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35
A PRACTICAL GUIDE
TO AVOIDING
STEAM PURITY PROBLEMS
IN THE INDUSTRIAL PLANT
AN ASME RESEARCH REPORT
prepared by the
FEEDWATER QUALITY TASK GROUP
for the
INDUSTRIAL SUBCOMMITTEE
OF THE
ASME RESEARCH AND
TECHNOLOGY COMMITTEE ON
WATER AND STEAM IN
THERMAL POWER SYSTEMS
Copyright © 1995 by
THE AMERICAN SOCIETY OF MECHANICAL ENGINEERS
All Rights Reserved
Printed in U.S.A.
❒ PREFACE ❒
iii
iv
❒ ACKNOWLEDGEMENTS ❒
This document was prepared by the Steam Purity Task Group of the
Industrial Subcommittee of the ASME Research and Technology
Committee on Steam and Water in Thermal Power Systems. Recognition
is hereby given to the following members of these groups for their contri-
butions in preparing the document.
Industrial Subcommittee
James O. Robinson, Chairman R. W. Lane
Anton Banweg P. J. Latham
T. Beardwood Roger V. Long
Jesse S. Beecher D. E. Noll
James C. Bellows, Ph.D. Thomas H. Pike
Wayne E. Bernahl F. J. Pocock
Deborah M. Bloom L. Rosenzweig
Irvin J. Cotton J. K. Rice
Robert J. Cunningham J. J. Schuck
David Daniels John W. Siegmund
Douglas B. DeWitt-Dick David E. Simon II
S. B. Dilcer, Jr. P. M. Thomasson
Arthur W. Fynsk T. J. Tvedt, Jr.
F. Gabrielli John R. Webb
S. Goodstine W. Willsey
Karl W. Herman J. F. Wilkes
Robert T. Holloway David K. Woodman
K. Kelley
v
vi
❒ C ONTENTS ❒
1❒ Introduction 1
2❒ Steam Purity 3
Tables
Figure
References 39
vii
viii
❒ SECTION 1 ❒
INTRODUCTION
1
2
❒ SECTION 2 ❒
STEAM PURITY
3
4
❒ SECTION 3 ❒
PROBLEMS CAUSED
BY POOR STEAM PURITY
❒ 3.1 Superheaters
Superheater deposits are usually caused by the entrainment of boiler
water in the steam. A portion of the entrained boiler water adheres to the
superheater tube surface and leaves solid deposits when the water is
evaporated. This buildup of deposits may coat the internal surfaces of the
superheater elements or wash down to the lower bends during shutdown.
If sufficient deposit accumulates in the tube, metal temperature will in-
crease to the creep range, forming blisters and often leading to tube fail-
ure. Deposits sometimes accumulate enough to restrict the steam flow
and cause downstream failures.
5
Carryover can also cause corrosion of the superheater. Attack may vary
from gouging to stress corrosion cracking. Gouging attack usually occurs
at the lower bends since soluble alkaline contaminants that wash there
during shutdown concentrate when condensate is boiled off during
startup. Because oxygen corrosion during shutdown causes pitting of the
lower bends, care must be taken to avoid confusing the two types of cor-
rosion.
Caustic embrittlement occurs from caustic contamination of the steam,
and both halides and caustic have been known to cause stress corrosion
cracking in austenitic stainless steel superheater tubes.
The level of steam purity required to protect superheaters from damage
varies with the superheater design and boiler operation. While individual
plant operating experience must dictate system requirements, a steam
solids level of less than 0.3 ppm (less than 0.1 ppm sodium) is satisfactory
for most industrial boiler superheaters.
6
valves, and governor valves on turbines to stick. The potential danger of
overspeed and resulting failure is a real concern. Deposits on the blades
can lead to reduced efficiency and turbine imbalance.
Steam contamination can also cause corrosion. As the contaminants
pass through the turbine, a concentrated solution that is corrosive may
form on the system metal. Localized pitting and cracking of the disks and
blades can occur. Solid particles and liquid droplets in steam can cause
erosion damage. Salt deposits often cause severe pitting corrosion during
out-of-service periods when oxygen and moisture are both present.
