissolved in water and steam a corrosive impurity as well as tioning methods described here is the reguiremenf thai~ minimum pH and olher
nlhor inor{lnnic :mrl ornnnic acids undor GQrtaln circumstances. Carbon dioxide is conditions be adhered to and thallhe a<illi;16n"15t~arious chemicals promotes the
(llwllY" p'os"nl tlurillU slarl-up. II allecl9 Iho pH and conducllvlly of stearn contlen- formation of a hig~corrosion:reslstant layer on metal surfa~~s. .r;};T;-;;~:
salo and when it Is concentratod, It can cause corrosion, especially in heat ex. !,.f'k-%,.dV ':5....
'~,'~1 i-
The dissolution 01 iron in pure, vjrtually oxygen-I roe water involves a hydrogen
ehllngers. Inoru"nic and organic Bclds can be formed as a resull of Ihe hydrolysis reaclion, i.e. the formation of iron(lI) hydroxide and hydrogen. The oxidation of
or inorganic salls or Ihe decomposition of organic compounds and also lead to Fc(lI) 10 Fe(lIl) and the subsequenl condensation to oxides which can form a pro-
tlcid corrosion. .".' teclive layer are nol possible with water as Ihe oxidizing ?gonl af tel)1peratures of
Dissolved solids enter Ihe steam duo to their solublllly In sleam or by carried.nver f ':. d 1/2 0 -' < 180 "C. Condensate and 'eedwater always conlain'ifabes of oxygen, which pro-
wnlcr droplets. The solubility of waler soluble solids in steam depends on pres. I
f',./ n(J) -1" I-ft mote these reactions at Ihe phase boundary, therebY~iJillipg layer formalion,
sure and temperature. For the malerials Involved here, solubility is hIghest in salu. Z , albeil slowly, if the low oxygen lovol is malched by corre'Spo'!\'8ingly low concentra-
raled steam, which corresponds to supersaturalion at other pressure and temper. ../ \ oi' K .e/'tions 01 iron(lI) hydroxide. Tilis condition can be salisfletl by raising lile pH above
"Iuro conditions of the slonm in the water/stearn cycle. Dissolvod solids can there- ,)~1,' ~ the saluration pH of Fo(OH), (pH = 9.25 at 25 0c) in order to suppress the solu-
fOle prccipil31e In superheaters and on turbine blades to form deposits and - , blilly of Ihe lion (II) hydroXido and thus irI\O
lion dissolution Itself (condltlol1lng With
alkalizing agenls, see Section 3.1). -

10
" 11
Oxldlliioll of 1'0(11)to 1'0(111),
tho IImlllng slage of Ihe Schlkorr reaction with waler
lUI lho oxidillllU agont, clln bo brought obovo by addition of oxygon. This gr,ootly denser plant and Is generally kept below 9.5. There Is no upper limit 10ammonia
rodUCC5 tho solubility of tho corrosion product and makes possiblo the formation concenlrations with tubing made from steel, chromium-nickel sleel or tilanlum.
01an oxidic protective layer, II oxidation occurs near Ihe metal surtace. The oxide Air-cooled condensers made of aluminium only permit a pH of no more than 8.
Inyer inl,illile. 1110mOlal dissolution which Is delermin.ed by the solubility of the The optimum pH level for the whole plant musl be estabtished In the conden-
1""'(11)hydroxlrJo, which Is In lurn dopondont on pH"R,;oli'irlas II reducoslhe area sate/feodwater train upstream of the LP heaters to ensure maximum corrosion
whoro wnter comas Into contact with melal. Transport of corrosion products per- proteclion for these preheaters. Where a condensate polishing planl is instailed,
sisfs 10 11 HrTlulIoxlonl through poro dlfluslon. If lho U}Uo botwoon Fe(lI) and tho ammonia must therefore be dosed upstream of the LP prehealers. In cycle'; with-
oxygen concentration shifts, when a film is present, whi2h is caused by initial oxi- out'a condensate polishing plant - where the ammonia therefore remains in the
dalion, for example, the catalyzed oxidation of Fe(lI) produced by hydrated Fe(lIl) waler/sleam cycle and the pH only has to be adjusted in accordance with the
oxide lends 10a growlh in Ihe oxide layer and reduces the corrosion producl carry- make-up water quantity - ammonia can also be dosed additionally at olher points,
over \0 the lccdwulcr. This is lho underlying principlo of conditioning with oxidiz- for example in the make-up water on the suction side of the feedwaler pump. The
ing agenls (sec Section 3.2). latter allernative is not feasible, if large quantities of make~up water are fed into

