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A General Correlation for Accurate


Prediction of the Dew Points of Acidic
Combustion Gases in Petroleum Industry
a
B. ZareNezhad
a
Faculty of Chemical, Petroleum and Gas Engineering, Semnan
University, Semnan, Iran
Published online: 06 Jun 2014.

To cite this article: B. ZareNezhad (2014) A General Correlation for Accurate Prediction of the Dew
Points of Acidic Combustion Gases in Petroleum Industry, Petroleum Science and Technology, 32:16,
1988-1995, DOI: 10.1080/10916466.2012.730596

To link to this article: http://dx.doi.org/10.1080/10916466.2012.730596

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Petroleum Science and Technology, 32:1988–1995, 2014
Copyright 
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ISSN: 1091-6466 print / 1532-2459 online
DOI: 10.1080/10916466.2012.730596

A General Correlation for Accurate Prediction of the Dew


Points of Acidic Combustion Gases in Petroleum Industry

B. ZareNezhad1
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1
Faculty of Chemical, Petroleum and Gas Engineering, Semnan University, Semnan, Iran

A general correlation has been proposed for the first time for accurate prediction of the acidic combustion
gases dew points to mitigate the corrosion potential in pollution control and energy recovery equipments.
Acidic combustion gases can cause rapid corrosion when they condense on the surfaces of the heat
recovery and flue gas treatment equipments. The most important acidic gases, namely, SO3 , SO2 , NO2 ,
HCl, and HBr, are considered in this investigation. The presented correlation can be used for accurate
prediction of the flue gas acid dew point temperatures over wide ranges of acid and water vapor
concentrations in oil and gas industries.
Keywords: acid dew point, combustion gas, correlation, corrosion, energy recovery

1. INTRODUCTION

Acid dew point corrosion results from condensation of flue gas acid species on low temperature gas-
path surfaces. This kind of corrosion differs from general atmospheric corrosion and causes heavy
corrosion not only of ordinary steels but even stainless steels (Rockel and Bender, 2008). Corrosion
failures often occur because of condensing flue gasses containing SO3 , SO2 , NO2 , HCl, HBr, and
H2 O. Dew point temperature is a function of the water vapor concentration and the concentration
of acid species in the flue gas (Blanco and Peña, 2008). The condensed acids are corrosive to steel
and almost all plastics, as well as hydraulic cement composites. Further, gas cooling below this dew
point by radiation or convection forms a mist of corrosive acid droplets that is highly detrimental to
the stack and heat recovery equipment (Cherif et al., 2002). Many of the processes for improving the
thermal efficiency of combined cycle plants can also result in lower flue gas temperatures leaving the
heat recovery steam generators or increased flue gas moisture content. These conditions can increase
the potential for corrosion of the low temperature gas-path components (Lins and Guimaraes, 2007)
Sulfuric acid and hydrochloric acid dew point corrosion occur in flue gas treatment systems of
waste incineration facilities. For a typical flue gas (SO3 = 3 ppmv; HCl = 300 ppmv; H2 O = 30
vol%), the H2 SO4 and HCl dew points are about 136 and 72◦ C, respectively. At temperatures between
72 and 136◦ C, the H2 SO4 condensation is the main cause of steel corrosion failure. Improvement
of the thermal efficiency of flue gas treatment equipment may need further cooling to a temperature
as low as 72◦ C. At flue gas temperatures below 72◦ C, the HCl condensation is also an important
influencing factor regarding corrosion failure.

Address correspondence to B. ZareNezhad, Faculty of Chemical, Petroleum and Gas Engineering, Semnan University,
PO Box 35195–363, Semnan, Iran. E-mail: Prof.b.zarenezhad@gmail.com

1988
ACCURATE PREDICTION OF ACID DEW POINTS 1989

The following correlation (Verhoff and Banchero, 1974) was provided for predicting flue gas
sulfuric acid dew point:

(1)

where TDew is the sulfuric acid dew point in K and the partial pressures (pSO3 and pH2O ) are in mm
Hg.
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The previous correlation (the Verhoff and Banchero [V.B] correlation) does not apply to halo-
genated or nitrated acid gases. To overcome this shortcoming. Kiang (1981) proposed different
correlations for estimating the NO2 , HCl and HBr dew points. However there are usually significant
deviations between predicted and experimental dew points over the concentrations prevailing in
combustion gases.
It should be noted that there are some disagreements between the experimental data and the Verhoff
and Banchero (1974) correlation especially at low acid concentrations and high H2 O contents. Dew
points predicted in the range of 120–140◦ C have a positive deviation of 4◦ C and more. Also in
the range of 100–121◦ C, the predicted dew points are usually 4◦ C low. Okkes (1987) proposed a
correlation to overcome some of these shortcomings, which can be written as follows:

(2)

Where the partial pressures are expressed in atmosphere and the sulfuric acid dew point is in

C. Although this correlation is more accurate at H2 O concentrations higher than 25%, but it
significantly underpredicts the sulfuric acid dew points at low H2 O concentrations prevailing in
oil and gas industries. Since the above correlations are not accurate enough for proper design of
combustion equipments and heat recovery systems, a general correlation has been presented for
accurate prediction of the most important acid gases dew points.

PROPOSED CORRELATION

In this work, a general correlation based on all verified experimental data is proposed for accurate
prediction of flue gas acid dew points. A set of 940 dew point temperatures is determined for the
most important acidic gases namely, SO3 , SO2 , NO2 , HCl, and HBr by using the most accurate
vapor-liquid equilibrium data (Perry et al, 1999; Ullmann’s, 2001; Gmehling et al., 2004; Nippon
Oil Company, 2008). Studies have found that the following general correlation can be used for
accurate prediction of the dew points of acidic combustion gases:

(3)

where TDew is the acid dew point in ◦ C and the partial pressures (pAcid and pH2O ) are expressed in mm
Hg. It should be noted that the parameters Ai , Bi , Ci , and Di are not dependent on acid species and
are always fixed. The parameter, λ and molecular weight, Mw are given for the relevant condensed
acid. The optimum values of all parameters determined by the genetic algorithm (Goldberg, 2007)
are displayed in Table 1.
1990 B. ZARENEZHAD

TABLE 1
The Optimum Values of Parameters in Eq. (3)

Condensed
Acids H2 SO4 H2 SO3 HNO3 HCl HBr

λ 0.011283 0.005164 −0.00614 −0.04165 0.00466


Mw 98.0 82.0 63.0 36.5 80.9
Indices i=0 i=1 i=2 i=3 i=4
A 160.4 −45.57 −1320 372.4 770.2
B −1.365 4.031 138 −34.88 −78.01
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C 18.93 −7.466 −115.1 31.96 65.95


D −0.4365 0.1829 3.622 −0.9925 −2.165

Equation (3) with the parameters displayed in Table 1 yields the smallest sum of the squared errors
for the whole range of acid dew point temperatures. The performance of the proposed correlation is
elaborated in the following section.

RESULTS AND DISCUSSION

Predicted flue gas sulfuric acid dew points by using the proposed correlation (Eq. [3]) are compared
with experimental data at different acid and moisture concentrations in Figure 1. Whenever fossil
fuels containing sulfur are fired in heaters or boilers, sulfur dioxide, and to a small extent sulfur
trioxide are formed in addition to carbon dioxide and water vapor. The SO3 combines with water
vapor in the flue gas to form sulfuric acid and condenses on heat transfer surfaces that could lead to
corrosion and destruction of the surfaces. This condensation occurs on surfaces that are at or below
the dew point of the acid gas.
As shown in Figure 1, the acid dew point is very sensitive to the flue gas SO3 concentration
such that a small increase in SO3 concentration leads to a significant increase in sulfuric acid dew
point at a given H2 O concentration. The moisture content is also an important influencing parameter.
However, as the moisture concentration is increased, effect of vapor H2 O on sulfuric acid dew point

FIGURE 1 Comparison of the proposed correlation with experimental sulfuric acid dew points at different moisture
and acid concentrations.
ACCURATE PREDICTION OF ACID DEW POINTS 1991
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FIGURE 2 Comparison of the proposed correlation with experimental sulfurous acid dew points at different
moisture and acid concentrations.

is gradually reduced. Since the sulfuric acid, which is formed through the reaction of SO3 and H2 O
in the flue gas, is usually condensed at relatively high temperatures, the corrosion risk in the waste
heat recovery system is too high. As shown, the vapor phase sulfur trioxide concentration has a
very strong influence on flue gas dew point especially at SO3 concentrations below 100 ppmv. Thus
the accurate prediction of sulfuric acid dew points at low SO3 concentrations prevailing in process
industries is very important to control the corrosion problems in thermal waste treatment plants and
energy recovery equipments. In most installations the formation of sulfuric acid is prevented by
keeping the temperature above the sulfuric acid dew point as well as possible.
Predicted and measured flue gas sulfurous acid dew points are compared in Figure 2. As shown
in this figure, the sulfurous acid condensation temperature is mainly influenced by the water vapor
concentration. Since the sulfurous acid is always formed through the dissolution of SO2 in condensed
water below the water dew point, the corrosion risk in the stack is lower as compared to the case
of sulfuric acid. However the sulfurous acid formation at the temperatures around 60◦ C speeds up
the metallic corrosion in heat recovery systems. The trend of dew point variation with respect to the

