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Corrosion of Type 316L Stainless Steel Piping in Synthetic Gas Plants

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DOI: 10.5006/0759

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Corrosion of Type 316L Stainless Steel Piping
in Synthetic Gas Plants
Sungkyu Lee,‡,* Seok-Woo Chung,* Seung-Jong Lee,* and Yongseung Yun*
AbstrAct
Corrosion behavior of Type 316L (UNS S31603) stainless steel
piping used in integrated coal gasification combined cycle
(IGCC) plant facilities processing coal (0.9 MPa to 1.1 MPa and
150°C to 300°C) and industrial waste (0.11 MPa and 40°C
to 60°C) was explained using scanning electron microscopy-
energy dispersive x-ray spectrometry (SEM/EDS), x-ray dif-
fraction (XRD), and a thermodynamic Ellingham-Pourbaix
stability diagram. Material wastage and pitting were observed
on the inner wall of Type 316L stainless steel piping used in
Institute for Advanced Engineering (IAE) coal and industrial
waste syngas plant facilities after 720 h and 170 h (total
hours) of operation, respectively. Relevant corrosion mecha-
nism was suggested based on SEM/EDS examination and
thermodynamic inferences: the observed material wastage
and corrosion behavior of the Type 316L piping material cut
off from the coal syngas IGCC plant were explained by com-
bined effects of evaporation of iron chlorides and subsequent
transformation into thin oxides. On the other hand, the pitting
corrosion phenomenon observed on the inner wall of Type
316L piping cut off from industrial waste processing IGCC
plant was attributed to modified pitting mechanism caused by
the preferential growth of corrosion pits in horizontal direction
under aqueous condensate environment containing hydrochlo-
ric acid (HCl).
Submitted for publication: June 11, 2012. Revised and accepted:
February 20, 2013. Preprint available online: April 16, 2013, doi:
http://dx.doi.org/10.5006/0759. Work leading to this manuscript
was conducted at Institute for Advanced Engineering, Korea (IAE),
and all of the legal claims for the research belong to the IAE.
‡
Corresponding author. E-mail: sklee@ajou.ac.kr.
* Advanced Materials & Processing Center and Plant Engineering
Center, Institute for Advanced Engineering (IAE), 633-2 Goan-ri,
Baegam-myeon, Cheoin-gu, Yongin-si, Gyeonggi-do, 449-863,
Korea.
ISSN 0010-9312 (print), 1938-159X (online)
CORROSION—Vol. 69, No. 9 13/000167/$5.00+$0.50/0 © 2013, NACE International
CORROSION SCIENCE SECTION
KEY WORDS: condensate, integrated coal gasification com-
bined cycle, mixed oxidant corrosion, pitting, synthetic gas
(syngas), Type 316L stainless steel
IntroductIon
Coal is an abundant and low-cost fuel, and it will be
used to generate power for generations to come.1 The
technology of coal and industrial waste gasification
allows the environment-friendly use of coal for power
generation.1-2 Coal and industrial waste are intermit-
tently gasified to form synthetic gas (syngas) at the
integrated coal gasification combined cycle (IGCC)
facility affiliated with the Institute for Advanced Engi-
neering (IAE). The IAE syngas thus produced essen-
tially contains a mixture of H2, carbon monoxide (CO),
carbon dioxide (CO2), H2O, N2, and minute quantities
of hydrochloric acid (HCl) and hydrogen sulfide (H2S),
along with some 10,000 mg/m3 to ~12,000 mg/m3 of
particulate materials. Many conditions contribute to
the aggressive conditions to which a particular com-
ponent in an IGCC system is exposed. Therefore, the
input gas composition used in the present research
could lead to degradation of piping material in mixed
oxidants atmospheres.3-4 If the corrosive conditions
encountered within the IGCC system are fully defined
and the operation of the system is fully understood,
proper alloys could be applied to build an IGCC sys-
tem that would give many years of dependable service.
To specify confidently the use of lesser alloys in an
IGCC system, limits to the use of the alloys must be
defined.1 For this purpose, dew point, temperature,
921
CORROSION SCIENCE SECTION
Figure 1. Dotted square below process no. 28 is the location where the corroded samples were retrieved in coal syngas
IGCC plant of IAE.
Figure 2. Pitting is observed in the piping of the dotted square area in the industrial waste IGCC plant of IAE.
and partial pressures of individual gas constituents in
the mixed oxidants must be considered in defining the
corrosiveness of the environment.1,4-5
In the coal-gasifying IGCC pilot plant facility af-
filiated to IAE, material wastage and reduction of wall
thickness were found extensively on the inner surface
of Type 316L (UNS S31603)(1) stainless steel piping,
which connected particulate removal unit and water
scrubber and was exposed to temperature range be-
tween 150°C and 300°C. Figure 1 is a schematic dia-
gram of the location where the corroded samples were
retrieved in coal syngas IGCC plant of IAE. On the
(1)
UNS numbers are listed in Metals and Alloys in the Unified Num-
bering System, published by the Society of Automotive Engineers
(SAE International) and cosponsored by ASTM International.
922
other hand, industrial wastes are also intermittently
processed in the different IGCC plant of IAE to gener-
ate syngas of essentially similar composition to that of
coal syngas IGCC of IAE, but the IAE industrial waste
syngas was found to contain 10 ppm to ~200 ppm
of HCl, which turned out to be significantly higher
than 7 ppm of IAE coal syngas. In the IGCC plant of
IAE where industrial wastes are processed, extensive
pitting was observed on the wall of Type 316L stain-
less steel piping, which connected syngas cooler and
cleanup units and was exposed to temperatures of
40°C to ~60°C. The schematic diagram of the pitting
failure location is given in Figure 2. Therefore, actual
Type 316L piping was taken from the failed spots of
the IAE pilot plants to investigate the root cause of the
CORROSION—SEPTEMBER 2013

