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Effects of Feed Composition on Boiler Corrosion in Waste-to-Energy Plants

Article · January 2004

DOI: 10.1115/NAWTEC12-2215

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 12th North American Waste To Energy Conference (NAWTEC 12)

Effects of Feed Composition on Boiler Corrosion in Waste-to-Energy Plants

DIONEL O. ALBINA, KARSTEN MILLRATH, AND N. J. THEMELIS

Earth Engineering Center, Columbia University

500 W 120th Street, 918 Mudd
New York, NY 10027
Tel.: (212) 854-0307 e-mail: doa2001@columbia.edu

Keywords: high-temperature corrosion; fuel chemistry; corrosion; municipal solid waste combustion, waste-to-
energy, WTE, combustion chamber

Abstract

Municipal solid wastes (MSW) typically contain plastic materials, leather, textiles, batteries, food waste and
alkalis. These materials are sources of chlorine, sulfur, potassium, zinc, lead and other heavy metals that can
form corrosive media during combustion of the MSW in waste-to-energy (WTE) facilities. Chlorides and
sulfates, along with fly ash particles, condense or deposit on the waterwall surfaces in the combustion chamber
and on other heat exchanger surfaces in the convection path of the process gas, such as screens and
superheater tubes. The resulting high corrosion spots necessitate shutdowns and tube replacements, which
represent major operating costs. The aim of ongoing research at Columbia University is to gain a better
understanding of the effects of fuel composition, products of combustion, and chemical reactions that lead to
the corrosion of metal surfaces in WTE boilers. The potential chemical reactions and their chance of
occurrence were determined by means of thermochemical calculations of the respective equilibrium constants
as a function of temperature and gas phase composition.

1. Introduction maintain uniform combustion conditions that are

desired in steam boilers. Also, the poor combustion
A major problem in the operation of WTE
characteristics of the MSW fuel result in incomplete
facilities is the high corrosion of the heat exchanger
combustion, i.e. localized high CO levels, occasional
tubes through which thermal energy from the
high heat flux on the wall caused by flame
combustion gases is transferred to the high-pressure
impingement, and the formation of aggressive
steam that is used to operate the electricity
deposits. MSW contains alkali metals such as sodium
generators. The rate of corrosion in MSW
and potassium, heavy metals such as lead, tin, and
combustion chambers is reported to be much higher
zinc and various chlorine-containing compounds, all
than for conventional coal-fired power plants that
of which can form potential corrosive agents.
operate at higher temperatures than WTE facilities. It
is generally assumed that this high rate of corrosion is The surface temperature of the metal wall, gas
inherent to the heterogeneous nature of the MSW temperature, gas composition and deposit
fuel and its variable chlorine content. This characteristics are main factors that influence the
heterogeneity makes it difficult for operators to high-temperature corrosion of WTE boilers. High

