Corrosion of Carbon and Stainless Steels
in Flue Gases from Municipal Incinerators
PAUL D. MILLER and HORATIO H. KRAUSE
Battelle, Columbus Laboratories
Columbus, Ohio
ABSTRACT
INTRODUCTION
Both field and laboratory corrosion studies are
discussed. The field work involves operation of corrosion
probes and/or analyses of gases and deposits in
municipal incinerators in Miami County, Ohio, at
Oceanside, New York, and in the Navy Salvage Fuel
Boiler at Norfolk, Virginia. Examinations of the
surfaces of these probes and of the deposits coming from
them using X-ray diffraction and the electron micro­
probe have shown that compounds containing sulfur,
chlorine, lead, zinc, and potassium are contributing
to the corrosion reactions.
The results have shown that the corrosion of the
carbon and stainless steels used increases as the metal
temperature rises from about 350 to 1000 F. The
temperature gradient moving from the metal through
the deposit to the surrounding gases is also of
importance.
The field studies have also included analyses of
furnace gases from several incinerators. Average con­
centrations of corrosive gases such as S02 and HCl were
found to be about 100 ppm. Laboratory work and
field results have provided an explanation of the
corrosion reactions. As might be expected, they are
complex and interrelated. It is suggested that HCl,
C12 , K2S207, KHS04, NaCl, ZnCl2, and PbCl2 are
involved.
Recommendations have been made that water-wall
incinerators be operated at low metal temperatures,
near 500 F, to minimize corrosion.
The disposal of solid waste is becoming of
increasing importance throughout this country. In­
cineration has several promising features, but the
technology needs further development. Of particular
importance are methods for incinerating municipal
refuse in such a way that offensive dusts and gases are
not emitted to pollute the atmosphere. Air-pollution
standards require that solid particulate matter be
removed from such flue gas. This cleaning of me
gases can be accomplished by mechanical collectors
or by electrostatic precipitators. but the volume
of gas must be as small as possible and the temperature
should not exceed about 600 F. Three basic methods are
used for accomplishing this cooling:
(1) Spraying water into the flue-gas stream;
(2) Diluting flue gas with cool air; and
(3) Absorbing heat in flue gas by water-cooled
tubes forming the furnace walls and convection
surfaces.
Cooling with water sprays results in wastage of
large quantities of water, the introduction of the need
for disposal of contaminated corrosive water. and
the production of an unsightly plume.
Cooling with air requires large fans and the power
to run them. Such cooling also requires much larger
sizes of pollution-control equipment because
of the greatly increased gas volumes.
For large-scale municipal units. it is advantageous
to absorb the heat from the flue gas. using the same
300
basic techniques as in conventional boiler furnaces.
In addition to simplifying requirements for pollution­
control equipment, a heat-utilization scheme
provides a useful outlet for the heat generated by
the combustion of the refuse by generating low-pressure
steam that can be sent to a turbine. An additional
advantage of this procedure is a possible increased
throughput because of the rapid heat absorption in
the water-cooled furnace.
An attractive design is one in which the refractory
walls of the usual incinerator are replaced with water­
cooled tubes, much as in modern boiler furnaces,
together with tube banks to cool the gases leaving
the combustion zone.
One problem faced in water-cooled incinerators is
a presently unpredictably severe loss of metal from
convective-heat-transfer tube banks, and also from the
furnace wall tubes. A number of instances of severe
metal wastage in incinerators have been reported, along
with other details of incinerator operation [1-14].
Most experience has been accumulated in Europe,
particularly in Germany where many plants with
boilers are burning municipal refuse. This experience
did not provide a complete explanation as to the
cause of the corrosion, but did indicate the possible
importance of operating conditions (oxidizing versus
reducing) and the effect of chlorine-containing com­
pounds in the refuse. That is, reducing conditions and
the presence of the chlorides enhanced corrosion.