failure. The failed piping thus revealed either mate-
rial loss, resulting in the thinning of the piping wall
or pitting; the former is a typically observed example
of corrosion phenomena under these mixed oxidants
environments.4
Therefore, metallographic examination using
scanning electron microscopy-energy dispersive x-ray
spectrometry (SEM-EDS) analysis and thermodynamic
calculations should be performed to closely examine
and explain the observed failures by mixed oxidant
corrosion, following the methods of references.3-4,6 By
this, mechanisms of materials degradation and root
cause of the observed corrosion behavior were ex-
plained.
ExpErImEntAl procEdurEs
Failed Piping from the Institute for Advanced
Engineering Syngas Plant
Two pieces of piping material were individually
cut off from two separate IGCC plant units of IAE,
one producing coal syngas and the other process-
ing industrial waste, to examine and characterize the
failures. Visual inspection combined with periodic
monitoring of the piping in both units clearly revealed
material loss, and it was quite evident that the two
corroded piping samples failed in different modes,
depending on its exposure condition: uniform corro-
sion and pitting of piping samples from coal syngas
producing and industrial waste processing plants,
respectively. The corroded piping retrieved from coal
syngas IGCC of IAE had been subject to 0.9 MPa to
1.1 MPa of internal pressure and the corrosive en-
vironment of Table 1(a). Regular replacement of the
piping with sufficient margin of safety was the only
preventive measures taken. On the other hand, the
industrial waste IGCC piping of IAE had been subject
to nearly atmospheric pressure of 0.11 MPa and cor-
rosive environment of Table 1(b). It was replaced only
when macroscopic pitting was visually confirmed. The
representative compositions of coal and industrial
wastes used in the IGCC of IAE are also shown in
Table 1. The original heat treatment conditions for the
examined samples were not clearly known.
Piping Sample from Coal Syngas Integrated Coal
Gasification Combined Cycle Plant — A piping and
flange made of Type 316L stainless steel was cut off
from coal syngas IGCC plant section between particu-
late removal unit and water scrubber (dotted part of
Figure 3), the internal part of which was exposed to
a temperature range between 150°C and 300°C. In
fact, cumulative, but not continuous, exposure time
was about 1 month, though duration of installation
before cutting off totaled about 54 months. One batch
of operation continued for about 8 h and combustion
operation was intermittently carried out throughout
54 months until total hours of operation totaled about
720 h.
CORROSION—Vol. 69, No. 9
CORROSION SCIENCE SECTION
Piping Sample from Industrial Waste Processing In-
tegrated Coal Gasification Combined Cycle Plant — An-
other Type 316L stainless steel piping was cut off from
industrial waste processing IGCC plant (dotted part
of Figure 4[a]): a section between syngas cooler and
cleanup unit was exposed to temperatures of 40°C to
~60°C before being cut off. In this case, cumulative,
but not continuous, exposure time turned out to be
about 7 days while the piping had been installed in
place for about 18 months. One batch of operation
also continued for 8 h and combustion operation was
intermittently performed throughout 18 months until
hours of operation totaled about 170 h. More severe
corrosiveness of the internal piping environment is
quite evident as judged from extensive macroscopic
pitting failures observed as shown in Figures 4(b) and
(c). Pits in different extents of progress are also macro-
scopically shown in Figure 4(c). Chemical composition
of those Type 316L stainless steel piping is indicated
in Table 2, according to ASTM A240 316/316L7 and
ASME SA240/SA240M 316/316L8 specifications.9
Specimen Preparation
The corroded piping samples from longitudinally
welded Type 316L stainless steel piping (ø 62 mm with
5 mm thickness) were sectioned into proper sizes
using a band saw to fit into the 30 nm and 40 mm
diameters of polyvinyl chloride (PVC) pipe, which was
cut into a cylindrical shape of varying heights, 8 mm
to 20 mm, to hold epoxy resin. The piping samples
of section 2.1 were subsequently cold-mounted,
ground, and polished on a variable speed rotating
wheel grinder-polisher. Grinding was performed with
rotating SiC papers from #200 to 2000, and the
mounted samples were further polished with a rotat-
ing cloth soaked with a suspension of alumina (Al2O3)
particles (size: 0.3 µm). Upon completion of polishing,
the mounted samples were properly etched using
Kalling’s no. 2 etch (“waterless” Kalling’s: 100 mL eth-
anol [C2H5OH], 100 mL HCl, and 5 g of cupric chloride
[CuCl2])10 and then further prepared following the
method of Singh, et al.,11 before examination and
characterization of microstructures by SEM and EDS.
Examination and Characterization by Scanning
Electron Microscopy, Energy-Dispersive
Spectroscopy, and X-Ray Diffraction
The morphological and microstructural analysis
was conducted using SEM and EDS analyses of the
mounted samples. Typical microstructure of the ex-
amined Type 316L piping sample is shown in Figure
5, revealing its grain boundaries. Surface chemical
composition of the samples along a selected line was
also examined. These analyses were made to iden-
tify any possibility of carburization, characterize the
observed corrosion products in the piping samples,
and to deduce and elaborate the mechanism of the
observed corrosion behavior prevailing in these spots
923
CORROSION SCIENCE SECTION