1
temperatures of metal surfaces, either due to high
radiation flux to the wall or inadequate transfer of
heat to the water/steam flow on the other side result
in the melting of deposits and acceleration of the rate
of corrosion. The temperature gradient between the
metal and gas temperatures determines the
condensation of vapor species, the rate of deposition
and the composition of the deposit.
For example, at large temperature gradients, the
concentration of chlorides in the deposit is higher
and the melting point of the eutectic solution
decreases [1]. Also, in WTE boilers, the presence of
lead and zinc in the deposits lower their melting
temperature. Examination of tubes that have been
subjected to severe corrosion showed that sulfate and
chloride salts of sodium and potassium concentrate at
the deposit/scale interface and become partially
fused. [2].
It has also been observed that the corrosion rate
increases with increasing thickness of the deposit [1].
The corrosion resistance of various steels and alloys
has been evaluated by means of several field
corrosion tests. However, the corrosion rates of
various high temperature steels and alloys seem to
differ between furnaces and even between tests
carried out in the same furnace at different times. As
noted above, this variation in corrosion rate of the
same materials has been attributed to the non-
homogeneity of the MSW fuel [2].
The objective of this study was to understand
the effects of MSW composition and MSW fuel
chemistry on the corrosion of tube metals in WTE
combustion chambers. The chemical composition of
different MSW fuels was determined in a literature
analysis. The effects of various fuel impurities on the
flue-gas composition were studied to understand the
factors that influence tube corrosion. Finally, the flue
gas and the molecular composition of the
compounds condensing on the metal surface were
computed in order to understand the effects of fuel
chemistry on the formation of vapor condensate
deposits in tubes. The thermodynamic calculations
were carried out using HSC Chemistry, a
2
thermodynamic software program developed by
Outokumpu Research in Finland [3].
2. MSW Composition
The ultimate (i.e., chemical) analysis of various
MSW fuel was determined from waste
characterization reports for New York City, [4], the
U.S. [5] and the U.K. [6]. For example, in New York
City, the typical MSW consisted of 31.3 % paper and
cardboard, 8.9 % plastics, 5 % textiles, 5 % glass and
4.8 % metal. The ultimate analyses of the MSW fuel
were estimated from these data and the ultimate
analysis of paper and other materials presented by
Tchobanoglous and others [7]. Tables 1-3 show the
estimated ultimate analysis for the selected three
MSW fuels. A detailed description of the chlorine
concentration in various MSW materials is shown in
Appendix 1.
3. Corrosion Mechanisms
It is generally accepted that high temperature
corrosion in WTE facilities is caused by chlorine
either in the form HCl, Cl2 or in the form of
chlorides of Na, K, Zn, Pb, Sn, and other elements
[6]. The most important factors in high temperature
corrosion are [1]:
1. Metal temperature: A basic factor in accelerating
the melt of deposits and activating corrosion
rates.
2. Gas temperature: Determines deposition rates and
deposit compositions and hence affects strongly
the corrosion rate.
3. Temperature gradient between gas temperature and metal
temperature: Driving force for condensation of
vaporized components such as chlorides on the
cooled surface.
4. Deposit characteristics: Increasing concentrations in
Cl, SO4, alkaline and heavy metal components
influence both the physical and chemical
 properties of deposits such as gas permeability.
The corrosion rates increases with higher
thicknesses of deposits.
5. Temperature fluctuations: Fluctuation of combustion
by non-homogeneous waste and soot blowing
cause sharp gas temperature fluctuation; this has
been reported to increase the corrosion rate
several-fold.

Table 1. Ultimate Analysis of MSW fuel based on New York City MSW composition [4]

Components of Waste % in Percent by Weight (dry basis)a

Stream MSW Carbon Hydrogen Oxygen Nitrogen Sulfur Ash Chlorineb
Paper 26.6 43.5 6 44 0.3 0.2 6
Cardboard 4.7 44 5.9 44.6 0.3 0.2 5
} 0.063
Plastics 8.9 60 7.2 22.8 - - 10 0.223
Textiles 4.7 55 6.6 31.2 4.6 0.15 2.45 0.059
Rubber and Leather 0.2 69 9 5.8 6 0.2 10 0.003
Wood 2.2 49.5 6 42.7 0.2 0.1 1.5 0.076
Glass 5 0.5 0.1 0.4 <0.1 - 98.9
Metals 4.8 4.5 0.6 4.3 <0.1 - 90.5
} 0.01
Others 4.6 26.3 3 2 0.5 0.2 68 -
Misc. organics 28 48 6.4 37.6 2.6 0.4 5 -

Ultimate Analysis of composite MSW 41.8 5.5 32.3 1.2 0.2 18.5 0.471
a
based on [7]
b
See detailed calculation in Appendix 1.

Table 2. Ultimate analysis of MSW fuel based on U.S. MSW composition [5]

Components of Waste % in Percent by Weight (dry basis)a

Stream MSW Carbon Hydrogen Oxygen Nitrogen Sulfur Ash Chlorineb
Paper and paperboard 35.7 43.5 6 44 0.3 0.2 6 0.071
Plastics 11.1 60 7.2 22.8 - - 10 0.278
Textiles 4.3 55 6.6 31.2 4.6 0.2 2.5 0.054
Rubber and Leather 4.6 69 9 5.8 6 0.2 10 0.058
Wood 5.7 49.5 6 42.7 0.2 0.1 1.5
Yard waste 12.2 47.8 6 38 3.4 0.3 4.5
} 0.224
Glass and Metals 13.4 2.5 0.35 2.9 <0.1 94 0.008
Food waste 11.4 48 6.4 37.6 2.6 0.4 5 0.034
Others (dirt, ash, etc.) 1.6 26.3 3 2 0.5 0.2 68 -
Ultimate Analysis of composite MSW 42.3 5.5 31 1.3 0.18 18.6 0.72
a
based on [7]
b
See detailed calculation in Appendix 1.