Operating experience suggests that the maximum acceptable level of
steam contamination for most continuously operating industrial turbines
is 60 ppb total dissolved solids, including 20 ppb sodium plus potassium
as Na and 20 ppb silica as SiO2 . For those systems without appreciable
sodium hydroxide or sodium carbonate in the boiler water, a degassed
cation conductivity of less than 1 micromho per centimeter is usually an
indication of acceptable steam purity. However, several factors should be
considered when stipulating the steam purity criteria for a specific tur-
bine, which include
• the steam conditions at the turbine inlet and exhaust
• the previous operating history of the turbine
• the anticipated operating conditions of the turbine
• the turbine manufacturer's specifications
Maintaining satisfactory steam purity requires continuous representa-
tive sampling of saturated steam, and, perhaps superheated steam if water
less pure than the saturated steam is used for direct spray desuperheating
or attemperation. The steam purity should be monitored by continuous
measurement of degassed cation conductivity and/or sodium. Silica con-
centrations are rarely monitored continuously, but may be checked rou-
tinely by manual analysis of grab samples of steam.
7
❒ 3.4 Manufacturing Processes
Steam is widely used in industrial manufacturing processes for heating,
evaporating, reforming, reacting, distilling, etc. Where steam is used di-
rectly in the process, impurities can lead to catalyst fouling, fiber staining,
and product contamination.
Where steam is used for indirect heating, the major concern is the con-
centration of corrosive gases in the condensed steam. Oxygen, carbon
dioxide, ammonia, and sulfur dioxide are the most common corrodents
and must be kept at low levels, or neutralized, to avoid corrosion and
equipment failure. These gases and other non-condensable ones can also
greatly reduce heat transfer.
Because steam is used in such a wide variety of manufacturing
processes, the steam purity requirements for these processes vary over a
broad range. In general, the steam purity required for use in turbine drives
is more than acceptable for manufacturing processes. There are notable
exceptions, however, including operations in which steam is used directly
in a process, e.g., catalytic processes, hospital sterilizers, pharmaceutical
manufacturing, and food processing. In many cases there is a limitation on
specific contaminants rather than the total level of contaminant. The steam
purity criteria for each process must be established individually.
8
• octadecylamine
• trisodium nitrilotriacetate
have specific limits on the concentration allowable in steam used for food
preparation. The use of these six substances is prohibited where the steam
comes in contact with milk or milk products. Their use is also prohibited
where the steam contacts drug components, in process materials, and in
the manufacture of drugs, drug products, and drug contact surfaces.
(Federal Register, June 1, 1976, Section 212.227).
❒ 3.6 Humidification
The improper use of neutralizing amine treatments in steam systems
can lead to adverse health effects where steam is used for direct injection
to a humidification system. Instances of skin irritation, dizziness, and
lacrymation due to overfeed have been reported.
The potential long-term effects of amine exposure are being scruti-
nized. A recent detailed study of health risks associated with the use of
morpholine and DEAE for the Department of the Navy notes uncertainties
and gaps in data that make it difficult to assess the long-term effects of
their usage. The report recommends continued research. [1,2]
The permissible airborne exposure limits established by OSHA are 20
ppm (by volume) for morpholine, 10 ppm for DEAE, and 1.0 ppm for hy-
drazine. These limits are applicable only to the workplace, with maxi-
mum exposure of 8 hours a day, 5 days a week. The American Conference
of Governmental Hygienists (ACGIH) has set a Threshold Limit Value-
Time Weighted Average (TLV-TWA) of 20 ppm (by volume) for morpho-
line and 10 ppm for DEAE, 10 ppm for cyclohexylamine, and 0.1 ppm for
hydrazine. Sylvia Edgerton, et. al. of Battelle (Columbus) conducted a 30-
hour study in an indoor office/laboratory steam humidified by a system in
which cyclohexylamine and DEAE were added for corrosion control. The
concentration in the air of each amine was less than 1 ppb. [3]
Amine use in systems in which steam is used in humidification should
be approached with caution. The treatment control must be fully reliable
to avoid overfeed. The best method is to feed in proportion to system flow.