Table 1
Ranges of Input Gas Compositions Corresponding to the (a) Coal Syngas IGCC and (b) Industrial
Waste Processing IGCC Plant. The Relevant Compositions of Coal and Industrial Wastes are also
Presented in (c) and (d), Respectively. The Range of Input Gas Compositions in (a) and (b) also
Cumulatively Reflect Seasonal as well as Extensive Periods of Shutdown Effects.
(a) input gas composition of coal syngas igCC plant
CO 38% to 48%
H2 17% to 25%
CO2 4% to 10%
N2 10% to 20%
H 2S 250 ppm to 600 ppm
Particulate materials 10,000 mg/m3
HCl 7 ppm
H2O 5%

(b) input gas composition of industrial waste processing igCC

CO 30% to 35%
H2 30% to 35%
CO2 25% to 35%
N2 3% to 7%
H 2S 250 ppm
Particulate materials 12,000 mg/m3
HCl 10 ppm to 200 ppm
H2O 2% to 3%

(c) representative composition of coal used in igCC: initial deformation temperature (iDT), softening
temperature (SF), hemispherical temperature (HT), and fluid temperature (FT) have their usual
significance
Proximate Analysis(1) Moisture 6.77
(wt%) Volatile Matter 40.07
Ash 5.90
Fixed Carbon 47.26
Ultimate Analysis(2) C 68.16
(wt%) H 5.62
N 2.69
S 0.40
O(3) 18.94
Ash Fusion IDT 1,230
Temperature ST 1,250
(°C) HT 1,270
FT 1,290
Gross Heating Value(2) (kcal/kg) 6,576
(1)
As received, (2) Moisture free basis, (3) by difference

(d) representative composition of industrial wastes used in igCC: volatile matter (VM), fixed carbon
(FC), higher heating value (HHV), and moisture free (MF) have their usual significance
Proximate analysis (wt%) HHV
Constituents (%) Moisture VM FC ash (Dry, kcal/kg)
Paper 9.9 7.79 71.45 9.49 11.28 4,158
Fiber 14.2 11.83 60.60 7.90 19.68 3,437
Wood 13.7 15.97 64.57 16.64 2.83 4,300
Vinyl/plastic 28.7 3.66 77.56 0.75 18.04 6,786
Rubber 6.5 1.06 61.96 8.59 28.40 4,468
Noncombustible 27.1 3.55 8.31 1.90 86.24 —
Total 100.0 6.71 52.99 5.61 34.68 3,723
ultimate analysis (MF, wt%)
Constituents (%) C H N S O ash
Paper 9.9 46.25 6.65 0.05 34.74 34.74 12.23
Fiber 14.2 49.11 4.41 9.10 14.87 14.87 22.32
Wood 13.7 43.73 5.66 2.50 44.46 44.46 3.36
Vinyl/plastic 28.7 70.46 10.53 0.03 0.22 0.22 18.73
Rubber 6.5 41.13 5.53 0.05 24.50 24.50 28.70
Noncombustible 27.1 100.00
Total 100.0 40.39 5.44 0.09 13.26 13.26 39.17

924 CORROSION—SEPTEMBER 2013

 CORROSION SCIENCE SECTION

(a)
Figure 3. Corroded section between particulate removal unit
and water scrubber at coal syngas IGCC plant of IAE is marked as
dotted square.

of the IGCC plant. Powdered corrosion products were

scraped off the inner walls of failed piping samples by
using a proper file for XRD analysis.

rEsults And dIscussIon

Thermodynamic Perspectives
Although an extensive literature survey was
made, corrosion of Type 316L stainless steel piping
(b)
under similar IGCC operating environments rarely
has been considered.12 In view of the observed results
from the present experiments, uniform corrosion and
pitting were main modes of corrosion for Type 316L
stainless steel piping samples from coal syngas and
industrial waste IGCC pilot plants, respectively. A
literature result on corrosion tests of the commercial
alloy sample (0.04 C-2.5Si-0.8 Mn-13.1 Ni-17.3 Cr-Fe
balance in wt%) subject to 500 ppm and 1,000 ppm
HCl-containing gas mixture of 8% O2, 12% CO2, 15%
H2O, and 100 ppm SO2 at a temperature range from
480°C to ~580°C revealed increased (uniform) corro-
sion rates of test samples.12
As a starting point of mixed oxidants corrosion
study, Ellingham-Pourbaix stability diagrams were (c)
constructed using FactSage† software ver. 6.2 to in- Figure 4. (a) Corroded section between syngas cooler and
vestigate the thermodynamic stability of metal chlo- cleanup unit of industrial waste processing IGCC plant at IAE
marked as dotted square. Extensive pitting failure observed
rides and oxides at the test temperatures and define
externally and internally as shown in (b) and (c), respectively. Some
equilibrium conditions of the corrosion test.4,12-13
pits in different extents of progress are also observed in (c).
Other important thermodynamic parameters such
as carbon activity and dew points of corrosive gases
were also calculated using FactSage† steel (FSstel) <0.045%P, <0.03%C, <0.03%S, and balance Fe) at
and oxide (FToxid) databases. 300°C and 60°C for piping samples from coal syngas
Figures 6(a) and (b) show the stability of the reac- producing and industrial waste processing plants, re-
tion products from uniform corrosion and pitting of spectively. Solid squares represent partial pressures
Type 316L piping material (composed of 16% to 18.5% of chlorine and oxygen calculated by using actual cor-
Cr, 10% to 14% Ni, 2% to 3% Mo, <2% Mn, <1% Si, rosive environments of mixed oxidants encountered
†
Trade name. in the present research as a bases for aforementioned