3
Table 3. Ultimate Analysis of MSW fuel based on MSW composition in the U.K. [6]

Component of Waste % in Percent by Weight (dry basis)a

Stream MSW Carbon Hydrogen Oxygen Nitrogen Sulfur Ash Chlorineb
Paper and Cardboard 33.2 43.8 6 44.3 0.3 0.3 5.4 0.066
Plastics 11.2 60 7.2 22.8 - - 10 0.28
Textiles 2.1 55 6.6 31.2 4.6 0.2 2.5 0.026
Glass 9.3 0.5 0.1 0.4 <0.1 - 99
Metals 7.3 4.5 0.6 4.3 <0.1 - 91
} 0.01
Putrecibles 20.2 47.9 6.2 37.8 3 0.4 4.7 0.061
Others 16.7 53.5 6.8 18.8 3.1 0.3 18 -
Ultimate Analysis of composite MSW 41.2 5.4 28.9 1.3 0.23 22.6 0.45
a
based on [7]
b
See detailed calculation in Appendix 1.

produce pyrosulfate at temperatures between 320 and

3.1 Corrosion mechanism by chlorine containing gas [6]
480°C according to the reactions (3) and (4).
Chlorine-driven corrosion is expected to occur at
metal temperatures above 450°C. Alkali chlorides, i.e. Na 2 SO4 + SO3 = Na 2 S 2 O 7 (3)

NaCl, CaCl and KCl can be formed by combustion
and subsequent reaction of alkali oxides as shown in
reaction 1. Under ideal conditions such as good
mixing and sufficient residence time, alkali chlorides
can be sulfated, as shown in reaction 2, in the
presence of sufficiently high SO2 and O2. This results
in the formation of sulfates and volatile HCl.
Na2 O + 2 HCl = 2 NaCl + H 2 O (1)
1 Na2 S + 2O2 = Na2 SO4
2 NaCl + SO 2 + O2 + H 2 O = Na 2 SO 4 + 2 HCl
2
At relatively low tube wall temperatures, the
sulfates are not very harmful and the HCl formed is
transported away by the flue gas and cleaned-up in
the air pollution control system. However, if the gas
reaches the cooler tube walls before the reaction is
completed, the alkali metals condense on the cooler
metal and the probability of corrosion increases.
3.2 Corrosion mechanism by sulfates [6]
At high metal temperatures, sulfur compounds
will induce other corrosion reactions if the deposits
contain compounds like iron oxides that can catalyze
the reaction from SO2 in SO3. For example, the
partial pressure of SO3 may be high enough to
Na 2 S 2 O7 + 3Fe = Fe2 O3 + FeS + Na 2 SO4 ( 4)
At 500°C sulfates and pyrosulfates can become
unstable and react with protective oxide layers on
metal surfaces; at temperatures above 550 °C, the
trisulfates can attack the metal according to reactions
(5) to (8).
19 Fe + 2 Na3 Fe( SO4 ) 3 = 6 Fe3O4 + 3FeS + 3 Na2 S (5)
(6)
( 2)
3FeS + 5SO2 = Fe3O4 + 3SO2 (7 )
2 SO2 + O2 = 2 SO3 (8)
The SO3 can react with Na2SO4 resulting in
cyclic corrosion reactions, which are enhanced in the
presence of chlorides. The sulfate-driven corrosion
phenomena can occur in large boilers of power
stations, operated with substantial impurity levels in
the fuel and at high steam temperatures.
4. Calculation Method
Equilibrium calculations in HSC Chemistry use
the Gibbs energy minimization method [3]. The
program finds the most stable phase combination

4
and seeks the phase composition, for which the
Gibbs free energy of the system reaches its minimum
at a fixed mass balance (constraint minimization
problem), constant pressure and temperature. Table 4
shows the ultimate analyses and the estimated
elemental composition for the three selected MSW
fuels, as were inputted in the HSC software.
Metal compositions were calculated based on the
metal composition of a reference waste and
subsequent extrapolation as reported in [2, 7, 8]. For
computing the elemental composition of the
reference waste, it was assumed that the heating value
of MSW (as fired) is 11 MJ/ton and 3.7 % of metal
content in the waste [8]. Metal compositions were
then calculated by extrapolating the actual metal
composition of the selected fuels. The moisture
content was assumed to be uniform at 25 % for all
three fuels.