The lacl thai Ihn oxidation 'Oto of dissolvod 1'0(11)In Iho homogenous phase is the condenser. Ip ~ ~ ..•.
-->
-----'i "-1'. '1' .
11Ilih1ydopolldolll 011 tI", pH lind can bo lIcceleraled by Increasing Ihe pH Is Invok- Hydrazine is alsp often used to lower/Ihe corrosion rate of plant in contacl with
ocr In tho r;nrnhiliod c;ondltionlnn with nrnmonln nmJ oxyoen (BOO Socllon 3,3) - In fecdwater. Contrary to what was previ6usly believed, hydrazine is nol only an oxy-
1l1h procIl:Jfi loworllllllllfl Fn(lI) hydroxldo aolublllly nlao hos n favourablo oUocl gen bonding agent but also acts as a corrosion inhibitor in feedwater. Hydrazine
Ull oxiuation lind 1I1OroUY protoctlvo layar 'ormation. showSthis corrosion.lnhlbiling effect, which requires the presence 01 a small
amount of oxygen, predominantly in Ihe colder section of a water/steam cycle,
which Is Ihe main source of corrosion product lake-up by Ihe leedwaler.
Passivation of the steel is then based on activation of molecular oxygen in the
form of induced oxidatlon, where tho chomical roaclions in the aroo of the phase
3.1 Feedwaler conditioning with alkalizing agents (all volatile treatment) boundary are calalyzed by interaction ofthe hydrazlne with oxide-coated surfaces.
lroll dissolutloilis docroased by raising Iho pH. Planls with once-through boilers The effecl of hydrazlne can be described as anodic Inhibition of the iron dissolu-
c;:m only ll::iO volnlilo f1lknlizing agents, these have the advantago of alkalizing tion by partial oxidation of the initially formed corrosion products, Le. on the ono

holh tho foodwator and tho condonsato. Drum-type boilers, as explainod in more hand, lhamolecular oxygen activated bl' hydrazine promotes Ibe oxidation of
detail below (Soction 3.4), normally require the additional dosing of solid alkaliz- Fe(lI) to Fe(lll), and on the other hand, hydrazine as e reducing agenllimits oxi-
inq :IDonlr., sinco lho rH 01 boiler water can only bo significantly raised, when alka. dation 10 the magnetite stage, which in this case forms the corrosion-Inhibiting
lis "I II If) IYPfll1f(Jusod, wl,lch slrongly dissociate even at high temperalures. oxide layor.

Aflllllonin I~I Oln "'o~llcommon volntllo alkalIzing noon!. In domlnornllzod wfllor. To make the best possIble use of the corrosion-inhibiting effect of hydmzjoe it
IrOll (j1~solullon 011 cud.JOn steol or low~alloy 51001 In the aroa of tho proheators, musl be dosed In Ihe condenser discharge pressur.~.p!p.!'_I?efore the LP preheaters
IF Irather Ihan)afler the Ihermal deaerator, as was the practice In the pasI with chem-
and Ihus corrosion product take-up, is not reduced to a minimum untilihe pH Is ",/.