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CORROSION SCIENCE SECTION

Table 2
Chemical Composition as Represented by ASTM A240
and ASME SA-240 Specifications9 is Indicated in the Table
Below, Where –ab Denotes b—a Range of Compositions(A)
Chemical
Percentage by Weight Composition
(maximum unless of the
range is specified) analyzed Tube
Carbon 0.030 0.035
Manganese 2.00 >2.00
Silicon 0.75 >0.75
Chromium 16.00 16.00
18.00 18.00
Nickel 10.00 10.00
14.00 15.00
Molybdenum 2.00 2.00
3.00 3.00
Phosphorus 0.045 <0.045
Sulfur 0.030 0.005 Figure 5. Typical microstructure of Type 316L piping sample
0.017 examined by SEM.
Nitrogen 0.10 0.1<
Iron Bal. Bal.
(A)
The chemical composition of the analyzed tube is also shown in Corroded Piping Sample from Coal Syngas
the third column. Integrated Coal Gasification Combined Cycle
Plant
thermochemical softwares: the process streams of From Figure 6(a) and Table 3(a), it is strongly in-
coal syngas IGCC and industrial waste processing ferred that mixture of the metal, oxides, and complex
IGCC plants could be regarded as belonging to reduc- oxides are stable at 300°C: Fe (face-centered cubic
ing environments. The ranges of input gas composi- [fcc]) + magnetite (Fe3O4[s]) + tephroite (Mn2SiO4[s]) +
tions are described in Table 1. The detailed reaction pyroxmangite (MnSiO3[s]) + chromite (FeCr2O4[s]) are
products corresponding to the numbers in the phase thermodynamically stable phases of a process stream
stability diagrams of Figures 6(a) and (b) are listed in environment as designated by no. 29 in Figure 6(a).
Tables 3(a) and (b), which represent many thermody- The XRD results (Figure 7[a]) of piping corrosion prod-
namically stable phases available at the given tem- ucts from the coal syngas producing plant revealed
peratures and corrosive environments. The reaction strong peaks of SiO2 and austenite, giving partial jus-
products from uniform corrosion and pitting at 300°C tification of the proposed reactions.
and 60°C could be experimentally differentiated using The observed failure was in the form of (rather
XRD analysis, which is shown in Figure 7. uniform) material loss on the inner wall of the piping,

(a) (b)
Figure 6. Stability diagrams calculated by commercial thermochemical software: (a) at 300°C and (b) at 60°C. Solid
squares represent partial pressures of chlorine and oxygen calculated by using actual corrosive environments of mixed
oxidants encountered in the present research as bases.

926 CORROSION—SEPTEMBER 2013

 CORROSION SCIENCE SECTION

Table 3
Detailed Reaction Products Corresponding to the Areas
Given by Numbers in the Phase Stability Diagrams
of Figures 6(a) and (b)
(a) T = 300°C
1) fcc + CrCl2(s) + MnCl2(s) + SiO2(s) + FeCl2(s)
2) fcc + MnCl2(s) + Cr2O3(s) + SiO2(s) + FeCl2(s)
3) fcc + FeCl2(s) + MnCl2(s) + FeCr2O4(s) + SiO2(s)
4) bcc + SiO2(s) + FeCr2O4(s) + Fe3O4(s) + MnSiO3(s) +
(NiO)(Fe2O3)(s)
5) M23C6 + CrCl2(s) + MnCl2(s) + SiO2(s) + fcc + FeCl2(s)
6) M23C6 + MnCl2(s) + Cr2O3(s) + SiO2(s) + fcc + FeCl2(s)
7) M23C6 + FeCl2(s) + MnCl2(s) + SiO2(s) + fcc + FeCr2O4(s)
8) M23C6 + Fe2SiO4(s) + FeCl2(s) + MnCl2(s) + fcc + FeCr2O4(s)
9) fcc + Fe2SiO4(s) + MnCl2(s) + Fe3O4(s) + FeCr2O4(s)
10) M7C3 + MnCl2(s) + FeCr2O4(s) + Fe3O4(s) + MnSiO3(s) +
(NiO)(Fe2O3)(s)
11) M7C3 + MnCl2(s) + Cr2O3(s) + SiO2(s) + fcc + FeCl2(s)
12) M7C3 + FeCl2(s) + MnCl2(s) + SiO2(s) + fcc + FeCr2O4(s)
13) M7C3 + Fe2SiO4(s) + FeCl2(s) + MnCl2(s) + fcc + FeCr2O4(s) (a)
14) M23C6 + Fe2SiO4(s) + MnCl2(s) + Fe3O4(s) + fcc + FeCr2O4(s)
15) M7C3 + Fe2SiO4(s) + MnCl2(s) + Fe3O4(s) + fcc + FeCr2O4(s)
16) fcc + FeCl2(s) + MnCl2(s) + FeCr2O4(s) + SiO2(s)
17) M7C3 + FeCl2(s) + MnCl2(s) + SiO2(s) + fcc + FeCr2O4(s)
18) fcc + Fe2SiO4(s) + FeCl2(s) + FeCr2O4(s) + MnCl2(s)
19) M7C3 + Fe2SiO4(s) + FeCl2(s) + MnCl2(s) + fcc + FeCr2O4(s)
20) bcc + MnCl2(s) + SiO2(s) + fcc + M7C3 + FeCr2O4(s)
21) bcc + Fe2SiO4(s) + MnCl2(s) + fcc + M7C3 + FeCr2O4(s)
22) bcc + MnCl2(s) + MnSiO3(s) + fcc + M7C3 + FeCr2O4(s)
23) bcc + Mn2SiO4(s) + MnSiO3(s) + fcc + M7C3 + FeCr2O4(s)
24) bcc + Fe2SiO4(s) + Mn2SiO4(s) + fcc + M7C3 + FeCr2O4(s)
25) 7C3 + Fe2SiO4(s) + MnCl2(s) + Fe3O4(s) + fcc + FeCr2O4(s)
26) M7C3 + Fe2SiO4(s) + Fe3O4(s) + Mn2SiO4(s) + fcc + FeCr2O4(s)
27) M7C3 + Fe2SiO4(s) + Fe3O4(s) + Mn2SiO4(s) + fcc + FeCr2O4(s)
28) M23C6 + Fe2SiO4(s) + Fe3O4(s) + Mn2SiO4(s) + fcc + FeCr2O4(s)
29) fcc + Fe3O4(s) + Mn2SiO4(s) + MnSiO3(s) + FeCr2O4(s)
30) M7C3 + FeCr2O4(s) + Fe3O4(s) + Mn2SiO4(s) + MnSiO3(s) +
(NiO)(Fe2O3)(s)