Table 4. Ultimate analysis of typical MSW fuels and concentration of metals used in the calculations
Element NYC MSW U.S. MSW U.K. MSW
Ultimate (%)
Carbon 41.8 42.3 41.2
Hydrogen 5.5 5.5 5.4
Oxygen 32.3 31 28.9
Nitrogen 1.2 1.3 1.3
Sulfur 0.2 0.18 0.23
Chlorine 0.5 0.71 0.45
Ash 18.5 18.6 22.6
Moisture 25% 25% 25%

Metals (g/ton) 4.8% by weight 7.9% by weight 7.3 % by weight

Asa 24 31 29
Cab 9200 15300 14100
Cda 42 70 64
Cra 57 95 87
Cua 475 788 726
Feb 2000 3400 3100
Kb 1180 1960 1800
Hga 1.1 1.9 1.7
Nab 600 980 900
Nic 29 48 45
Pbc 2050 3400 3130
Sbc 200 332 306
Snc 230 381 351
Zna 1760 2918 2686
Sources:a[8],b[2],c[7]Assuming 11 MJ/ton MSW as fired

5. Computational Results combustion of 1.33 kg fuel at 25 % moisture (i.e., 1kg

of dry MSW) with air at 5 standard cubic meters per
Flue-gas compositions were calculated using the
kilogram (equivalent to the typical air usage in WTE
estimated ultimate analysis of the three MSW fuels.
facilities) was calculated at temperatures ranging from
The equilibrium flue gas composition resulting from
400°C -1200°C using the HSC software. For

5
simplicity and due to program constraints, not all 9E-05
kmol File: C:\HSC5\Gibbs\msw\equilibrium_calculation_nyc.OGI

HCl(g)

metals listed in Table 4 were included in the 8E-05

calculation. 7E-05
SO2(g)
6E-05

5.1 NYC MSW Fuel 5E-05

4E-05

The calculated flue-gas composition upon 3E-05

KCl(g)

combustion of 1kg (dry) NYC MSW was 7.4 % CO2, 2E-05

NaCl(g)

11 % H2O and 7.2 % excess O2 and the balance 1E-05

nitrogen, with a few hundred ppm of HCl and NO 0E+00

400 500 600 700 800 900 1000 1100 1200

and SO2. These results are in relatively good Temperature (degree C)

agreement with flue-gas compositions obtained in the Figure 1. Calculated flue gas concentrations of
combustion chambers of present WTE facilities. HCl, SO2, KCl and NaCl resulting from the
Typical HCl concentrations in combustors were in combustion of NYC MSW (compare Table 4)
the range of 200-900 ppm while SO2 concentrations
were in the range of 10-300 ppm [9]. Concentrations
of gaseous NaCl, KCl, Na2Cl2, NaOH and ZnCl2
were also present, with NaCl and KCl concentrations
over 100 ppm; Na2Cl2, NaOH and ZnCl2 range from
0.5 to 1 ppm at 1000°C flue-gas temperature.

Equilibrium flue-gas concentrations for gaseous

HCl, NaCl, KCl and SO2 are shown in Figure 1.
Concentrations of gaseous HCl, NaCl, KCl, and SO2
were observed to increase at 600 °C and to peak at
900°C with the exception of HCl that started to Figure 2. Calculated flue gas concentrations of
increase at 400°C. Equilibrium flue-gas K2Cl2, Na2Cl2, ZnCl2, KOH and NaOH from the
concentrations of gaseous Na2Cl2, K2Cl2, ZnCl2, combustion of NYC MSW fuel (compare Table 4).
KOH and NaOH are also shown in Figure 2. It can
be seen that K2Cl2 and Na2Cl2 are present at 500°C, 7E-05
kmol File: C:\HSC5\Gibbs\msw\equilibrium_calculation_nyc.OGI

increase abruptly, peak at approximately 750°C, and 6E-05

CaSO4

then decrease sharply with flue-gas temperature. On

5E-05
the other hand, concentrations of ZnCl2, KOH and CaCl2
4E-05
NaOH increase with flue gas temperature, with
KCl
3E-05
ZnCl2, KOH and NaOH appearing at 600-700°C, ZnO
NaCl

900°C, and 1000°C, respectively. 2E-05

1E-05
The molar quantities of pure compounds of
0E+00
condensed phases (solid/liquid) at equilibrium are 400 500 600 700 800 900 1000 1100 1200
Temperature (degree C)
shown in Figure 3. Solid NaCl and KCl are at
equilibrium below 750°C while solid CaSO4 and Figure 3. Calculated molar quantities of
compounds of condensed phases at equilibrium
CaCl2 are at equilibrium at about 1000°C and lower
with flue gas, corresponding to the combustion of 1
temperatures. Solid ZnO is stable over the entire
kg of NYC MSW fuel.
temperature range.