mound 9.5. Correspondiflgly high ammonia concentration levels are usually nol ical residual deaeration. However, hydrazlne cannot be used alone as a volatile
permitted with bmss-tubod condensers, as copper dissolution is caused by,con- Jl!.Iialjzjng agent, since hydrazine would be needed in very high concentrations to
ccntrntions 01 nmmonia rosulting from the design characteristics, particularly in reach pH levels above 9 and, after thermal decomposition in the stearn genera-
U10 air extraction zone. The alkaline conditioning thus necessitates a compromise. tor, Ihe result would be ammonia concentration levels harmful 10 brass-tubed con-
8ccrJ,use of lhe iron materials, the recommended pH in the feedwater is 9 or densers. The base pH musl be adjusted or maintalnedyy ammQ!lia.. In closed
above. II copper malerials aro prosent In the water/steam cycle the upper limit systems without ammonia removal in a condensate polishing plant, minor ammo-
lIlusl 00 sot according 10 lhe desIgn ctlaracterisllcs and the materials of the con- nia losses may result from exlraclion or deaeration - generally 0.1 mg/I in the
feedwaler- and Ihese can be compensated for by hydrazine dosing. Furfhermore
12
13
...-----------------------------------------------------
.~l.""
--.J
hydrazino, in cpilo of its weak alkoli;dng effect, is botter suitod to alkalizing con.
dOfl~uluI" Ihu ~tuurll/wulurtJl-plmso uren lhon ammonia, because It .185 a morc
ravourable distribution coclficient.
Tho oxidation and Ihormol docompositon 01 hydrnzino only produco harm loss
prodlJcls. Howevor, It Is nocossary 10 follow special procodures when hendling .
hy,J""ino 13,~I.
Once-Illrougll bollors and spray-typo desuperhealors lor stoam temporaturo con-
trol must only be supplied with water, which exclusively contains volatile alkaliz-
ing agonts. Accordingly, the leedwaterof drum-type bailors operated with deminer-
alized loodwater can only be conditioned with volatile alkalizing agents up to the
exlmction point olllle spray water, when spray type desuperhealers are filled.
3,2 Feedwater conditioning with oxidizing agents ~ ..:!ci/>Y
(llcutmi cj!lJdltlolll\,g) [5J 0)j~, L .
("7/~--- .,::..J l __
~ /
Iron lako.up by tho loedwulor Is reducod by dosing with g?seous oxygen or n
t'yc1rouurl puroxido 50lulion. This mnkos it possiblo to disponso, with alkalizing in
tile condensate and feedwater zone, if ammonia-free steam is desired or, if ammo-
nia must nol bo prosont in tho waterlsh~,a~:rtcyclolor any ro~~on. The solubility of
iron is greatly reduced by oxidizing the 'Qtlm.tuycorrosio1;-p;baQct, iron(lI) hydrox-
ido. wtlicll.c,:.~ IIIQ cQrldilions necessary for protective oxide layer formation.
. (y~,)(;-=:I().,.l_«,..-~
Accorulng 10 lhe rule that the metal Ions at a surface In contact with water must
be maintilined at the lowest possible valency state, the oxide forming directly on
1110 slool musl hnvo an oxcess 01 Iron and thus be magnellte in nature, With re-
dUf:od iron din~olulionnnd on l,(r~c6'ss of oxidizing agont this primary oxldo layer
i" ovorwown by iroo(lll) ilydroxldo, Ihis Is prosont as ".FoOOH whon molocular
oxygen is used as the oxidIzing agent at temperatures up to 160 "C and as
y-FeOOH or hydrated haematite at higher temperatures. Such protective layers
UfO loss soluble in neulral waler lhan magnetite. Oxidation by hydrogen peroxide
follows somewhal different laws.
Condit.ionina wilh oxidi7.ing Rgants Is only used In plants with once-through boi/-
ors, with some exceptions. Dosing with gaseous oxygen or a hydrogen peroxide
solution must lnko plnco upstroam of tho LP preheators. The oxidizing agent con-
centration must bo adjusted so as to minimize dissolved divalent iron In tho feed-
water upstream ollho boiler inlet.
1~
------------- -- ------
3,3 Feedwater conditioning with alkalizing and oxidizing agents
(combined conditioning)
':;--u-2' ,
Iron absorption by the feedwater is reduced by adding both gaseous oxygen and
ammonia, The alkalizing agent prom~~'l!.the oxi~~ti~~)1.':ocessof Fe(U) to Fe(lIl) ).
In water contaIning oxygen and also offers a ~.!i~aln 'a_~o~nt. of ~Q!gfJ!On.ag.alnst-f../; ">
the harmful e.llilcl of anions on Ihe protective layor in the event of salt penetiatfons .. - -
..J.';..JJ:..A- - ;;-(;J ,J.•.•.~-'-l'-:V J.... ---'~~itI
J;;Jw
CombIned conditioning Is IImltod. wl1l1 some oxcoplloris, ~to planls with onco-
through boilers. Ammonia and molecular oxygen musl be fed separately into the
feedwater upstream of the LP preheaters in concentrations, which ensure that the
conditions stipulated in Table 1 are fullilled in the leedwater upstream of the boil-
er inlet. The small increase in pH encourages profective film formation on steel in
water containing oxygen without the ammonia reaching concentration levels harm-
lui to copper materials, even in the air extraction zone of a condenser. In com-
parison with alkaline conditioning, the ammonia concentration of the steam con-
densato with combined conditioning is so much lower that the run length of the
condensato polishing plants until ammonia ion breakthrough is extended.
I
l
3.4 Conditioning the boiler water 01 drum-type boilers
In drum-type boilers operating at the pressures under considered here, the tern.
peratures in the boiler water circulating system are such that a protective layer is
produced by spontaneous magnetite formalion, Tile very low solubility 01 magne-
tite depends on the pH, with a minimum at around pH 10 (measured at 25 "C). AI
much lower pH values, the magnetite solubility increases considerably, likewise
in the highly alkaline range. In principle, a solution balance is esfablished in Ihe
circulating system, which, however, is disturbed by the evaporalion process. Tilis
results In suporsaturation leading to carry-over of corrosion products and the
dopositing of corrosion products on the heated side of the evaporator tubes.
The pH of the boiler water must be maintained within a specific range in order 10
minimize the solubility of the magnetite and to counteract the effect of conta-
minanls, which reduce the pH and can be carried over with Ihe feedwater and
concentrated in the boiler. This cannot be achieved using volatile alkalizing agents,
because in the boiler waler circulating system they play vinually no part in increas-
ing the pH due to their equal distribution between water and steam In the drum
and their dissociation behaviour at high temperatures. The recommended stand-
,I
ard procedure for drum-type boilers operating at less than 160 bar is the applica-
tion of volatile and solid alkalizing agents. The aim is for the volatile alkalizing
I
I,
15 1"
..f
t:£;
r.',.
 -----------_._~_._--~--.--_._--~
I@ ,,,,,,,",I