(b) T = 60°C
1) bcc + CrCl3(s) + FeCl2(s) + MnCl2(s) + SiO2(s) + NiCl2(s)
2) bcc + Cr2O3(s) + FeCl2(s) + MnCl2(s) + SiO2(s) + NiCl2(s)
3) bcc + FeCl2(s) + MnCl2(s) + FeCr2O4(s) + SiO2(s) + NiCl2(s)
4) bcc + MnCl2(s) + FeCr2O4(s) + Fe2O3(s) + SiO2(s) + NiCl2(s)
5) bcc + MnCl2(s) + FeCr2O4(s) + Fe2O3(s) + SiO2(s) +
(NiO)(Fe2O3)(s2)
6) M7C3 + FeCl2(s) + MnCl2(s) + FeCr2O4(s) + SiO2(s) + NiCl2(s)
7) bcc + Fe3O4(s) + MnCl2(s) + FeCr2O4(s) + SiO2(s) +
(NiO)(Fe2O3)(s2)
8) bcc + FeCr2O4(s) + Fe2O3(s) + MnSiO3(s) + SiO2(s) +
(NiO)(Fe2O3)(s2)
9) M7C3 + Fe3O4(s) + MnCl2(s) + FeCr2O4(s) + SiO2(s) +
(NiO)(Fe2O3)(s2)
and it was visually observed. Considering a uniform
type of corrosion of the retrieved piping without any
visible failure observed on the external part of the pip-
ing, the corroded part of the internal piping was ana-
lyzed after it had been sectioned properly, mounted,
and polished as described in the “Specimen Prepara-
tion” section. Typical cross-sectional microstructure
of the inner wall of the piping is shown in Figure 8.
The observed thinning of the internal piping wall,
presumably at 150°C to ~300°C, could create a leak
path, which could have led insidiously to fire and ex-
(b)
Figure 7. XRD patterns of powdered corrosion products from Type
316L piping samples exposed to 300°C and 60°C at (a) coal syngas
producing and (b) industrial waste processing plant, respectively.
plosion hazards and necessitated plant shutdown for
regular checkup and replacements for prevention of
unexpected disaster. Judging from Figure 8, the
thickness of corrosion product was observed to be
about 20 µm. Therefore, the rate of metal loss during
the cumulative exposure time of 1 month is calculated
to be approximately 240 µm/y, which is acceptable
for coal syngas IGCC piping application. However, in
view of the compound form of corrosion product as
revealed in Figure 7(a), it also has to be noted that
corrosion products are normally much less dense
than the underlying Type 316L stainless steel base
metal. Therefore, the thickness of the corrosion prod-
uct layer is equivalent to a much smaller loss of thick-
ness in the base metal, which represents the true
corrosion rate. Such a calibration was not made to
compensate for actual loss of thickness in the present