6
5.2 US MSW Fuel increase with flue-gas temperature, with KOH and

The calculated flue-gas composition resulting NaOH appearing at 1000°C and ZnCl2 appearing at

from combustion of 1 kg of US MSW fuel at 1000°C 600°C, respectively.

was 8.5% CO2, 18% H2O and 6.9% O2; the balance
was nitrogen, with a few hundred ppm of HCl, NO
and SO2. Calculated HCl, SO2 and NO
concentrations were 680 ppm, 275 ppm and 200 ppm
respectively. Concentrations of gaseous NaCl, and
KCl were a few hundred ppm while Na2Cl2, NaOH
and ZnCl2 varied from 1-5 ppm at 1000°C flue-gas
temperature. It is striking that these concentrations
are relatively higher than the concentration resulting
from combustion of NYC MSW, apparently due to
the higher chlorine content of the US MSW fuel.
Figure 5. Flue gas concentrations of K2Cl2, Na2Cl2,
Equilibrium flue-gas concentrations for gaseous ZnCl2, KOH and NaOH resulting from the
HCl, NaCl, KCl and SO2 are presented in Figure 4. It combustion of US MSW fuel.
can be seen that all concentrations started to increase
at 600°C and reached a maximum at 950°C with the
exception of HCl that started to increase at 450°C.

kmol File: C:\HSC5\Gibbs\msw\equilibrium_calculation_us.OGI

1E-04

1E-04 HCl(g)

1E-04

9E-05

8E-05

7E-05

6E-05 SO2(g)
KCl(g)
5E-05

4E-05
NaCl(g)
3E-05

2E-05
Figure 6. Calculated molar quantities of
1E-05 compounds of condensed phases at equilibrium
0E+00
400 500 600 700 800 900 1000 1100 1200 with flue gas, corresponding to the combustion of 1
Temperature (degree C)
kg of US MSW fuel.
Figure 4. Calculated flue gas concentrations of
HCl, SO2, KCl and NaCl resulting from the
combustion of US MSW fuel (compare Table 4) The molar quantities of pure compounds of the
condensed phases (solid/liquid) at equilibrium are
shown in Figure 6. Solid NaCl and KCl are at
Equilibrium flue-gas concentrations of gaseous
equilibrium below 800°C, solid CaSO4 at 800°C and
Na2Cl2, K2Cl2, ZnCl2, KOH and NaOH are shown in
below, and CaCl2 at 1100°C and below. Solid ZnO is
Figure 5. It is noted that concentrations of gaseous
stable over the entire temperature range. It should be
Na2Cl2 and K2Cl2 did not increase with temperature.
noted that this behavior is similar to the combustion
The concentrations of K2Cl2 and Na2Cl2 start to
of NYC MSW fuel.
increase rapidly at 600°C, peak at about 800°C, and
then decrease sharply with flue-gas temperature. On 5.3 UK MSW Fuel
the other hand, concentrations of KOH and NaOH

7
 The calculated flue-gas composition from the
combustion of UK MSW fuel at 1000°C consists of
6.5% CO2, 10.1% H2O, 7.1% O2, and the balance
nitrogen with few hundred ppm of HCl, NO and
SO2. The calculated HCl, SO2 and NO
fuel (as for the US MSW fuel) resulted in increased
concentrations of gaseous HCl, NaCl and KCl, and
the condensed phases of solid NaCl and KCl.
8E-05
kmol File: C:\HSC5\Gibbs\msw\equilibrium_calculation_uk.OGI

CaSO4
concentrations were at 155 ppm, 263 ppm and 200 7E-05

ppm, respectively. Figure 7 shows the equilibrium 6E-05

flue-gas concentrations at 400°C -1200°C for gaseous 5E-05

KCl
ZnO

4E-05
HCl, NaCl, KCl and SO2. Concentrations of gaseous NaCl

3E-05
HCl, NaCl, KCl, and SO2 increased with higher flue-
2E-05

gas temperatures. It was observed that HCl appeared 1E-05

CaCl2

at 450°C while NaCl, KCl and SO2 were formed at 0E+00

400 500 600 700 800 900 1000 1100 1200

600°C. Temperature (degree C)