agonls 10mainlaln a pH above 9 In the condensate/feedwijter area and for the It can be assumed that in water/steam cycles using demineralized feedwater car.
solid alkalizing egents 10achieve satisfactory boiler water alkalinity. In order 10 bon dioxide Is only present as a trace contaminant in continuous operation. In
ensure thorough mixing, the solid alkalizing a90nl- usually sodium hydroxide or order to prevent carbon dioxide In the atmosphere from affecting the measure-
possihly Iri-sodium phosphate - must be added to the feedwater upstream of the ments, t~e conductivity must be measured in a flowing sample in the absence of
(Iconoml.ur bul downslreem of the spray watar tapping point. Alternatively. the oxygen. A strongly acidic cation exchanger before Ihe conductivity cell (Tables 1
uolkJ lllknli1.ing agonls can bo dosod In the bollor drum, if the dosing pofnts arc to 3) ensures Ihat Ihe measurement is not affected by alkalizing agenls, since the
rlosl!Jned 10onsuro good dlslrlbutlon and avoid local overdosing, presence at free bases is naturally not detected by the conductivity mea:surement
aftar calion exchangor. At the some lime, the cations of salls are exchanged in
Volalile alkalizing agenls can be used by Ihemselves in the waterlsleam cycle of an exchanger of this type and the corresponding acids are released thus increas-
drum-Iype boilors when operaling with demineralized feedwater on condilion Ihat ing the response sensivity of the measurement by a factor of 3 104 due to their
tllO conduclivlty of Ihe boiler water can be maintained et e very low level, i.e. Ihe higher specific conductivity, On Ihe other hand, when operating with demineraliz-
ingress 01 traco contamInants can bo virtually elimInated. Whon drum.type boll.
ed feedwater (conductivity downstream of the strongly acidic cation exchanger
ers use only feedwater conditioned with oxidizing agents in accordance with Sec- 0,2 ~S/cm) direct conductivity measuremenls wilhout a cation exchanger can be
lion 3,2 or alkalizing and oxidizing agents in accordance with Section 3,3 (neulral
applied as an auxiliary variable to determine the pH and 10conlrol the alkalizing
01 COrl1!lllllld comllllon1nn). lho oxygon conlonl should bo rnolnlulnod 01 tho lowor agent dosing in the feedwaler.
limit ul tho rucommondod ronno. The bollor walor should thon bo condilloned with
II nolid 111lmlil.illO Iluont 1,13ohoWIl In Toblo 2. Continuous, recorded conductivity measurements alter cation exchanger in vir-
tually demineralized water facilitate rapid detection of changing trends; the differ-
ence In conductivify between two measurement points can provide valuable infor-
t.. mation about Ihe causes of these changes under optimal measuring conditions.
For example, a drop In conductivity belween wei sleam and superheated steam
/_R .~. LJ L. 0i~,J\ _~ Of"- (,J-:. C-:!' condensation Is an Indicator for salt deposition in the superheater; higher con-
v
4 Expianations concerning the significance ductivity in the turbine condensate compared to the superheated steam indicates
of the parameters assogiated with specifi~d values condenser leaks; a difference In conductivity between demineralized feedwater
".r~b <.' --t,l)
and steam points to a carry-over of boiler water in drum-type boilers or 10non-
find their analytical monitoring . ,'0..Y,
~;>~8; \ ..
'~\/l.>~j ionogenic organic substances in the feedwater, which only decompose into ionic
TtlO srod11od vnlues in Tnbles 1 103 should not be used without considering tho substances al high temperatures.
following inform:lllon nboutlhe paramoters In the tablos and their analytical monl-
loring, Analytical monitoring of Ihe specified values requires regular and appro-
prioto sompling and correspondingly son~itive analysis mothods 16, 71,
....
r.J [_ - -r".
>:~-"b
, -~./~" ,;.
-_.
?"J'J~
,\1 ,!I.2 pH. I /;
j~.Jv-" J - c-.bJ .) ~.J....."1;L
L Tho reasons for neoding to maintain a minimum pH in fcedwator nnd boiler water
are e;plained in Section 3. -~ .... ~
4.1 Conductivity
0-

Conductivity is lhc most important test parameter for monitoring water and steam
purity in water/steam cycles, because it is a sensitive Indicator of electrolytes in
wllter nnu cnn be nccurolcly on.d continuously monHored without major ouUoy
using recording devices. However, conductivity-iS not substance-specific so that
il is sometimes necessary 10identify impurities revealed through conductivity by
means of specinl onolytical methods such as ion chromatography or potentio-
motry with lon-sensltlve eloctrodes.
When operating wilh demineralized feedwaler and conditioning wilh alkalizing
agents, it is necessary to verify the pH using auxiliary variables (directly measur.
od conductivity, ammonia concentration), since it is not possible 10 r:1easuro tho
pH accurately In low-Ion wator by simple maons, On tho other hund, tho pH of
boiler water can be measured directly. Alternatively, with sodium hydroxide Con.
dilioning. pH can be determined from the direclly measured conductivity and the
conduclivity measured downstream of Ihe calion exchanger (see Appendix).

16 17
 .,
With 1l0lHllkull/lld, (jollllrllllalllOu walor, compliance wilh the conducllvlty In In planls wilh drum-Iype boilers. whose waler is conditioned wilh solid alkil!izing
11Ihiu 1, bolh tliruclly rTluU:iUruu und rnouBurod altor cutlon oxchanger,onsuros agenls, the sodium concentration in Ihe steam complies with the normal operat-
lhallho minimum pH In tho feedwater does not drop bolow 7. ing value in Table 3, II the sodium hydroxide or tri-sodium phosphato concentra-
/ ,. tions are held within the pH and phosphate limits In Table 2, Levels which exceed
/ / ()J' ,n&- . ~ .~)v~ the specified values point to unfaivourable water/steam separation in the drum and
L»)'u:.,V"- ) r. /" ~ \..}I

4,3 OXYlJon e ,> .