CORROSION—Vol. 69, No. 9 927

CORROSION SCIENCE SECTION
Figure 8. Typical cross-sectional microstructure of the inner wall
of pipe connection between particulate removal unit and water
scrubber of IAE IGCC pilot plant producing coal syngas, with
thickness of corrosion products shown by arrows: the section was
exposed to temperature range between 150°C and 300°C.
study and it was regarded within a margin of safety
for replacement criteria.
The higher magnification SEM-EDS analysis per-
formed, as shown in Figure 9, enabled the cause and
possible mechanism of the observed failure to be iden-
tified. In the predominantly reducing environments of
the present research, oxide phases could be absent or
discontinuous and metal chlorides could form directly
on the metal surface as follows:
M(s) + Cl 2 (g ) → MCl 2 (s) (1)
where M signifies either Fe, Cr, Ni, and other metal-
lic constituents of the Type 316L stainless steel. The
formation of metal chloride could strongly be favored
at the oxide/metal interface where partial pressure of
oxygen could become quite low. The metal chloride is
subsequently transformed to oxides. This is strongly
inferred from the suggested reaction mechanism in
Reference 4, and the observed chlorine peak of Figure
9(c) gave suitable justification of the proposed mecha-
nism.
Besides, it is also well known that the rate of
corrosion is strongly temperature-dependent. The
chlorine peak of Figure 9(c) detected along the marker
line scanned across the discontinuous boundary be-
tween the corrosion product and Type 316L substrate
strongly suggest formation of iron chloride,4,14 as pre-
viously suggested, according to thermodynamic impli-
cations of Reference 3.
Since FeCl2(s) melts at 303°C and its tempera-
ture at which the chloride vapor pressure is equal
to 10–4 atm is 167°C,14 the detected chlorine peak is
accounted for by evaporation of the low melting iron
chloride and subsequent active oxidation as suggested
in Reference 4.
928
Also, Figures 9(d) and (k) revealed almost similar
intensity level peaks of Mn and S, which could indi-
cate feasibility of MnS inclusion across the corroded
area. Direct evidence of MnS inclusion could not be
obtained and it is strongly inferred that the MnS dis-
solved by catalyzation reaction of the chloride ion:15
+
2MnS + 3H2 O + 2Cl – → 2MnC
nCl – + S 2 O2–
2MnCl 3 + 6H + 8e
–
(2)
Therefore, EDS peaks of Figures 9(d) and (k)
could be attributed to the result of MnS dissolution
by chloride ion catalyzation. This argument is further
substantiated by the strong sulfur peak of the XRD
result (Figure 7[a]).
It was also necessary to examine feasibility of
metal dusting with carbides as reaction intermedi-
ates and thermodynamic activity of (graphite) carbon
was calculated using a commercial thermochemical
software with bulk concentration of carbon as a ba-
sis. The carbon activity was calculated to be 1.2×10–8,
and it was hardly sufficient to ensure any feasibil-
ity of carbide intermediates, which are required for
carburization and metal dusting.16-20 Therefore, the
observed corrosion behavior is rather attributed to
unprotective and presumed porous metal oxide forma-
tion, which was preceded by formation of volatile iron
chlorides.4,14
Dew point of the process stream was also calcu-
lated by a commercial thermochemical software and
dew point of the coal syngas IGCC process stream
(CO: 31%, H2: 31%, CO2: 31%, N2: 5%, H2S: 300 ppm,
HCl: 7 ppm, H2O: 1%) turned out to be 78.6°C, which
is significantly lower than the reaction temperature of
300°C encountered by the Type 316L piping sample.
In view of these, metal dusting and dew point corro-
sion are practically excluded from the possible cause
of the observed corrosion behavior for the Type 316L
piping sample of coal syngas IGCC plant facility.
Piping Sample from Industrial Waste Processing
Integrated Coal Gasification Combined Cycle
Plant
From Figure 6(b) and Table 3(b), it is strongly in-
ferred that mixture of the metal, oxides, and complex
oxides are stable at 60°C, which was calculated by the
a commercial thermochemical software, although the
Type 316L stainless steel maintains its fcc structure
at 60°C:
Fe( BCC) + Fe 3O 4 ( s) + MnCl 2 ( s) + FeCr2O 4 ( s) +
(3)
SiO2 ( s) + NiO ⋅ Fe 2O3 ( spinel )
The observed iron(III) oxide-hydroxide/chloride
XRD peaks of Figure 7(b) and EDS spectra of Figure
10 gave suitable justification of the proposed corro-
sion products of piping sample from industrial waste
processing IGCC plants.
CORROSION—SEPTEMBER 2013
 CORROSION SCIENCE SECTION

(l)

Figure 9. Higher magnification SEM-EDS analysis of typical cross-sectional microstructure of the inner wall: chlorine (c), manganese (d),
and sulfur (k) peaks were detected along the marker line vertically shown in (b). The solid scale bar in (b) corresponds to 60°C. (c) through
(k) represent EDS peaks of respective elements as captioned. Weight percent of individual elemental mapping is analyzed in duplicate and
tabulated at the end. EDS scan was made across the discontinuous boundary between the corrosion product and Type 316L substrate of
pipe connecting particulate removal unit and water scrubber of IAE IGCC pilot plant producing coal syngas: the section was exposed to
temperature range between 150°C and 300°C, and the corrosion product is indicated by two arrows in (b).

CORROSION—Vol. 69, No. 9 929

CORROSION SCIENCE SECTION

(l)

Figure 10 (continued on next page). SEM-EDS analysis of pitting initiation (a), where horizontally scanned cross section was W-shaped
and concave downward toward the bottom of the paper. Strong chlorine, manganese, and sulfur peaks of (c), (d), and (e) observed along the
marker line scanned across the bright ring pattern (a) suggest formation of metal chloride and MnS. (f) through (k) represent EDS peaks of
respective elements as captioned. For reproducibility check, SEM-EDS analysis of the other pit (m) of different extent was similarly made in (n)
through (w). (o) through (w) also represent EDS peaks of respective elements as captioned. Weight percent of individual elemental mapping
for (b) and (n) are analyzed and tabulated in (l) and (x), respectively. The negative quantity for Mn in (x) is attributed to experimental uncertainty
since a finite intensity of Mn spectrum is observed in (u).

930 CORROSION—SEPTEMBER 2013

 CORROSION SCIENCE SECTION

(x)

Figure 10 (continued). SEM-EDS analysis of pitting initiation (a), where horizontally scanned cross section was W-shaped and concave
downward toward the bottom of the paper. Strong chlorine, manganese, and sulfur peaks of (c), (d), and (e) observed along the marker line
scanned across the bright ring pattern (a) suggest formation of metal chloride and MnS. (f) through (k) represent EDS peaks of respective
elements as captioned. For reproducibility check, SEM-EDS analysis of the other pit (m) of different extent was similarly made in (n) through
(w). (o) through (w) also represent EDS peaks of respective elements as captioned. Weight percent of individual elemental mapping for (b)
and (n) are analyzed and tabulated in (l) and (x), respectively. The negative quantity for Mn in (x) is attributed to experimental uncertainty since
a finite intensity of Mn spectrum is observed in (u).

CORROSION—Vol. 69, No. 9 931

CORROSION SCIENCE SECTION

(a) (b)
Figure 11. Extensive pitting failure (a) and inside the Type 316L pipe connection (b) between syngas cooler and cleanup
unit of IAE IGCC pilot plant where industrial wastes are intermittently processed: the spot was exposed to temperature
range between 40°C and 60°C.