Do not slug feed these materials at any time. Because of the obvious
short-term effects of overfeed and the uncertain long-term effects, the best
approach is to use a separate system to generate steam for humidification
in order not to introduce into the air the amine used for condensate sys-
tem protection.
9
10
❒ SECTION 4 ❒
CAUSES OF POOR
STEAM PURITY
11
100.0
80.0
60.0
40.0
20.0
10.0
Boiler Water Silica, ppm
8.0
6.0
4.0
2.0
1.0
0.8
0.6
0.4
0.2
0.1
400 800 1200 1600 2000 2400 2800 3200
12
4.2.1 ■ Chemical Factors.
The chemical factors are those species that decrease the surface tension of
the boiler water and thus promote the formation of a stable foam. The mate-
rials that commonly cause this effect are total dissolved solids, alkalinity, cer-
tain organic compounds, and suspended particulate matter. Suggested limits
for the maximum concentrations of contaminants in industrial boiler water
have been published by ASME [4] and ABMA [5].
The worst problems occur when the surface tension is decreased so that
steam bubbles accumulate, raising the level in the steam drum. This foam-
water mixture can carry huge amounts of boiler water out of the drum into
the steam line or the superheater. However, even at a lower concentration of
surface-active solids, entrainment carryover of a lesser but still undesirable
amount can result from the failure of the steam bubbles to break cleanly.
Another aspect of foaming is the development of level control problems.
The building or breaking of a foam layer may be interpreted as a water level
change by the feedwater control system. This misinterpretation of the foam
level as the water level will cause the feedwater regulator to respond erro-
neously, producing real changes in boiler level that can cause steam conta-
mination.
4.2.2 ■ Mechanical Factors.
The design of the steam drum and the steam/water separation devices
within the steam drum affects the amount of boiler water carryover. The drum
should be designed with sufficient area to permit good steam/water separa-
tion in the space above the normal water level. Internal steam separation de-
vices should improve steam/water separation without creating excessive pres-
sure losses. Several separator designs are used by the various boiler manu-
facturers. These devices must be maintained as clean as possible and kept
properly fastened in the correct position. Any loosening, misalignment, or
cracking of baffles or buildup of heavy deposition on the screens can cause
separators to malfunction and increase the mechanical carryover dramati-
cally.
4.2.3 ■ Operational Factors.
The operational factors that can cause entrainment carryover are numer-
ous. Some can be conveniently corrected by modifying operating practices
while others are so much a part of industrial processing requirements that
making changes is difficult. Operating the boiler above its rated steam gener-
ation capacity can overload the steam-water separators. They can also be over-
loaded by operating the boiler below its design pressure because lower pres-
sure increases the steam velocity through the separators. Operating the boiler
with high water level can also overload the separators with too much water.
Boilers are operated with a high water level for several reasons. Sometimes the
13
operator intentionally maintains a high water level to avoid other prob-
lems. Other times the drum level instrumentation gives a false indication
of the level over the full length of the steam drum, or the steam load
swings are of sufficient magnitude that a loss in pressure causes a surge
in drum water level.
14
❒ SECTION 5 ❒
METHODS OF DETECTING
STEAM PURITY PROBLEMS
15
evaporate carryover moisture.
(5) Increasing superheater tube temperatures. An increase in metal
temperature as measured by thermocouples on individual supe
rheater circuits may indicate a buildup of deposit inside the tubes.
(6) Turbine pressure. A buildup of first stage turbine pressure is often a
sign of turbine fouling. By maintaining a record of turbine stage
pressure vs. steam flow under similar operating conditions, turbine
fouling can be detected.
(7) Loss in turbine generator or compressor capacity. As a turbine
becomes fouled with deposition, the maximum output from the dr
ven machine is reduced.
(8) Sticking steam admission, regulator and stop valves. The buildup of
deposits on valve stems can cause malfunctions and are usually a
sign of steam contamination.
16
tinuous basis. The type of monitoring required will depend on the ulti-
mate steam purity requirements; however, sodium analysis and/or de-
gassed cation conductivity measurement will usually prove satisfactory.