/ j

L!f'U' "//
AI 1 boiler waler droplet entrainment Carry-over of sodium compounds to the steam
can resull In superheater and tu blne deposits possibly also in corrosion. .
/ In viuw 01 till] Inllibiliny ~ct 01 O)(y~r.l.on sloelln-deminor:allzed fuedwater, cor-
rosion erevenlion no longer demands, the previdCs string~nt limitation of oxygen
h~f,.
,'I ""

(.'1
I

+" concentrations. However. if the conductivity specified value for demineralized feed-
water « 0,2 pS/em) is exceeded over a period of several days due to condenser 4.6 Silica
f" ••.,f'-""l.

loaks, impuritios in recyclod condensato or Ion sllppago In the walor lmatrnen!

Silica conconlrations in Ihe leedwaterol once-through boilers and Iho boiler waler
planl, l110n It is necessary to adhere to on oxygon spocifiod value of loss Ihan
0,02 mg/I, of drum-type boilers must nol exceed cortaln values because ollhe requirement
concerning Sleam purity for turbine operation, The solubility 01 silica in sleam
Wlwrl ct>lldlllolllllU with uxldllll1l1 ugol1ls, complionco with tho oxygen spociliod Incroasos Wiltl pressure. When operating with fully demineralized make-up water,
1>0rnonilurod by continuous mousuromonls or tho oxidizing agonl
vnllj(l~l ~ih()lJld
the silica concentration in the feedwater and steam of once-through and drum.
dO!ilno ~hOlJld t,)O cl.lIrlod so lllal tho 10101Iron value In the foodwalor allains Iho type boilers remains far below the specified values in Tables 1 and 3,
lowost possiblo lovel.
Even when the specified values are complied with, silica deposits in the high pres.
sure section of the turbine cannol be excluded under the most unlavourable con-
ditions, especially In Ihe presence of substances such as aluminium.
4.4 Tolnl Iroll. tolul coppor
If lhere are differences between the silica concentration in the fecdwaler and in
Iron and copper concentrations in feedwater and steam are an indicator of the the sleam or it the silica concontration in Ihe boiler waler is higher Ihan Ihe prod-
olficioncy 01 condilioning, Thoy supply informalion on tho melal dissolulion proc- ucl 01 concontration coelliclent and silica concenlration of Ihe feedwaler, Ihen Iho
OS"o,; in Iho "yslorn "nd Iho rnolallake-up by tho water as woll as possible depos- raw water probably conlains colloid,al silica, which was not retained in the make-
lIs in IIUl boilor and turbino (cp. Seclions 2.2 and 2.3). Changos in iron and cop- up waler trealment plant and has hydrolysed to lorm soluble silica in the boiler.
per cOnColllrillions due 10 load lIuclualions cannol be Influenced by chemical
measures.

III ro~;ror;l of c:orro!>iollrroducl nbsorpllon, WO ognln rofor to Iho roqulrernent In

4,7 Phosphate
S(~C'irHlI Ihal r:olldnn~alo~ ~holll(1 notlnlluonco Iho characteristics of feedwnlor
Of llUij", wulm.
When oper~tlng wlih softened leedwaler. coniaining salis, trl-sodium pllosphale, I"
was and slill Is usod to condition tho bOII~r wafer in ordor to provont adl1eront_" :A,_'Y~"
, c_ .I ' hardnes~recipilation and bond any ~sid~al hardness as a salt ,(matile sludge, - --( ,
~v./_ U~,. rd--Tri-sodium phoshate hydrolyses to giv?f'-se5diumhydroxide and sim~ly}neously_:>".>-~ ).>~,.P
4.5 Sodium

Sodium Is usod 10 condition Iho bollor wator 01 drum-type boilers In the form 01
produces an alkali.zing e~e?t. It is th~refore somcti~es used ~llh demjneraliz~d
feedwater as a solid alkalizing agent Instead of sodium hydrOXIde, for example In
.!: ,',:--
..-J
_',
F'J
t, .,
t
sodium hydroxido and lrj-sodium phosphate, but II also occurs as a contaminant sen woler coolod condonser power plants not oquippod wilh II conclonsnlo rurifl. r
in Iho wnlor!nlonm cyclo IhrollOh slirraoe from ion oxchnngors or heat exchanoar cation plant or spray-type desuperheaters. Minor cooling water leakage can then ~
IOllkllUO, MUII~llflrlU !flO comllJc!lvliy or tile sodium level with an lon-sensitive (pNa) be kopt in check as a result of the bonding of the hardness ions and increased i:
oloclrodo i~)n s~,,:o indiCAtor of impurity Ingress, typically due 10cooling water. continuous blowdown of the boiler water, eliminating the need for immediate shul- i.'
~~
18
19
 c'