(a) (b)

(c) (d)
Figure 12. (a) through (d) three-dimensional SEM profiles of W-shaped pits of Figure 10(a) taken by appropriately tilting
samples at different angles.

Extensive pitting failure was visually observed as
shown in Figure 11. On the other hand, an example
of pits was visually observed in Figure 4(c) and the
three-dimensional shape of pit initiation is shown in
Figure 12. Figure 4(c) shows various pits of different
extents of progress. Although pitting failure is typi-
fied by a relatively small proportion of corroded piping
and is somewhat insidious, it could lead to sudden
and quite unpredictable disaster caused by leaking
syngas. Therefore, corrosion mechanism was inferred
again from SEM-EDS analysis of pitting initiation il-
lustrated in Figure 10(a), where the scanned cross

932 CORROSION—SEPTEMBER 2013


section was W-shaped and concave downward toward
the bottom of the paper. The W shape of the pit is also
further inferred from its three-dimensional profiles
shown in Figures 12(a) through (d), which were taken
by appropriately tilting samples at different angles.
Complete penetration of Type 316L stainless steel pip-
ing was observed after cumulative exposure time of
about 1 week, and the maximum pitting rate was cal-
culated using the equation:
pit depth (mm) × 365
Pit mm/y = (4)
exposure time in days
The result calculated is inordinately large
(>260 mm/y) and the Type 316L piping should be
replaced with more corrosion-resistant alloy piping.
Strong chlorine, manganese, and sulfur peaks
were observed along the marker line scanned across
the bright ring pattern in Figures 10(c), (d), and (e),
respectively. For reproducibility check, SEM-EDS
analysis of another pit (Figure 10[m]) of a different
extent of progress was similarly made in Figures 10(n)
through (w). Therefore, it is strongly inferred that for-
mation of chloride and sulfide is highly feasible. As for
the feasibility of metal dusting with carbides as reac-
tion intermediates, thermodynamic activity of (graph-
ite) carbon was again calculated using a commercial
thermochemical software with bulk concentration of
carbon as a basis. The carbon activity of 6.8×10–15 at
60°C thus calculated was too small to ensure any fea-
sibility of carbide intermediates and the metal dusting
mechanism is again completely excluded.
However, the dew point of the process stream cal-
culated by a commercial thermochemical software for
the industrial waste processing IGCC process stream
(CO: 46%, H2: 23%, CO2: 8%, N2: 17%, H2S: 300 ppm,
HCl: 7 ppm, H2O: 5%) is 74.15°C, which is higher
than the reaction temperature of 60°C for the Type
316L piping. It is well known that the acid dew point
of corrosion in furnaces, especially in air preheaters,
commonly occurs at bulk temperatures well above the
dew point and localized cold spots on the metal pip-
ing can create surface temperatures much lower than
the bulk temperature, resulting in the condensation
of corrosive liquids. Since actually measured internal
tubing temperature varied from 40°C to 60°C, the po-
tential for dew point corrosion of internal tubing was
based on actually monitored bulk process tempera-
ture of flowing syngas stream.
In view of these, dew point corrosion by aqueous
HCl condensate is a strong possibility while metal
dusting is completely excluded. From the definition of
the dew point it is inferred that wet corrosion mecha-
nisms occur when stainless steel is exposed to con-
densed vapor. The electrochemical reactions are the
same as for wet corrosion.21 For aqueous condensate
systems containing HCl, such as encountered in the
present research, metal dissolution takes place and
CORROSION—Vol. 69, No. 9
CORROSION SCIENCE SECTION
hydrogen evolution controls the cathodic reaction
rate.21
According to a dew point corrosion mechanism
suggested by Kivisäkk,5 HCl in contact with air could
decompose to water and chlorine gas, which occurs
at temperatures below 600°C, and the driving force
increases with decreasing temperature. Although the
corrosive environment of condensate encountered
in the present research at 60°C cannot be deduced
quantitatively, the 1% HCl concentration obtained by
Kivisäkk5 for flue gas with 300 ppm to 400 ppm HCl
(condensing at 40°C), it is quite likely that less than
1% HCl concentration was present in the condensate
of the present environment. However, Kivisäkk5 also
observed a significant corrosion rate of ≈3.21 mm/y
for Type 304L samples located in the inlet of the heat
exchanger, which strongly implied effect of specimen
exposure condition on the observed corrosion behav-
ior of pitting failure.
It is well known that MnS inclusion plays a role
of initiation site for pitting corrosion,21 and the con-
centric ring structure of Figure 10(a) observed in the
corroded area was analyzed further by EDS as shown
in Figures 10(c) through (e). Also, pitting corrosion
mechanism should be modified to consider a thin
layer of condensate, where pitting progresses prefer-
entially in the horizontal direction,21 unlike a deep-
type pit formed in the bulk chloride solutions. This
difference of pit morphology is attributed to differ-
ences in the mass transport and effective cathode
area.21 To clarify the distribution of MnS on the cor-
roded stainless steel surface, an EDS scan was per-
formed and the observed EDS spectra of Figures 10(d)
and (e) revealed almost similar intensity level peaks
of Mn and S, which strongly indicated feasibility of
MnS inclusion across the corroded area. The MnS
most probably could have dissolved by catalyzation
of chloride ions following the similar arguments dis-