Because there is increasing interest in the United
States in the construction of large water-wall
municipal incinerators, the Solid Waste Management
Office of the Public Health Service, Environmental
Protection Agency, commissioned Battelle-Columbus
to study the fireside wastage that could be anticipated
in such units and to devise possible methods of allevia­
tion. This research began on March I, 1969, under a
gran t program [15] .
As the work progressed, it became apparent that
other areas of an incinerator were subject to corrosive
attack. Wet scrubbers in particular are quite vulnerable.
Accordingly, a companion study has been initiated
during the third year of the program on corrosion
in wet scrubbers.
Miami County, Ohio, and in a water-wall incinerator
operated by the Navy Public Works Center at Norfolk,
Virginia [16] . Deposits and gases from an incinerator
at Oceanside, New York, were also analyzed. Eleven
corrosion probes made up of the following metals were
run under controlled-temperature conditions:
AI06-Grade B and A213-Grade TIl carbon steels,
and AISI Types 304, 3 10, 316, 321, and 446 stainless
steels. Metallic coatings of chromium and aluminum
were also evaluated.
The probe was designed to include 34 cylindrical
specimens nested together end to end and then inserted into the incinerator through a side wall. The
section of the probe extending through the wall was
water cooled. The specimens exposed within the furnace
were cooled by air flowing inside the tubular specimens.
A computer analysis was used to ascertain the geometry
of the internal support tube required to give the most
linear specimen-temperature variation over the range
of about 350 to 1 100 F for a probe with 34 specimens.
Each specimen was about 1.25 in. in OD, 1.00 in. in
ID, and 1.5 in. long.
Fig. 1 is a schematic of the final exposure-probe
apparatus. The specimens are nested together with lap
joints as shown in Detail A, and retained axially at
the cooling-air-outlet end by a retainer which is fixed
to the internal support tube with webs as shown in
Section A-A. The axial restraining force in the internal
support tube is obtained by compressing the spring on
the air-inlet end of the probe at assembly. The spring
compensates for differential thermal expansion between
the specimens and the internal support tube.
Specimen temperatures are measured at four stations
with Type K thermocouples either welded into the
wall of the specimens or inserted into recesses
drilled lengthwise into one end of the appropriate
specimen.
The thermocouple lead wires are brought out of the
probe through the center of the internal support tube,
so that temperatures can be recorded continuously on a
strip-chart potentiometer recorder. Since the computed
results indicated that the temperature variation is
linear for regions with a constant gap between the in­
ternal support tube and the specimens, the four
temperatures accurately define the specimen
temperatures.
The specimen temperatures are controlled by
regulating the amount of cooling air admitted to the
probe. The output from a control thermocouple,
which is attached to the specimen at the same axial
location as the Thermocouple 3, is monitored by a
proportional temperature controller. During a run,
the controller maintains this temperature by varying
CORROSION-PROBE STUDIES IN THE FIELD
Procedures
In order to obtain realistic estimates of tube wastage
and deposit formation, it was necessary to operate
probes in the field over extended periods. These were
inserted in a refractory-lined municipal incinerator at
301
Sirip Chorl
potenhometric
Spring 10 compensate
tor d"terentlal
thermol expanSion
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motor
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Speci men Detoils Enlorged
Fig.
1
Section A-A
Enlorged
Schematic of specimen-exposure-probe apparatus.
over the surface. Thus, the hydrolytic properties of
salts present on the surfaces could be determined.
Selected specimens were retained intact for special
examinl)tion by X-ray, electron-microprobe, and metal­
lographic procedures.
The other pieces were descaled by methods which
prevented attack of the base metal. The carbon
steel specimens were stripped cathodically in 10 percent
H2 S04 containing 1-ethylquinolinium iodide inhibitor.
The stainless steel specimens were descaled in a two­
step process: first with 1 1 percent NaOH and 5 percent
KMn04 at 212 F, and then with a mixture of 20
percent HN03 and 2 percent HF at 130 F.
The amount of metal wastage was determined by
weight-loss measurements.
On the basis of OD and ID micrometer measure­
ments, the overall weight loss was adjusted to reflect
the proportion of loss which occurred on the outside
surface. This was of significance only in the cases where
appreciable oxidation had occurred on the inner surfaces.