dow". Howuver, will, Irl-sodlum phosphale boiler water conditioning, measuring

References
1110conduclivily dowl1!:jlrourn of lha culion oxchangor will no longor idontify ion
Irnpurillug IlOCUUgOIholr conducllvity Is maskod by thai of Ihe phosphate Ions. Itl Technical regulaUons lor sleam bOilers. TAD 611 MFeedwaler; loodwaler and boiler water 01 group
M

v' IV steam generalors , Carl Heymanns Verlag KG: Cologne and Berlin; Bouth Vorlag GmbH. Ber-
017 >'" ~ Tho solubilily of sodium phosphates in water decreases at higher temperatures. lin.
'- /' ~v;;r)Qrullon cun crrLli6-dlssolvod bollor water substancos to concentrato 10such 12] Tho slgnllicanco of tho lerms guide value, IImil value and operating valuo In power slation chemis.
/ nn oxlon! in tho wnll moa of hoat-stressod bollor tubes that tho solubility product try. Paper Irom the VGS Goneral Committee "Power Siallcn Chemistry". VGS KHAFTWERKS-

.,Y /-')~'

of Iri-sodium phospllale Is exceeded. This then precipitates (physical hideout); it

(3)
TECHNIK 63 (1983). Vol.tB, pp. 1006-1008 .

Technical regulations lor hazardous auxiliary substances; TRgA 550 "Hydrazine~. Bundesarbclls'
d./ /'" may also react with the protective layer to form iron phosphate (chemical hide- blan NO.5 (1984). pp. 49-51.
out), which locally hydrolyses to give iron hydroxide and phosphoric acid. Under
[41 Technical rcgulalions lor hazardous auxiliary substances; TRGS 100 'Irlggolln9 threshold lor dan.
-"' 'l:. L: .d/tJlllavouroblo coneJilions lhoso hydrolysIspreducls~~ot:, theformationof dopos- gerous substances". Bundesarbeilsblan No. 11 (1986), pp. 91 H.
'- ,)l;! it!. ilnd conlribulo 10 local corrosion. UI'I ~,.,..'!./
T echnicaf rcgulnllons lor hazardous auxiliary subslances: TRgA 133 ~Triggering threshold lor hydra.
(:;,y~~~ V,I,~// zine~, Oundosnrboitsblall No.4 (1986)

15J VGO-M 411 L Momorandum "CondiUoning walorlsioam cyclos using oxygen or hydrogen peroxide
in conventional once-lhrough sleam generators". VGB.KRAFTWERKSTECHNIK GmbH. Essen.

IOJ VGO Manual "Powor station chemi9lry~. Vol. II, Method or analysis. VG!3-KRAFTWERKSTECHNIK
,",,' ) GmbH, Esson.
\ __
J '_) f"

4.0 Orgnnlc nuhalonco9 17J VG!3-R 123 C Guideline "Colloction 01VGS Guidelines and recornmondations lor control and ins'ru-
monlBUon~:

Organic subslances, which are carried over wilh the feedwaler into Ihe sleam Pnrt 1.2 "Selecting moasuring and sampling lines for tho water and sleam areas 01 'hormal power
slalions"
I),",,,,"t,,,, """, IIllor Ilel"u conconlrulutllnlhu bailor wOlor of drum-typo bailors,
jf1r.roll~O ltBlonrning tondency nnd causo carry.over of boiler wator droplets, thus Part 1.5 ~Technical process measuring poinls in waler and steam convoying systems •.

Illllifoclly afluctillu lhe stOEHllquality. Docomposltion products of organic sub. VGO.KRAF1W[;RKSTECHNIK GmbH. Essen.

stances formed under boiler conditions can directly affect the pH of boiler waler
Dnd, il VOiDtile, the sleDm qualily.

OrUHrlh: 5ubslnllcos 1111110 Wu!or oro bost dotaclod by determining Ihe dissolved
orn<lnic carbon (DOC) conlon!. The DOC content of completely demineralized
mako.up waler should not oxcood 0,2 mg/f [01. Whore organic substancos can
enter tho water/steam cycle from other sources, e.g. return of unpuritied con-
dOfl!";ato in indw;trial powor planls, continuous monitoring of the DOC contont in
tho condollsulo or '!eedwutor Is recommondod. Whon operating with demincral.
\.leu lut1UwalOr, 1110ellccls 01 such occurrences usually also show up on olher
rTleaslJrillO inslrumonls, lor example In ttlO form 01 a drop in the pH of boiler water,
nn increaso in the conductivity of steam or a difference in conductivity bel ween
unhoDIod foedwDlcr Dnd steDm as a result of tho decomposition of organic sub.
stances.
11 is nol rossible 10 specify generally applicable specified values. Where naces- "2
...•/ .
~", 0"" 0
\.
J -/ ~
1,1... ".' 1
SillY, :155CSSmenlcrilorla must be established concornlng lho possIble Inlluenco
of oil, 01her organic substances or their decomposition products and the maxi-
mum permlsslblo DOC contonl bused on spoclflcoperoling experience and require-
mont:;,

20
21
 Table 1. Fully demineralIZed feedwater. c~m!Ir.UOU5 coeration.