cussed in the “Corroded Piping Sample from Coal
Syngas Integrated Gasification Combined Cycle Plant”
section. EDS analysis of the pit was made in duplicate
to corroborate aforementioned arguments, and the
result is comprehensively presented in Figures 10(m)
through (w), where line scanning results are individu-
ally or collectively identified as legends in Figures
10(b) and (m).
Figures 10(q), (r), and (u) also corroborate the
arguments on MnS inclusion as a probable pit initia-
tion site.
In view of these, pitting corrosion mechanism of
the Type 316L piping under condensate is suggested
following Tsutsumi, et al.21 MnS dissolved first by the
reaction:
2MnS + 3H2 O → 2Mn 2 + + S 2 O 2– +
3 + 6H + 8e
–
(5)
This reaction decreases pH in the vicinity of the
MnS inclusion on the corroding surface, which initi-
933
CORROSION SCIENCE SECTION
ated dissolution of constituent metals, Fe, Ni, and
Cr. The pH is further lowered by the hydrolysis reac-
tions of:
Fe 2 + + 2H2 O → Fe(OH
OH)2 + 2H +
e( OH) (6)
Ni 2 + + 2H2 O → Ni(OH
OH)2 + 2H +
i( OH) (7)
Cr 3 + + 3H2 O → Cr(OH
OH)3 + 3H +
r(OH) (8)
The metal ions migrate and diffuse outward
through the thin water layer, lowering pH of the sur-
roundings by the hydrolysis reactions, which further
increased the corroded area. Pitting corrosion under
a droplet progresses laterally since low-pH regions
are more widely formed around a pit, compared to
pitting corrosion in the bulk solution. Besides, the
solution over the corroded area is immediately satu-
rated with the dissolved metal ions because of an ex-
tremely limited amount of solution. The saturation
may reduce the dissolution rate in the center of the
corroded area, which could explain the W-shaped
cross section in Figure 10(a). Since the metal ions do
not saturate yet at a circumference of the corroded
area and the circumference is closer to the cathode,
the metals dissolve at a higher rate, leading to the
preferential growth of pitting corrosion in the horizon-
tal direction.21
Corrosion Mechanisms
Uniform Material Loss on the Piping Sample of Coal
Syngas Integrated Coal Gasification Combined Cycle
Plant — Under the predominantly reducing environ-
ment encountered, oxide phases could be discontinu-
ous and metal chlorides could form directly on the
metal surface:
M(s) + Cl 2 (g ) → MCl 2 (s) (9)
and M is Fe, Cr, or Ni. The formation of metal chloride
could be strongly favored at the oxide/metal interface
where partial pressure of oxygen could become very
low. The metal chloride is subsequently transformed
to oxides, following the arguments of Asteman and
Spiegel.4
Besides, it is strongly inferred that the MnS in-
clusion dissolved by catalyzation reaction of chloride
ion:21
2MnS + 3H2 O + 2Cl – → 2MnCl + + S 2 O2– +
3 + 6H + 8e (10)
which could further accelerate corrosion of the piping.
Pitting Failure of the Piping Sample from Industrial
Waste Processing Integrated Coal Gasification Com-
bined Cycle Plant — Extensive pitting by condensation
of acids accounts for most of the corrosion failures,
where metal dissolution takes place and hydrogen
evolution controls the cathodic reaction rate.21
934
MnS inclusion plays a role of initiation site for
pitting corrosion21 and MnS dissolved under acid con-
densate by the reaction:
2MnS + 3H2 O → 2Mn 2 + + S 2 O 2– +
3 + 6H + 8e
–
(11)
The pH is lowered further by the hydrolysis reac-
tions of:
Me 2 + + 2H2 O → Me(OH
OH)2 + 2H +
e( OH) (12)
where Me represents either Fe, Ni, or Cr.
Pitting under a droplet progressed laterally be-
cause of the widely formed low-pH region around a
pit. The condensate over the corroded area is immedi-
ately saturated with the dissolved metal ions, owing to
the extremely limited amount of solution. The satura-
tion could reduce the dissolution rate in the center of
the corroded area, which could lead to the W-shaped
cross section.
conclusIons
❖ Corrosion behavior of Type 316L stainless steel pip-
ing used in IGCC plant facilities processing coal and
industrial waste was explained using SEM/EDS, and
relevant corrosion mechanism was suggested based
on SEM/EDS examination and thermodynamic calcu-
lations. The observed material wastage and corrosion
behavior of the Type 316L piping material cut off from
the coal syngas IGCC plant were explained by com-
bined effects of evaporation of iron chlorides and sub-
sequent transformation into thin oxides. On the other
hand, the pitting corrosion phenomenon observed on
the inner wall of Type 316L piping cut off from indus-
trial waste processing IGCC plant was attributed to
modified pitting mechanism caused by the preferential
growth of pitting corrosion in the horizontal direction
under an aqueous condensate environment contain-
ing HCl.
❖ Type 316L stainless steel with nominally 2.0% mo-
lybdenum offered less than marginal resistance to the
ordinary IGCC environments. Attempts to use Type
316L stainless steel were mostly unsuccessful, and
pH and acid condensate must be limited and closely
controlled to avoid pitting corrosion.
AcKnoWlEdGmEnts
This work was supported by the Energy Efficiency
& Resources Program of the Korea Institute of Energy
Technology Evaluation and Planning (KETEP) grant
funded by the Korea Government Ministry of Knowl-
edge Economy (no. 2008-C-CD11-P-05-0-000). Y.-B.
Kang (Pohang University of Science and Technol-
ogy, Pohang, Korea), J. Park, and B. Kim (of IAE and
Yonsei University, Korea, respectively) are gratefully
acknowledged for their experimental and editorial
CORROSION—SEPTEMBER 2013

assistance. Last, but not least, thanks are due to re-
viewers for helpful comments and suggestions.
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