FIGURE 3 Comparison of the proposed correlation with experimental nitric acid dew points at different moisture
and acid concentrations.
1992 B. ZARENEZHAD
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FIGURE 4 Comparison of the proposed correlation with experimental hydrochloric acid dew points at different
moisture and acid concentrations.

moisture content is similar to the case of sulfuric acid such that the H2 O content is less influential
at higher moisture concentration. According to Figure 2, the sulfurous acid dew point temperature
is always below 70◦ C as long as the moisture concentration is not higher than 30 vol%.
Predicted flue gas nitric acid dew points by using the proposed correlation are compared with
experimental data at different acid and moisture concentrations in Figure 3. The NO2 condenses as
nitric acid below the nitric acid dew point or it dissolves in the condensed water below the water dew
point to form nitric acid solution causing very severe stress corrosion cracking. In a gas, containing
50 ppmv NO2 and 5 vol% water (a typical high NO2 containing GT gas) the NO2 dew point (28◦ C)
is lower than the water dew point (33◦ C). During operation of the Heat-Recovery Steam Generators
(HRSGs), the inlet temperature is at least 70◦ C, which excludes water and nitric acid condensing.
In this case, only during shutdowns, nitric acid can be formed by solving of the gas in the water
droplets. At high flue gas NO2 concentrations, the NO2 dew point is usually higher than water dew
point such that the nitric acid condensation takes place directly from the gas phase below the nitric

FIGURE 5 Comparison of the proposed correlation with experimental hydrobromic acid dew points at different
moisture and acid concentrations.
ACCURATE PREDICTION OF ACID DEW POINTS 1993
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FIGURE 6 Comparison of the proposed correlation with Verhoff and Banchero (V.B) and Okkes correlations and
experimental data.

acid dew point. Predicted nitric acid dew points are in good agreement with the experimental data
as shown in Figure 3.
Predicted flue gas hydrochloric and hydrobromic acid dew points by using the proposed correla-
tion are also compared with measured data at different acid and moisture concentrations in Figures 4
and 5, respectively. In municipal solid waste fired plants, in addition to sulfuric acid, one has to
deal with hydrochloric and hydrobromic acid formation. Also the halogenated compounds used in
various types of plastics are released in waste incinerators such that the dew point corrosion due to
HCl or HBr condensation may take place. Similar to the previous cases, effect of H2 O concentration
on acid dew point is more important at low moisture concentrations as shown in Figures 4 and 5.
According to these figures, the flue gas hydrochloric and hydrobromic acid dew points are usually
below 80◦ C in most practical cases. Predicted results are in good agreement with experimental data
as shown in Figures 4 and 5.
The proposed correlation (Eq. [3]) is compared with the V.B (Eq. [1]) and Okkes (Eq. [2])
correlations regarding the prediction of sulfuric acid dew points at a moisture concentration of

FIGURE 7 Comparison between the proposed correlation predictions with the experimental acid gases dew points.
1994 B. ZARENEZHAD

20 vol% in Figure 6. As shown in this figure, the Verhoff and Banchero correlation leads to a
considerable acid dew point overprediction. In such a case the operator may incorrectly increase the
air preheating level to combat the cold-end corrosion problem. On the contrary, using the Okkes
correlation leads to a significant dew point underprediction such that the air preheating level may not
be adequate to overcome the corrosion risk. The dew points predicted by the proposed correlation
(Eq. [3]) are much more accurate than those predicted by the V.B and Okkes correlations and are in
excellent agreement with measured acid dew points as shown in Figure 6. According to Figures 1–5,
the limiting dew point is that due to sulfuric acid and thus any heat transfer surface should be kept
above H2 SO4 dew point if acid condensation is to be avoided. The accurate prediction of flue gas acid
dew point is quite important for optimization of energy consumption in combustors and incinerators.
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The average absolute deviation (AAD%) in sulfuric acid dew point predictions is about 0.5541%,
which is small enough for design calculations. Since the sulfuric acid dew point is usually higher than
that of the other acids, it is important to predict the H2 SO4 condensation temperature accurately. In
fact the sulfuric acid dew point temperature is the main bottleneck for increasing the performance of
heat recovery systems. The overall AAD%, RMSD and R2 values regarding the proposed correlation
are about 1.055%, 0.9815, and 0.9994 respectively, suggesting that Eq. (3) is accurate enough for
predicting the dew points of the different acid gases.
The predicted flue gas acid dew points according to Eq. (3) are also compared with all available
experimental data regarding all aforementioned acid gases in Figure 7. As shown, the proposed
correlation can be used for accurate prediction of the flue gas acid dew point temperatures over wide
ranges of moisture and acid gas concentrations.

