SUBJ ECT.

" Boiler Water Contamination

Troubleshooting l ow or high pH in
boilers that use high purity water
High pressure boilers and the associated use of demineral-
ized wat er are now common in the pulp and paper industry.
Demineralized wat er is also being widely used for both
recovery and power boilers operating below 1000 psig.
Use of high purity (demineralized) wat er presents dif-
ferent problems for operators than do zeolite softener
makeup systems.
The Wat er Treatment Subcommittee of the TAPPI
Steam and Power Committee has prepared a series of five
articles that describe recommended actions to address the
t ypes of contamination t hat can occur in high puri t y
feedwater. The first two, on low pH and high pH, appear in
this issue. The others, on silica intrusion, black liquor con-
tamination, and feedwater hardness excursion, will appear
in future issues.
Operators should be trained in what actions to take in
response to contamination and to initiate action before
significant equipment damage occurs.
Every boiler system is different. These recommenda-
tions should be used as guidelines that can be adapted to
one's situation. In all cases, when a deviation from normal
wat er quality occurs, notify your wat er t reat ment consult-
ant/supplier.
The following members of the Wat er Treatment Sub-
committee of the TAPPI Steam and Power Committee
worked to prepare this series of articles:
James N. Arntson--Temple-Inland Forest Products Corp.
George H. Bodman--Halliburton Industrial Service
Paul R. Cai n--Sent ry Equipment Corp.
Kenneth P. Hagadorn--W. R. Grace & Co.
Charles R. Hoefs Nalco Chemical Co.
Ralph L. Mason--Weyerhaeuser Paper Co.
John M. Pace--Cal gon Corp.
Donald E. Riggs Betz Industrial
Joel D. Robbi ns--Fi nch Pruyn & Co.
Strati Yorgiadis--Sheppard T. Powell Associates
Low p H
Background
Use of deionized wat er as a makeup source has increased
the need for operator awareness of boiler wat er chemical
control, testing, and response. High purity makeup wat er
does not contain measurable alkalinity, therefore boiler
wat er usually contains a very low to zero level of hydroxide
alkalinity. Boiler wat er alkalinity acts as a buffer. Caustic
can be added to increase alkalinity in boiler water; however
as operating pressures increase over 1000 psig, this can
lead to a problem of caustic concentration and correspond-
ing corrosion.
Boiler wat er alkalinity is a pH buffer against feedwater
contamination. A buffer is defined as a substance in solu-
tion which accepts either hydrogen ions (acids) or hydroxyl
ions (bases) entering the system, t hereby minimizing a
change in pH.
With very low hydroxide alkalinities, the buffering ca-
pacity of the boiler wat er becomes reduced and feedwater
contamination more significantly influences the pH. Where
a coordinated phosphate program is being used, buffering
capacity is minimal and pH can change rapidly with the
slightest amount of feedwater contamination.
Cont ami nat i on sources
Contamination of high purity feedwater can occur from
several sources.
1. Salts entering the feedwater from condenser leaks or
demineralizer leakage. If the leakage is high in magnesium
chloride (brackish water) the chance of a low pH condition
is greater. A small amount of hard wat er leakage could
cause a pH of 4 or less in an unbuffered boiler water.
2. Demineralizer regenerant leakage. Cation exchange
resin requires a strong acid for regeneration, usually sulfu-
ric or hydrochloric. The regenerant can enter the feedwater
when valves do not close properly during regeneration.
The most common causes of this phenomenon are a power
outage and leaking valves or both.
3. In boilers over 1000 psig pressure, black liquor con-
tamination may cause the boiler wat er pH to drop due to
organic acids, high magnesium, or high sulfidity.
Immediate action
Low pH exclusions require immediate action to minimize
the effects on boiler waterside surfaces. A summary of pH
levels and appropriate actions to be taken are shown. Boiler
wat er pH tests should be conducted frequently until the
problem is corrected.
For the following boiler wat er pH ranges, continuing
actions should include:
September 1992 Tappi Journal 275
1. p H 8. 6 t o 9. 2
Action
Add trisodium phosphate and back out any monosodium
phosphate being fed.