''"" Requirements on demineralized leedwarer lor once.through-

lor steam lemDeralure conlrol.
and drum-type boilers as well as on water for injection coolers

Measuring point boiler inler (upstream ot a possible dosing Joearion for solid alkalizing 8genl).

Slandard value. i.e. normal opera ling value (2j S:andard value Normal operatir:g value

I (lot condensing power plants)

General conditions clear and colourless

Tolal iron (Fe) mgJ/ <0.020 0.010

< 0_003 0.001

Total copper (Cu) mg/'
I
Silica (Si02) mg!' < 0.020 0.005

Sodium INa) mg!' < 0.010 0.002

Organic substances see section 4.8 of the Guideline

Conductivity at 25 ~C downstream of a slrongly acidic ,I

sampling cation exchanger ~Slcm <0.2 0.1
contir.uous measurement at lhe sampling point

Neutral operation Combined Operation1 , Alkalir;e Operafion

Conductivity at 25 ~C, direct and continuous measurement

at the sampling point IJSlcm <0.25 nol soecifie&

pH at 25"C i
(for once-through
volatile alkalizing
boilers and injection ccoler,
agents are permitted only)
I
,
I
7t08
I
8 to 9
I 91010

I
Oxygen (°21
I mg/'
!
0.050-0250
,I 0.030-0.150 <0.100

I regardIng applIcatIOns 01 these o,..oera.rngmodes of crum-lype bellers, see section 3.4 of the present Guidehne
reccmmended as auxilial)' vanable for pH setting and instead of ~H andlor ammonia measurement
(see sectiOl"'s 4.1 and 4.2 of the present Guideline)

.--.-?

>
Table 2. Boiler waler cf demineralized feedwarer, o::r.tJ1x.Jous operarion_
R~rs on boiler water of once-tflrCu;r1l boilers whic:1 are fed with demineralized water accordng :0 Table 1.

Precoodition .j, Alkalizing of the beJElr 'fo'aler Alkalizing of the feedwater

, , 'tfrith solid aJkalizin; agents' with volatile agents
I, according to section 3,1;
no additional alkalizing

I ot the boiler water

Permissible coe!'ating pressure ,i oar

I < 136 i > 136 aI opera:ing ~ures

Heal flux densOy

I >;II!m'
I aD heat Ilux cet':SCties <250 i >250

I
CooductMtya!25'C I, <; <3
dcwnstream d a s:trorM;Iy acidic sampling
cation exchanges'. c::ntinuous mea:surement ,
I
a! the samptir:q :om ! .,scm
I <50 ;

pH at 25 "C I 10:::02 I 9.5" 02 the cH of the feedwater has to be set

lor alkaline operating :nodes
continuous measuemer.t
I, if necessary with :he aid
of auxiliary va."'abIes
i (seeton 4.2}
I
In ::i:so:fumpl'x::.s::t-.a~ is cosed: i
!_ .•,elPa,,! II
, ~! !, <6 <3
I c<M:ed
I
~e cH!eveis T-6ica:ed are prerera.."I/y;O ~ sel .••• .;:, ~~.: ~ 'J".soiT-,""i:C,"lC:S::hale 1S:csed. ao:itional wch:axr: of NaCH is required cr,y
il T.e reccmr,-e-oe.::i::r-: :evels ca:-.t'lCl~ achie-.1lC~' ec-....:s.w a::cng ~?Ot anc:Je 3c--erence to:-e?Cot s:anda~ 'i3Jue.

attention: correction on page 23

.'
Appendix
.~
•
"
~.
e
..=!..':!l

> "
e •
to lha VGB Guidalina Jor Boiler Foadwalar, Boilar Willer ond Sinorn of Siomll
Generators Wilh a Permissible Operating Pressure> 68 bar - (VGI3-R 450 Le,
" &.
~f!'
1l._
owe
_ "
81~1818
o 0 0 0
edition 1986),

Major outlays are required when maasuring accurately the pH of low-ion walers,
••
n e,g, boiler faedwater or condensate. This does nol apply 10 lho pH of feedwalor
00
z~ or drum-type boilers whose water Is conditioned wilh solid alkalilillO lIgullis. Ilmu
g the pH can be measured directly with a cooled sample. II, however, Ihe boiler
w
foodwfller is condilionod wllh sodium hydroxido only, find domj flO! contnin ilny
•,
sodium phosphates, tho pH can be derived lrom the conductivity valuos wtlich
">

.~
cnn bo moasurod accurately wilh lho aid of rolativoly slrnplo oquipmont. Bosiuos,
]ii these data should be recorded continuously in any caso,
~ 1l
"l'
>
a
l'i
a
N
a
g a
o
o Auxiliary variables necessary for determining the pH are the directly measurod
"
N