4. CONCLUSIONS

A general correlation has been presented for accurate prediction of the flue gas acidic dew points over
wide ranges of moisture and acid gas concentrations. Acidic combustion gases (SO3 , SO2 , NO2 , HCl
and HBr) can cause rapid corrosion when they condense (as H2 SO4 , H2 SO3 , HNO3 , HCl and HBr
respectively) on the surfaces of the heat recovery and flue gas treatment equipments. The accurate
prediction of flue gas acid dew point is quite important for optimum control of corrosion rate and
energy consumption in combustors and incinerators. The proposed correlation (Eq. 3) outperforms
the other alternatives regarding the prediction of acid dew points in chemical process industries.
The predicted flue gas acidic dew points are in excellent agreement with experimental data with the
overall average absolute deviation of 1.055%.

ACKNOWLEDGMENTS

The authors would like to thank the cooperation of National Iraninan Gas Company (NIGC) during
the preparation of the manuscript.

REFERENCES

Blanco, J. M., and Peña, F. (2008). Increase in the boiler’s performance in terms of the acid dew point temperature:
Environmental advantages of replacing fuels. Appl. Therm. Eng. 28:777–784.
Cherif, M., Mgaidi, A., Ammar, M. N., Abderrabba, M., and Fürst, W. (2002). Representation of VLE and liquid phase
composition with an electrolyte model: application to H3 PO4 -H2 O and H2 SO4 -H2 O. Fluid Phase Equilib. 194:729–738.
Gmehling, J., Menke, J., Krafczyk, J., and Fischer, K. (2004). Azeotropic Data (2nd ed.). Berlin: Wiley-VCH.
Goldberg, D. E. (2007). Genetic Algorithms in Search, Optimization, and Machine Learning. Boston: Addison Wesley.
ACCURATE PREDICTION OF ACID DEW POINTS 1995

Kiang, Y. H. (1981). Predicting dew points of acid gasses. Chem. Eng. 9:127–128.
Lins, V. F. C., and Guimaraes, E. M. (2007). Failure of a heat exchanger generated by an excess of SO2 and H2 S in the Sulfur
Recovery Unit of a petroleum refinery. J. Loss Prevention Proc. Indust. 20:91–97.
Nippon Oil Company. (2008). Sulfuric acid dew point measurement. Technical document. Tokyo, Japan.
Okkes, A. G. (1987). Get acid dew point of flue gas. Hydrocarb. Process. 7:53–55.
Perry, R. H., Green, D. W., and Maloney, J. O. (1999). Chemical Engineers Handbook (7th ed.). New York: McGraw-Hill.
Rockel, M. B., and Bender, R. (2008). Corrosion Handbook. Frankfurt, Germany: Society for Chemical Engineering and
Biotechnology.
Ullmann’s. (2001). Ullmann’s Encyclopedia of Industrial Chemistry (6th ed.). New York: Wiley.
Verhoff, F. H., and Banchero, J. T. (1974). Predicting dew points of flue gases. Chem. Eng. Prog. 70:71–72.
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NOMENCLATURE

TDew sulfuric acid dew point yNO2 concentration of NO2 in


temperature,◦ C the flue gas, ppmv
pH2O partial pressure of H2 O yHCl concentration of HCl in
in the flue gas, mm Hg the flue gas, ppmv
pSO3 partial pressure of SO3 in yHBr concentration of HBr in
the flue gas, mm Hg the flue gas, ppmv
pAcid gas partial pressure of acid RMSD root mean square devia-
gas (SO3 , SO2 , NO2 , tion
HCl, HBr), mm Hg AAD% percent of average abso-
yH2O concentration of H2 O in lute deviation
the flue gas, vol% R2-value correlation coefficient
ySO3 concentration of SO3 in i index (from 0 to 4) in Eq.
the flue gas, ppmv (3)
ySO2 concentration of SO2 in Ai , Bi , Ci , Di and λ parameters defined in
the flue gas, ppmv Eq. (3)
Mw molecular weight