The wastage rates for the specimens were calculated
and expressed as "mils per month" penetration. Fig. 2
illustrates data for one of the runs made at Miami
County.
Comparison of the results from many probes, when
the amount of cooling air bypassing the probe through
a motorized butterfly valve located between the blower
and the probe. A Roots-blower air pump delivering
up to about 34 cfm was used with a 5-hp motor
as a drive
The corrosion probes as removed from the in­
cinerators are covered with scale and deposits. More
of these deposits were found at Miami County than at
Norfolk. The deposit built up into a V-shaped layer
of varying depth lengthwise along the probe, with the
apex or point of the V projected into the oncoming
gas stream. These deposits were removed from all
probes in a numbered sequence. Thus, the variations
in composition as a function of temperature could be
determined when the deposits were analyzed.
Corrosion Measurements and Examinations
Individual specimens were separated and examined.
They were tested first for the presence of sui fide by
placing a drop of sodium azide solution on the surface
and viewing the reagent under a binocular microscope.
Evolution of nitrogen gas bubbles gave a positive
identification of sulfide. Another area was checked for
pH by placing a moistened strip of Universal pH paper
302
Several trends of importance were found when re­
sults of all runs were analyzed.
First, for all materials evaluated,
(i ) The temperature gradient through the deposits
that separate the tube metal and the hot gases is an
important factor. Corrosion rates were greater when
larger gradients were present. Thus, direct exposure
to the flame could increase the attack.
Second, for the A I06-Grade B and A213-Grade Ti l
carbon steels,
(I) The rate of corrosion increases as the
temperature increases and can range from 5 to 15
mils per month at 325 F to about 20 to 50 mils per
month at 950 F.
(2) The two steels are comparable in corrosion
resistance with the AI06-Grade B being slightly
superior to the A213-Grade Ti l steel.
Third, for the stainless steels,
(1) The corrosion resistance is superior to that for
the carbon steels.
(2) The rate of corrosion increases as the tem­
perature increases.
(3) Types 446 and 310 show less weight loss than
Types 304, 321, and 3 16.
arranged according to the time of exposure shows that
the initial corrosion rates are high and that they taper
off with time, as illustrated in Fig. 3.
The results suggest that the scale formed during
corrosion is protective to some extent and that the
rate of attack will decrease appreciably as the exposure
time is increased.
Because of this high initial rate, the penetration
rates shown in Fig. 2 should not be used to project
antiCipated wastage for long-time incinerator operation.
Metallographic studies of sections from specimens
of the AI06 and TI l carbon-steel alloys indicated
that the attack was uniform. Stainless steel specimens,
on the other hand, showed some structural changes
and varying degrees of intergranular attack.
Some of the stainless steels failed quickly by stress­
corrosion cracking when in contact with incinerator
deposits under humid conditions at 170 F. Both
sensitized and annealed Type 304 specimens cracked
after an exposure of one week. Type 310 cracked
after 10 weeks. Type 446 did not crack after 22 weeks,
but was pitted. Because of stress-corrosion cracking
and pitting, these stainless steels do not appear as good
choices for boiler construction.
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1100
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1130
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Fig. 2 Tube-wastage rate on probe exposed at Miami County.
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Metal wastage of carbon steel as a function of exposure
time. These probes were exposed at the Miami County,
Ohio, incinerator.
303
700
100
9
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elements. An electron microprobe was used to exan1ine
the area at the interface of the base metal and the
corrosion scale on sections cut from corroded portions
of boiler tubes removed from the incinerator at
Oceanside in 1968, 1969, and 1970. Sections from
Miami County Corrosion Probes 2 and 3 were also
examined, as were sections of Probe 10 from Norfolk,
Virginia. None of these specimens was descaled prior to
sectioning so that the areas could be viewed with some
scale intact. It was found that the elements chlorine,
zinc, sulfur, lead, and potassium were concentrated
adjacent to the base metal. Table I includes the micro­
probe results for 18 specimens. The column designated
"inner layer" represents the interface between metal
and adherent scale, while that designated the "outer
layer" is in the scale, slightly removed from the metal
surface. They both are beneath what is normallY con­
sidered as deposit, i.e., the massive buildup of material
on the tube.