~ "
v
" " " "
v v v v
~
conductivity (Cdirecl) and the conductivity measured downstream of a sampling
cation exchanger (FIQure 1), With the aid of C(lllfld' tho loIn! conductivi .
in•
(CCA)
• ty of dosod soda lye as woll es of salls is recorded. CCA rollool" 1110condnotivlly
"
'0 of acids wilich havo boon releasad by salls In lha sampling cation axchnngor.
8,
e Since tha conductivity of acids is threa times higher than lhal of lheir salls, 1I1C
~
V;E
::1.
I~I~I~I~
~
E
•
"•
'1J, ~
E E
~
E E
shll!,!! of the salls in tha directly moasured conductivily amounls 10 approxilllil!C-
IY',;CCA' Thus, it cnn bo sIn led In simplo torm~ thAI lho cOflfJucllviiYlrllllo fnnd.
wator caused by soda lye Is tho difloronco botwoon CClltn':l nnd 1/'1 (;CI\' ny tnkino
• Into account lho mol or conducllvlly of sodium hydroxido (~'1J JISlcrn pOi fnlnol/r),
"•
~
."1l
",•
w
the following concenlrations to soda Iyo resull

C -', C
c (NnOH) = mmol/r
~ •~ "
>
'E' I
dlmel
243
J CI\

•
f 01
•,
~
g. E2.
.
~ ~
;;;
~
"•
;;;

.
and Ihe pH

~- ..
e
~
c'
gi5
8 ~ -o E
•
-
~.,;
" w
pH = 14 + log Ic (NoOH)}. rolorrod to moll!
••
"2. E w
• ~~
•

~~
o e
E
o

"Eg
•
l1!

~~~
.g~~
-5
.~
.~ ~

-.
E u
• c
pH = 11 + log {c (NaOH)j

C,,,,"c, - "3 CCA

referred 10 moll!

~~ U". 2:Q P H = 11 + Iog

}

BI-I-I- {
~~
.0
E'~
,!!Jg"
"'0;
.~
,;
,
"
>
~~~
N •
t;,g
f~~
e

'';:: en 0
E -- - 8-- --~
(i) ~

e
11~
.
,;:'\3
"g:2
E.
Eo
~
pH = 11 -log
243
243 + log {C,",nc,- "3 CCA}
l' 8=
M .g o
u ,
E !12~ pH = 6.60 + log {Cd,,"c'- "3 CCA}
~ ~~,~

GEe: g
~
~ in• (; ~ 8 in
]j
o
>--
]j
] =.~
W 0

'" • according 10 DIN. t31:3 IOI6qU(lI~ Ihe vnlu(l 01 a

24
• 25
(",
,_/

_. __ ._---_ ..•_ .."_ _-.-~.._

.. _----_.
.•.•.. __ ._- ---_ ..- '--'
 •

,
I

Table 2. Boiler warer of derrunerafized feedwarer. COt1:J.nUOUS

coefiWon.
Ae-quuemenrs an l>CiIJer water of once-througt'J boilers wrllcr. are fed wirtl demineralized ~a!!?f acc:roing to Table 1_

Preconci:lon Alk.alizing 01 the boiler water

, Alkalizing of the boiler wa,er
with solid atk.altZing agents I with volatile agents
according 10 seclion 3.1:
no addittonaJ alkaliZing
of the boiler water

Permissible ooera:ing pressure oa, < 136 :> 136 all operating pressures

Heal flux .:iens.'ty k.W!m2 : all heal flJx densities

I
<250 >250
I
Cood""""'Y at 25 'C i <5 <3
downstre.am ot a strongly addie sampling
cation ex:::nanger. continuous measuremer.t
i
at the sa.~ POint ~S/cm <50 I
pH al25"C
10.=0.2 , 9.5, 02 Ii the pH or !he leedwater has to De set
for alkaline opelC!ling maces
continuous measurement
If necessa."y .•••
,1tl me aid
of auxdlC!ry variables
Ii
(sedon ':.21
I,
litphospr.aE
lr.~.ate isdcse-j: c
(PO.'>-)
"'g':: <6 <3 I amrne<:i
i
Tne pH e-.oel:s rocaled eferabiy to t.;: s,.e.l.::;; .'~aOH: f ~"'Cn.lmphosp;.a:e
a~e : .•.. tS dcseO. aCoto-.ai a::oicaticn01 NaOH;s requi~ oniy
jf the ~oed pH lc'.',,>Jscar:nct De ac--Joeh' ••..=::•.exc!us.',,,,, a.:.:ir.g Na3PC~ a:;::r.e adt",ere..-c:e t tl"oe ~O. siar.can:: vail.;:.

',,:.
 ~ ..
'~

,', The graphical representation of this equation demo'llstrates the conductivity values
Cdireciand CCA at which the recommended pH level,s listed in Table of the present
VGB Guideline, i.e. 10:l: 0.2 for < 136 bar operating overpressure and 9.5:l: 0.2
for> 136 bar operating overpressure. are mel.

60

50

&

T
~
.s ""
~
•
~
~"
u
u
c "
0
0

d:
5
•ro
•E
""~
U

ii

o o '0 20 30 40 50
conduclivity (eCA) measured downstream of a calion exchanger in pS/cm ---e---
Fig. 1. Comlilioniflg of tim bOllor wntor of fllllurni circulntion boilers with sodium hydroxirlo.
Conneclion be/ween pH and directly monsurod conductivity nnd that
moasured downs/roam of a cation oxchanger.
,
26

.,