(3) Boiler Water Monitoring. Boiler water contamination can often lead
to steam purity problems. The boiler water conductivity should be moni-
tored on a regular basis and consistently maintained within a specified
control range that has been determined suitable for the plant. The pres-
ence of contamination as a result of ion exchange regenerant introduction
or condensate contamination should be detected and action taken to con-
trol boiler water chemical contaminant levels within a defined range at all
times.
17
18
❒ SECTION 6 ❒
INVESTIGATING A STEAM
PURITY PROBLEM
19
could also be present from attemperating water contamination. Silica de-
posits may be the result of either boiler water entrainment in the steam or
selective vaporization of silica from the boiler water. Sodium hydroxide
deposits may be present as the result of either boiler water entrainment in
the steam or demineralizer regenerant contamination of the attemperat-
ing water. Acidic sulfur deposits may result from the decomposition of
sodium sulfite in boilers operating above 900 psig, contamination of at-
temperating water, or acidic sulfur gases being returned with the conden-
sate. Other deposits such as aluminum, titanium, and barium need to be
traced for their source of entry into the system.
20
feedwater sampling while control room data is recorded. Steam samples
should be flowing for at least 24 hours before the test, and the sampling
rate should be in accordance with the ASTM specification for isokinetic
sampling. All samples should flow continuously throughout the test pe-
riod. A typical test procedure for determining boiler steam purity perfor-
mance under base load conditions is described below.
Several hours before the test, boiler water dissolved solids should be
established at the level normally maintained by the plant by adjusting the
continuous blowdown valve setting if necessary. Steam samples should
be collected through properly designed sampling nozzles and coolers
and fed to the bottom of an overflowing plastic bottle or to an on-line an-
alyzer. Drum water level should be established about 3 in. to 4 in. below
normal but definitely above the low water level cutoff. If possible, the
steam flow at the start of the test should be established at 50% of the de-
sign capacity. When the boiler has been stable for 15 minutes, collect a
saturated steam sample, a boiler water sample, and a feedwater sample.
Record time, date, steam flow, feedwater flow, drum water level, spray
water flow, drum pressure, load, and gauge glass water level.
When the above steps have been completed, increase the steam flow
to 75% of rated capacity and repeat the initial steps, then increase the
steam flow to 100% of rated capacity. By adjusting drum water level,
blowdown, and chemical additives such as antifoam chemicals, an over-
all picture of the boiler steam purity performance under base load condi-
tions can be developed.
Variations in boiler load, drum level, and header pressure frequently
cause a deterioration in steam purity not found at base load conditions.
Because many steam purity problems are caused by operating transients,
continuous monitoring of steam purity during normal operation is often
required to identify the operating conditions that cause steam purity prob-
lems.
21
22
❒ SECTION 7 ❒
CORRECTING A STEAM
PURITY PROBLEM
23
tors may be necessary.
24
a "swelling" of the boiler water in one area of the drum, which
causes carryover. Firing patterns should be checked and adjusted
if necessary.
4. Is the feedwater line intact, all openings clear and pointed in the
proper direction?
Improper feedwater distribution may cause spray in the steam
space and overloading of the steam separators.
5. Is the continuous blowdown line intact and properly located?
If not, samples can give a misleading indication of boiler water
concentrations.
It may also be possible to improve steam purity by adding new sepa-
rators or revising the existing design, but such changes should be ap-
proached very cautiously with before-and-after testing to ensure that the
change is beneficial.
External separators are a possible solution if additional mechanical
separation is needed that cannot be accommodated in the steam drum. A
major disadvantage of an external separator is that the piping between the
steam drum and the separator is especially susceptible to erosion and cor-
rosion because of the entrained water droplets.
25
26
❒ SECTION 8 ❒
OPERATING GUIDELINES TO AVOID
STEAM PURITY PROBLEMS
27
28
❒ SECTION 9 ❒
STEAM SAMPLING
AND ANALYSIS
29
❒ 9.2 Analyses
Analytical procedures may be found in the ASTM Power Plant Water
Analysis Manual and numerous other analytical documents.