The sodium azide spot test also revealed that sulfide
compounds were present near the metal surface on
(4) Stress corrosion cracking and pitting is a
severe limitation, particularly during down-time.
Studies of Mechanism
The composition of the deposits removed from the
corrosion specimens was carefully determined to pro­
vide some idea of possible causes of the corrosion.
Significant amounts of chlorine, sulfur, lead, zinc,
potassium, and sodium, along with other more inert
elements, calcium, silicon, and aluminum, were detected
in the deposits from the three incinerators mentioned.
The proportions of these constituents depended on
the corrosion probe-specimen temperature, and the dis­
tributions were consistent with known volatilities
of the compounds. A typical distribution of elements
in the deposits as a function of temperature is illustrated
in Fig. 4 for two of the Norfolk, Virginia, probes.
The electron microprobe is an instrument which
permits examination of a surface to determine the
location and relative concentration of individual
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Distribution of elements in deposits from Norfolk probes.
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750-1000 F
(825 on No. 10)
almost all the probe specimens, particularly on those
exhibiting the most severe corrosion.
X-ray diffraction studies identified over 20 com­
pounds in the scale and deposit. Fig. 5 summarizes
the data obtained.
Compounds of particular significance are FeCI2 , FeS,
KCl, NaCl, ZnS04, and mixed PbO·PbS04 salts.
LABORATORY STUDI ES
Laboratory studies were carried out to determine
the importance of individual factors on corrosion in
incinerators and also to help establish the mechanism
by which metal wastage occurs. Since the experiments
can be carried out under carefully controlled con­
ditions, it is possible to determine the role of such
factors as gaseous components, salts or deposits, and
temperature.
Experiments were carried out at 600, 800, and
lOOO F using a variety of salt compositions an d under
a simulated flue-gas atmosphere containing S02 , HCl,
and, on occasion, HCOOH (formic acid). The data
in Fig. 6 indicate that chloride salts added to sulfate
salts significantly enhance corrosion, particularly at
800 and 1000 F. For example, at 1000 F, the
corrosion rate of carbon steel Ttl is about 7 mils per
month in a mixed NaZS04-K2 S04 salt. When 1
percent NaCI was added, the corrosion increased about
10 times. It was also shown that S02 was a necessary
constituent in the gas atmosphere to provide the in­
creased corrosion. At 800 and lOOO F, ZnCl2 and
Gas Analyses
The compositions of the furnace gases at the three
incinerator sites mentioned earlier were measured to
assist in determining corrosion mechanisms. The sulfur­
and chlorine-containing constituents were of particular
interest. While the S02 content in incinerators is less
than is normally found in fossil-fuel-fired power stations,
the HCI content is greater. It was found, for example,
that average amounts of these gases in incinerators
were in the range of 100 ppm, although HCl
concentrations of 300 ppm were measured in one
instance. Nitrogen oxides were present in amounts near
100 ppm and organic acids ranged up to 340 ppm. HF
was detected in amounts ranging from 1 to 6 ppm.
Table 1.
Results of Microprobe Analyses
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305
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(NOK)ZS04' SiOz•
KzPb{S�)2 , Ca S04•
NaZS04•
AI,
ZnS041
PbS04
----�....-----1---___4 No2S(4,KOH,SiOz.MgzSiO.
White(NaK ) zSO.
N·0CI, KC)t AI , C0CO3' PbO ,
..
f..-----l CaSd4• 4PbO. PbS04
Mixed oxide
loyer adherent
a Fe:P!,Fe304,
FeS
Fe Clz,FeS
DiscontinOOJs white ond
blue-block
900-1100 F
FeClz
FeClz
Continuous white layer
Continuous gold layer
600-800 F
to substrate
300-500 F
Fig. 5 Schematic location of phases identified by X·ray
diffraction.