Figure 8. Calculated molar quantities of

It can be seen that concentrations of gaseous
Na2Cl2 and K2Cl2 did not increase with temperature
while concentrations of gaseous KOH and NaOH
increase with temperature. Figure 8 shows the molar
quantities of pure compounds of condensed phases
(solid/liquid) at equilibrium. Solid NaCl, KCl and
CaSO4 are at equilibrium below 750°C while CaCl2 is
at equilibrium at approximately 900°C and below. As
for other fuels, solid ZnO is stable over the entire
temperature range.
compounds of condensed phases at equilibrium
with flue gas corresponding to the combustion of 1
kg of UK MSW fuel.
6. Discussion of Results
6.1 Chlorides
The results of the thermodynamic calculations
showed that an increase in chlorine content of the
fuel has a significant influence on the production of
gaseous HCl, KCl, NaCl, K2Cl2 and Na2Cl2 and of
the condensed phases of NaCl, KCl, ZnCl2 and ZnO.
It should be noted that the molar concentrations of
these compounds were higher in the case of
combustion of US MSW fuel that contains 0.7%
chlorine than for the combustion of NYC MSW and
UK MSW that contain 0.5% and 0.45% Cl,
respectively.

Figure 7. Calculated flue gas concentrations of
HCl, SO2, KCl and NaCl resulting from combustion
of UK MSW fuel (compare Table 4)
Table 5 shows a summary of the equilibrium
flue-gas concentrations at 1000°C resulting from
combustion of NYC, US and UK MSW fuels. It is
apparent that higher concentrations of chlorine in the
6.2. Sulfates
In the equilibrium calculations, it was noticed
that the concentrations of gaseous SO2 and SO3
increased with flue gas temperature. However, the
molar concentration of SO3 was extremely low.
Hence, as long as the surface metal temperatures,
particularly on the superheater tubes in WTE
facilities, remain below 500°C, sulfate-induced
corrosion is not expected.

8
6.3 Corrosion induced by deposits of metal chlorides and higher for the US MSW fuel than for the combustion
sulfates of the NYC and UKMSW fuels. The Earth
Engineering Center (EEC) will conduct follow-up
In this study, the condensed phases of sulfates
studies to verify the molecular quantity of vapor
(such asCaSO4) and chlorides (such as NaCl, CaCl2,
condensate deposits at different flue gas temperatures
KCl and ZnCl2) were observed in the equilibrium
and surface (tube) temperatures, resulting from
calculations. It was also shown that molar quantities
combustion of different MSW fuels.
of these compounds of condensed phases were
higher in the case of the higher chlorine fuel. It can
be concluded that the likelihood of corrosion is

Table 5. Calculated equilibrium flue-gas concentration resulting from combustion of 1-kg MSW fuel at
1000°C

Element NYC MSW USA MSW UK MSW

CO2 (%) 7.4 8.5 6.5
H2O (%) 11.2 18 10.1
O2 (%) 7.2 6.9 7.1
HCl (ppm) 334 680 155
SO2 (ppm) 227 375 263
SO3 (ppm) >1 >1 >1
FeCl2 >1 2 >1
KCl (ppm) 118 227 167
K2Cl2 (ppm) >1 3 >1
KOH (ppm) >1 1 >1
K2SO4 (ppm) >1 >1 >1
NaCl (ppm) 103 285 140
Na2Cl2 (ppm) 1 3 >1
Na2O (ppm) - >1 -
NaOH (ppm) >1 >1 >1
Na2(OH)2 (ppm) - - -
NO (ppm) 210 200 208
NO2 (ppm) 1 1 >1
OH (ppm) 10 8 11
ZnCl2 (ppm) >1 >1 >1

7. Conclusions temperatures. It was also observed that the

This paper investigated the effect of fuel
chemistry on the formation of potentially corrosive
compounds in the combustion chamber of a WTE
facility. The calculations of flue-gas compositions at
equilibrium indicated that the corrosive
concentrations of gaseous salts and chlorides such as
NaCl, KCl, Na2Cl2, NaOH and ZnCl2, all of which
are generally perceived to be the precursors of
corrosion, are formed at different flue-gas
condensed phases of sulfates and chlorides, which
ultimately may be deposited in waterwall and
superheater tubes, are formed. The molar
concentrations of all these condensed phase
compounds were higher for fuels with relatively
higher chlorine contents.
Subsequent research will be conducted at the
Earth Engineering Center as continuation of previous
efforts as presented in this paper. The studies will

