Selection of Materials for Superheater Recovery Boiler

Harold Nikoue: Georgia Tech, SURF 2009 Fellow

Faculty Advisor: Dr. Preet Singh Mentors: Jamshad Mahmood, Kevin Chasse and Stephen Asher

The purpose of a superheater is to raise the steam vapor

temperature to generate power from pulp and paper byproducts. One way to maximize this self-generated
electricity is to increase the steam temperature. Any
elevation of temperature is limited; however, due to the
acceleration of carbon steel corrosion that would follow on
the surface of superheater tubes.
The main cause of metal degradation is the formation of a
molten salt deposit on the surface of superheater. The salt
lowers the first melting temperature of most metals to
560C, which leads to accelerated liquid erosion-corrosion.
To aggravate the situation, the high pressure gas flow is
both oxidizing and sulfidizing at this temperature
Materials that form a protective coating can withstand this
harsh environment, and therefore permit higher efficiency
in electricity generation. The present paper investigates the
corrosion behavior of austenitic stainless steels (SS304L,
310, 347), incoloys (I-800HT, I825), and superalloy 85H as
compared to A213T22 in simulated furnace environment.
Experimental procedure
1 inch by 1 inch coupons of each material were cut into two
equal sections and ground with SiC paper to a 600-grit
finish. The samples were covered by a finely ground smelt
composed at 96% of sodium sulfate (Na2SO4), at 3% of
sodium carbonate (Na2CO3) and of sodium chloride (NaCl)
in weight percent. Four different exposure tests were then
conducted on the prepared samples as shown in table 1.
Experiment 15
550C
Smelt #1 +
1%H2S+99%N2
(250sccm gas)+
0.4ml/min H2O
(250 sccm H20
vapor)

Experiment 16
480C
Smelt #1 +
1%H2S+99%N2
(250sccm gas)+
0.4ml/min H2O
(250 sccm H20
vapor)

Experiment 17
550C
Smelt #1 +
1%SO2+99%N2
(250sccm gas)+
0.4ml/min H2O
(250 sccm H20
vapor)

Experiment 18
480C
Smelt #1 +
1%SO2+99%N2
(250sccm gas)+
0.4ml/min H2O
(250 sccm H20
vapor)

Table 1. Experimental gas content.

After each 168 h. coupon exposure test, the specimens

were air cooled. The first section of each material was fixed
into a two part metallography epoxy, and ground with SiC
to a 1000-grit finish to reveal a cross-sectional area for
microstructure analysis. The samples of the second batch
were characterized ex-situ using XRD ranging from 10 to
70 2 with a step size of 0.08 2 and scan step time of 5
seconds. The surfaces were then sandblasted to remove
any formed film using standard practice, and weighed for
weight-loss corrosion rate calculation.
Results and discussion
Micrograph analysis

After each heat treatment, micrographs of the coupons were

taken at 100, 200 and 500 magnification. The micrographs
revealed general trends. In experiment 15, A213T22 created a
thick porous scale, with many cracks, an adherent scale at
480C and a non-adherent scale at 550C.This can explain the
high corrosion rate experimented at 550C by carbon steel,
since both gases were allowed to diffuse into the scale and
produce pitting. 310 was the only alloy to exhibit a uniform thin,
dense, coherent film at 550C in presence of SO2. , while most
other samples exhibited exfoliation, selective leaching or no
corrosion.
X-ray Diffraction
As shown in table 2, A213 forms iron carbonate, (FeCO3) at
550C after every coupon test exposure.
350

1. FeCO3
2. Na2SO4
3. MnS

1
300
250

Intensity

Introduction

200

A213_15
150
1
100

A213_17

50

0
0

10

20

30

40
2

50

60

70

80

Table 2. XRD pattern showing A213T22 at 550C,

comparing the effect of H2S with respect to SO2.
In presence of SO2 we have a high oxidation into
Manganese Chromium Oxide and iron oxide FeO, as well as
formation of Na2SO4 which might explain the non adherence
of the film. In presence of H2S, on the contrary, there is more
sulfidation with the presence of MnS which causes porosity
of the film.
Conclusion:
Using corrosion rate calculations, the behavior of the selected
materials were studied, allowing for comparison of these
materials over a range of environments. From microstructure
analysis, the nature of corrosion could be further investigated
leaving with only one candidate that formed a protective oxide
film 310, and two alloys (85H, I800HT) with little corrosion but
no surface films. Although the structure of the film could be
characterized with XRD, understanding the mechanism of
surface passivation would require other techniques such as
Cahn microbalance or spectroscopy.