PbCI2 were also very corrosive. At 600 F, the most
corrosive salts in decreasing order of activity were
KHS04, K2 S2 07, and ZnCI2.
DI SCUSSION
The corrosion probe results reported herein agree
fairly well with those observed in practice. For
example, Fassler [9] and his associates suggest that
high-temperature corrosion begins near 600 F.
Hilsheimer [2] has reported accelerated corrosion in
high·temperature areas of water·wall incinerators in
Germany. Tube life of less than a year has been reported
on occasion.
Maikranz [ 17] cited experience with the Munich
refuse-burning power plant in which metal wastage of
wall tubes amounted to 1.4 mm in 3500 h of operation.
This rate of corrosion is 11.3 mils per month, which
is comparable to the wastage found on many of our
probe specimens.
Comparison of these results with experience in
U. S. power plants is difficult, because few data of this
type are available. Barnhart [18] stated that the
corrosion rate in superheaters and reheaters is typically
about 20 mils per year. In extreme cases, austenitic
tube hangers have shown wastage rates of 250 mils
per year.
Correlation of the results of the different studies
306
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Fig. 6 Laboratory corrosion results showing effect of chlorides
and sulfur dioxide.
made on the deposits and corroded surfaces combined
with the laboratory results provided at least a possible
explanation of the corrosion mechanism.
It is proposed that HCI and Cl2 released adjacent
to the tube surfaces are important factors. In addition,
S02 and S03 gases, along with sulfur-containing com­
pounds, cause additional corrosion. The roles played
by the sulfur- and chlorine-containing compounds in the
refuse are of great importance and are closely inter­
related. The sequence of chemical reactions that are in­
volved in the corrosion mechanism is depicted in Fig. 7.
Chlorides and oxides reach the tube surface by direct
volatilization in the flames and by reaction of the
HCl formed during burning with the K2 0 and Na2 0
volatilized. Sodium salts are shown in Fig. 7 by way of
example, but similar reactions occur with potassium
salts. Chloride salts deposited on the metal surface
react with S02 and oxygen near the tube to evolve high
concentrations of HCl directly adjacent to the metal.
Some of this HCl reacts directly with the iron to
form FeCI2. However, a more serious condition may in­
volve catalytic oxidation of the HCl to C12. The
Cl2 is much more reactive with the tube metal and
can take part in a closed cycle of reactions in which
the product FeCl2 is converted to Fe2 03, and
Cl2 is regenerated, as shown on the left side of the
diagram.
The additional role played by sulfur is tha t of form­
ing low-melting pyrosulfates or bisulfates by reaction
of sulfates in the deposit with additional sulfur oxides.
This action is shown on the right side of the diagram,
where another closed loop is possible. In this case,
pyrosulfates or bisulfates react with the iron to form
FeS and FeO and regenerate Na2 S04'
The corrosion process is further complicated by the
presence of zinc and lead salts which serve to lower
the melting points of the mixtures on the metal surface.
It is concluded that water-wall incinerators using
the metals evaluated should not be designed to generate
superheated steam, but should be operated at relatively
low metal temperatures, near 500 F, to minimize
corrosion. The down-time of an incinerator can be im­
portant from the corrosion standpoint since acidic
salts can become wet by absorption of water when the
surfaces become cool.
ACKNOWLEDGMENTS
Louis W. Lefke and Daniell. Keller monitored this
program for the Solid Waste Management Office, EPA.
The cooperation of the administrative and operating
staffs of the incinerators at Miami County, Ohio; Navy
Public Works Center, Norfolk, Virginia; and Oceanside,
307
I
I
�
Deposit
-"
,
..... _ .......
....-:
--
---
-.,-
_
_
......
,, "
NaGI
o
Tube
metal
Fig.7 Sequence
of
chemical reactions explaining corrosion on
steel tube.
bined with Steam Boilers, Design and Planning", Proceedings
ASME, New York,
N.Y., pp. 73-86.