9
also address issues such as detailed deposit chemistry, for reducing the corrosion phenomena in WTE
kinetics and corrosion mechanisms with different combustion chambers will be investigated.
tube alloys. On the basis of the results, various means

References

[1] Kawahara, Y. (2002): “High temperature mechanisms and effect of alloying elements for materials used
in incineration environment.” Corrosion Science 44, pp. 223-245.
[2] Otsuka, N. (2002): “Effects of fuel impurities on the fireside corrosion of boiler tubes in advanced
power generating systems- a thermodynamic calculation of fuel chemistry” Corrosion Science 44, pp. 265-
283.
[3] Outokumpu HSC Chemistry: “Chemical Reaction and Equilibrium Software.” Outokumpu Research
Oy, Finland, ISBN 952-9507-08-9.
[4] Themelis, N.J., Y. H. Kim and M. H. Brady (2002): “Energy Recovery from NYC municipal solid
waste.” Waste Management and Research 20, pp. 223-233.
[5] US EPA (2003): “Municipal Solid Waste in the United States: Facts and Figures.” Office of Solid Waste
and Emergency Response, EPA530-R-03011, Washington, D.C.
[6] Redmakers, P., W. Hesseling and J. van de Wetering (2003): “Review on corrosion in waste
incinerators.” TNO report.
[7] Tchobanoglous, G., H. Theisen and S. Vigil (1993): “Integrated Solid Waste Management: Engineering
Principles and Management Issues.” McGraw Hill, USA.
[8] Sorum, L., F.J. Frandsen and J.E. Hustad (2003): “On the fate of heavy metals in municipal solid waste
combustion Part I: devolatilisation of metals on grate.” Fuel 82, pp. 2273-2283.
[9] D. Albina (2003): “Internship Report: A study on possible correlation between Hydrogen Chloride,
Sulfur Dioxide and HCl/SO2 to Corrosion of COVANTA WTE Facilities.” Columbia University, New
York, NY, (unpublished report).

Appendix 1: Chlorine Estimates

Table A1. Chlorine Concentration in NYC MSW fuel

Component of Waste Stream Mass in MSW Chlorine Content Chlorine in MSW
(%)a (g/kg of comp.)b (g/kg)
Paper/cardboard 31.3 2 0.63
Plastics 8.9 25 2.23
Food Waste 12.7 3 0.38
Textiles 4.7 12.5 0.59
Wood and yardwaste 6.1 12.5 0.76
Miss.Combustible 0.2 12.5 0.03
Glass and Metals 16.4 0.6 0.10
Total 80.3 4.71
Reference: aISWA Journal,: Waste Management and Research
b
P. Redmakers, W. Hesseling and J. van de Wetering (2003). Review on corrosion
in waste incinerators, TNO report

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 Table A2. Chlorine Concentration in U.S. MSW fuel
Component of Waste Stream Mass in MSW Chlorine Content Chlorine in MSW
(%)a (g/kg of comp.)b (g/kg)
Paper/cardboard 35.7 2 0.71
Plastics 11.1 25 2.78
Food Wastes 11.4 3 0.34
Textiles 4.3 12.5 0.54
Wood and yardwaste 17.9 12.5 2.24
Miss.Combustible 4.6 12.5 0.58
Glass and Metals 13.4 0.6 0.08
Total 98.4 7.26
Reference: a USEPA Report (2003), Municipal Solid Waste in the United States: Facts and Figures,
Office of Solid Waste and Emergency Response, EPA530-R-03011
b
P. Redmakers, W. Hesseling and J. van de Wetering (2003). Review on corrosion
in waste incinerators, TNO report

Table A3. Chlorine Concentration in U.K. MSW fuel

Component of Waste Stream Mass in MSW Chlorine Content Chlorine in MSW
(%)a (g/kg of comp.)a (g/kg)
Paper/cardboard 33.2 2 0.66
Plastics 11.2 25 2.80
Organic material (food, yardwaste) 20.2 3 0.61
Textiles 2.1 12.5 0.26
Glass and Metals 16.6 0.6 0.10
Others 16.7 0.6 0.10
Total 100 4.53
Reference: bP. Redmakers, W. Hesseling and J. van de Wetering (2003). Review on corrosion
in waste incinerators, TNO report

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