Sodium Ion
As a general rule, sodium ion in the steam from an industrial steam gener-
ator is considered to represent one-third of the total dissolved solids. It, there-
fore, provides a good means of monitoring steam purity. The sample can be
continuously analyzed by means of a sodium-specific ion electrode, or grab
samples can be analyzed by the same method or by flame photometry, atomic
absorption, ion chromatography, or inductively coupled plasma. The choice of
analytical method depends on the sodium concentration of interest, the loca-
tion of the test, and the duration of the testing. The specific ion electrode is the
most suitable for continuous measurement in most plant environments.
Silica
If the maximum allowable silica limits in the bulk boiler water are ex-
ceeded, excessive amounts of silica will volatilize and be carried over in the
steam as silicic acid. Where the steam is being utilized to drive rotary equip-
ment, the silica can deposit on the blading as the pressure and temperature
are reduced.
Silica in the steam can be monitored either on a continuous basis or on a
grab sample. In either case, the analysis is performed utilizing photometric
methods of either heteropoly blue or molybdosilicate. To avoid phosphate ion
interference, oxalic acid is added to the sample.
Specific Conductivity
Specific conductivity is an indirect method of determining the total dis-
solved solids. It is a measure of the ability of an aqueous solution to conduct
an electrical current — the greater the amount of dissolved solids in solution,
the more electrical current the solution can conduct. Specific conductivity is
an excellent monitor for the detection of high level steam contamination.
When lower level contaminant detection is required, the specific conductiv-
ity should be measured on a degassed sample since dissolved gases, i.e., am-
monia, volatile amines and carbon dioxide, have a great influence on con-
ductivity. To increase the sensitivity of anionic contaminant detection, de-
gassed cation conductivity is recommended; however, it should be noted that
cation conductivity will not detect sodium hydroxide.
Chloride Ion
The chloride ion has been shown to contribute to the deterioration of
turbine blading. It can be monitored either on a continuous basis or on
grab samples. Analysis can be performed either by chloride specific ion-
electrode or ion chromatography.
30
Metal Oxides
Since metal oxide particles may contribute to turbine blade damage
and may indicate superheater tube deterioration, their measurement is in-
cluded in this section. The analytical work is performed on a grab sample
and run either by atomic absorption or inductively coupled plasma. Low
level colorimetric tests are also available.
For gross suspended metallic oxides, 0 micron to 0.45 micron filters
can be utilized and compared to standard charts for an estimation of the
oxide content of the steam.
31
32
❒ TABLES ❒
33
34
TABLE 1
U.S. Customary SI
1 gallon 3.78 liters
1 inch 2.54 centimeters
1 micromho 1 microsiemens
o o
212 Fahrenheit 100 Celsius
1 part per million (ppm) 1 milligram per liter
1 psig 7.03 kilo pascal
1 part per billion (ppb) 1 microgram per liter
35
TABLE 2
36
Substances Limitations
37
Substances Limitations
Sodium humate Less than 1 part per million cyanide in the
Sodium hydroxide sodium glucoheptonate.
Sodium lignosulfonate
Sodium metabisulfite
Sodium metasilicate
Sodium nitrate
Sodium phosphate (mono-, di, tri)
Sodium polyacrylate
Sodium polymethacrylate
Sodium silicate
Sodium sulfate
Sodium sulfite (neutral or alkaline)
Sodium tripolyphosphate
Tannin (including quebracho extract)
Tetrasodium EDTA
Tetrasodium pyrophosphate
Substances Limitations
Cyclohexylamine Not to exceed 10 parts per million in steam,
and excluding use of such steam in con-
tact with milk and milk products
Diethylaminoethanol Not to exceed 15 parts per million in steam,
and excluding use of such steam in con-
tact with milk and milk products
Hydrazine Zero in steam
Morpholine Not to exceed 10 parts per million in steam,
and excluding use of such steam in con-
tact with milk and milk products
Octadecylamine Not to exceed 3 parts per million in steam,
and excluding use of such steam in con-
tact with milk and milk products
Trisodium nitrilotriacetate Not to exceed 5 parts per million in steam,
and excluding use of such steam in con-
tact with milk and milk products
(e) To assure safe use of the additive, in addition to the other informa-
tion required by the Act, the label or labeling shall bear:
1. The common or chemical name or names of the additive or ad-
ditives.
2. Adequate directions for use to assure compliance with all the
provisions of this section.
38
❒ REFERENCES ❒
39
40