Begin aggressive search for contaminant source includ-
ing alignment of regeneration valves, hardness checks on
boiler feedwater, and black liquor contamination.
Maintain phosphate in normal range.
2. pH 8. 0 to 8. 6
Action
Start feeding caustic to re-establish normal operating pH.
Increase continuous blowdown to maximum allowable rate.
If dispersant is being fed, increase feed to match in-
creased blowdown.
Add or increase boiler water antifoam to minimize
carryover.
Monitor steam purity:
(A) Monitor condensed steam for sodium level
(B) Monitor condensed steam for conductivity level
(C) Monitor superheater outlet temperature.
3. pH 7. 0 to 8. 0
Action
Notify downstream users of potential impact to their
system.
Continue actions shown in Step 2.
Reduce boiler steaming rate by 20%.
4. pH 6. 0 to 7. 0
Action
Reduce steaming rate by an additional 20% (total 40%).
Start to use all possible blowdown, both continuous and
manual.
5. pH 5. 0 to 6. 0
Action
Prepare to take boiler offline. I f pH continues to de
crease (below 5) the fire needs to be pulled immediately.
Continue heavy blowdown of boiler and drain at proper
time.
Refill with treated demineralized water, caustic, triso-
dium phosphate, or regular water treatment chemicals.
If the boiler is continuing to run at pH lower than 5 for
more than 4 h and the pH was brought back up with caustic
addition, large amounts of iron (corrosion product) will
precipitate as iron hydroxide. Iron deposits will form on the
hot surfaces of the radiant section and could cause tube
failure short-term (within weeks) or long-term (within
months). Chemical cleaning as soon as practical is recom-
mended to remove the deposited iron.
Hi gh p H
Background
High pH in a high pressure boiler system can cause dam-
age in two areas: (1) damage from corrosion in the high heat
release zone of the boiler and (2) sodium carryover into the
steam, resulting in possible superheater and turbine corro-
sion.
High pH, above 10.2, is desirable when running a posi-
tive hydroxide alkalinity program.
When running coordinated phosphate congruent con-
trol, boiler water pH is below 10.2, usually in the 9.2 to 9.8
range depending upon the specific control parameters. A
pH greater than 10.2 is undesirable; 10.2 is the maximum
pH for these guidelines.
Sources
Boiler water pH over 10.2 may occur in a high pressure
demineralized makeup system from:
Excess sodium leakage from the demineralizer make-up
system
Over feed of trim caustic
Black liquor contamination. (This will be discussed fur-
ther in the November issue.)
Symptoms
Symptoms of high pH in a high pressure boiler system
include:
High feedwater pH
High feedwater conductivity
High boiler water pH and hydroxide alkalinity
High boiler water conductivity.
I mme di at e action
1. pH 10. 0 to 10.5
Action
Increase continuous blowdown to maximum allowable
rate.
Shut off and block all caustic feed to the boiler.
Test feedwater, makeup water, and condensate for pH,
2 7 6 September 1992 Tappi Journal
dissolved solids, and alkalinity.
Operate st eam dr um level at lowest safe point to mini-
mize carryover.
2. pH 10.5 to 11.0
Action
Add or increase boiler wat er ant i foam to minimize
carryover.
Maintain continuous blowdown at maxi mum allowable
r at e and st ar t manual blowdown.
Monitor st eam purity:
(A) Monitor condensed st eam for sodium level
(B) Monitor condensed st eam for conductivity level
(C) Monitor superheat er outlet t emperat ure.
3. pH 11.0 to 11.5
Action
Not i fy downst ream users of potential impact to t hei r
system.
Consider load reduct i on if pH continues to climb and
sodium levels in the st eam exceed 100 ppb.
Caution--acid addition is not recommended for pH
excursion control.
I f sodium in t he st eam continues over 100 ppb for over 4
h, boiler or t urbi ne shutdown may be necessary to prot ect
t he st eam turbine. In cases of ext reme carryover (>500
ppb) a short er-t erm tolerance would be necessary. []
September 1992 Tappi Journal 277