[7] H. Eberhardt, "European Practice in Refuse and
Sewage Sludge Disposal by Incineration", Combustion, vol. 28,
no. 3, September 1966, pp. 8-15.
[8] K. Matsumoto, R. Asukata, and T. Kawashima, "The
Practice of Refuse Incineration in Japan- Burning of Refuse
With High Moisture-Content and Low Calorific Value", Pro­
ceedings of 1968 National Incinerator Conference, ASME,
pp.. 192-196, New York, N.Y.
[9] K. Fassler, H. Leib and H. Spahn, "Corrosion in Refuse
Incineration Plants", Mitt. V G.B., vol. 48, April 1968,
pp. 126-139.
[10] Rudolf Rasch, "Fireside Corrosion in Incinerators",
BrennstoffWarme-Kraft, vol. 19, October 1967, p. 498
[11] M. Hirsch, "Fireside Corrosion by Burning Chlorine
Containing Refuse", Brennstoff Warme-Kraft, vol. 19,
October 1967, p. 499.
[12] R. Huch, "Hydrogen Chloride Corrosion in In­
cinerators", Brennstoff Warme-Kraft, vol. 18, February 1966,
pp. 76-79.
[13] J. Angenend, "Behavior of Materials for Boiler
Tubes in Gases Containing Hydrogen Chloride", Brennstoff
Warme-Kraft, vol. 18, February, 1966, pp. 79-81.
[14] R. W. Bryers and Z. Kerekes, "Recent Experience
With Ash Deposits in Refuse-Fired Boilers", ASME paper
No. 68-WA/CD-4, Winter Annual Meeting, 1968, ASME.
[15] Paul D. Miller and Horatio H. Krause, "Factors In­
fluencing the Corrosion of Boiler Steels in Municipal In­
cinerators", Corrosion, vol. 27, January 1971, pp. 31-45.
Town of Hempstead, Long Island, New York, is
greatly appreciated.
The authors also wish to acknowledge the efforts of
Battelle-Columbus staff members W. K. Boyd, R. B.
Engdahl, R. D. Fischer, W. T. Reid, J. E. Reinoehl,
E. J. Schulz, D. A. Vaughan, P. R. Webb, and J. Zupan.
of 1968 National Incinerator Conference,
RE FERENCES
[1] F. Nowak, "Considerations in the Construction of
Large Refuse Incinerators". Proceedings of 1970 National
Incinerator Conference, ASME, New York, N.Y., pp. 92-96.
[2] H. Hilsheimer, "Experience After 20,000 Operating
Hours-The Mannheim Incinerator", Proceedings of I 970
National Incinerator Conference, ASME, New York, N.Y.
pp. 93-106.
[3J F. Nowak, "Corrosion Problems in Incinerators",
Combustion, vol. 40, no. 5, November 1968, pp. 32-40.
[4] H. Rousseau, "The Large Plants for Incineration of
Domestic Refuse in the Paris Metropolitan Area". Proceedings
of 1968 National Incinerator Conference, ASME, New York,
N.Y., pp. 225-231.
[5] Wolfgang Ficktner, Karl-Gerog Maurer and Harold
Miller, "The Stuttgart Refuse Incineration Plant: Layout
and Operation Experience". ASME Paper No. 66-WA/PID-I0,
Winter Annual Meeting, 1966, ASME.
[6] H. Everhardt and W. Mayer, "Experiences With Refuse
Incinerators in Europe-Prevention of Air and Water
Pollution, Operation of Refuse Incineration Plants Com-
308
[16] H. Carlton Moore, "Refuse-Fired Steam Generator
at Navy Base, Norfolk, Virginia", Proc. MECAR Symposium­
Incineration of Solid Wastes, March 21, 1967, pp. 10-23.
[17] F. Maikranz, "Corrosion in Three Differen t Firing
Installations", International Symposium on Corrosion in
Refuse Incineration Plants, Dusseldorf, West Germany,
April, 197 O.
[18] D. H. Barnhart, Discussion on papers in Section Ib,
The Marchwood Conference, The Mechanism of Corrosion
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309