Corrosion of Stainless Steel in High Solids Black Liquor

Margaret Gorog
Metallurgical Engineer
Weyerhaeuser
Federal Way, WA 98063-9777

ABSTRACT

Austenitic stainless steels are typically used for heavy black liquor service containing at least 68% solids. Reports in
the literature describe corrosion and cracking of these stainless steels. This paper covers specific mill experiences
and confirms the result that 304L has improved corrosion resistance over 316L. 304L is sufficient in most
applications, even up to 80% solids. Where it has not performed well, 2205 duplex stainless steel has been used in
its place. The use of 316L has resulted in catastrophic failures that could have seriously injured mill personnel.
Equipment affected includes concentrator tubes, piping and tanks. Though corrosion is the cause of thinning, all the
failures are affected by turbulence and high flow rates. Cold work from bending or cutting has been a factor in some
of the failures involving cracking.

BACKGROUND

At the 1996 TAPPI Engineering Conference, one paper(1) presented experimental results indicating that at high
enough concentrations, sodium hydroxide causes grain boundary corrosion of austenitic stainless steel in heavy
black liquor. At the time this type of liquor typically had a solids content between 65 and 70%. It was noted that this
definition was changing as mills were pushing black liquor evaporation upwards to 80% solids which demanded an
increase in the liquor temperature. This was expected to lead to higher corrosion rates. Other conclusions stated that
there was no gain by alloying stainless steel with molybdenum. Chromium on the other hand had a positive effect on
improving corrosion resistance.

In 2001, three papers (2, 3, 4) were presented at the 10
th
International Symposium on Pulp and Paper Industry
Corrosion Problems. They identified alkali content and temperature as the cause of corrosion. Other important
information presented was the improved corrosion resistance of 304L (nominal 18% Cr, 8% Ni) over 316L (nominal
16% Cr, 10% Ni, 2% Mo). 304L however was subject to stress corrosion cracking. 2205 (nominal 22% Cr, 5% Ni,
3% Mo) duplex stainless steel has even lower corrosion rates than 304L. To raise awareness of heavy black liquor
corrosion to pulp mills in North America, TAPPI published a journal article(5) summarizing the earlier
Scandinavian research. At the 11
th
ISPPICP, it was concluded that the degradation of lignin at higher solids and
temperature releases sulfurous gases that increase the risk for stress corrosion cracking of austenitic stainless
steel(6). It also confirmed once again that 316L does poorly in high solids black liquor(7).

Weyerhaeuser began experiencing occasional failures of stainless steel in high solids liquor by the late 1990s. The
damage had the appearance of erosion corrosion. The failures were occurring in liquors with a nominal
concentration of 70 -73% solids. The catastrophic rupture of six year old 316L piping in 2000 was an unexpected
introduction to high solids corrosion. The estimated corrosion rate was 20 mils per year. Since that time there have
been numerous failures of stainless steel. This paper gives examples of these failures. The resulting investigations
offer findings that can be used to deal with this type of corrosion.

MILL EXPERIENCES INVOLVING HIGH SOLIDS BLACK LIQUOR CORROSION

Piping

The first example involves piping associated with a high solids concentrator that started up in 1994. 316L was a
major material of construction for the piping in this system. This was not the first failure but demonstrates the
importance of stainless steel composition. The nominal solids concentration is 73% and temperature 230 F. A
thick, 316 stainless steel suction reducer leaked after nine years where the base material thinned to a hole. An
adjacent area is show in Figure 1. The interior surface appears to be polished. Initially erosion was thought to be the
thinning mechanism however SEM examination of the ID revealed intergranular attack as seen in Figure 2. This was
indicative of corrosion. It was in an area of higher flow so there was some element of erosion combined with
corrosion. The weld between the pipe sections had not thinned to the same degree. This is another sign that
corrosion was driving the failure. The chemistry of the plate and welds in the area of thinning is presented in Table I.
It shows that most thinning occurs where the chromium is less than 18%. The thinnest plate most closely matches
316L. The parts that matched 304L did not thin. All failed piping in the concentrator area has been replaced with
304L. There have not been any repeat failures since 2003.

Table 1 Chemistry comparison of various pipe segments. The thinned pipe matches 316L stainless steel.
















The next two examples involve high solids concentrator (HSC) recirculation piping. The failure mechanism was
catastrophic rupture due to thinning. The first came from a system that concentrates black liquor to 70% solids. The
line that failed had been in service for two years. Figure 3 shows the ruptured section and Figure 4, a view of the
internal surface. The pipe ID is grooved suggesting erosion. However the weld stands proud of the pipe indicating
that corrosion is also occurring. Figure 5 shows a Scanning Electron Microscope (SEM) micrograph of the damaged
surface. The pipe on each side of the weld reveals intergranular attack confirming the corrosion mechanism. Energy
Dispersive X-ray (EDX) semi-quantitative results are listed in Table II. It shows that the pipe alloying matches 316L
stainless steel. The weld, which was more corrosion resistant than the adjacent pipe had the highest concentration of
chromium. It also had the highest concentration of molybdenum which did not affect corrosion performance.

Table II Chemistry of 70% black liquor solids piping as determined using EDX. The closest match is 316L.

% Element Thicker Pipe Weld Matrix Ruptured Pipe
Chromium 18.3 19.61 17.1
Nickel 12.65 11.22 9.67
Molybdenum 2.22 2.31 1.97

The next example involves the failure of a section of 80% solids piping. The failed section was a smaller piece that
was spliced into a horizontal run downstream from a ball valve that was frozen in the open position and upstream
from an elbow. There were no records indicating when and why it had been installed. It may have been a
replacement for earlier corrosion. 304L was specified for the original piping. Figure 6 shows the remnants of the
ruptured pipe. Though no one was hurt, its obvious that this was a serious safety incident. The ID surface is
polished smooth with the appearance of erosion. It thinned to about 10 mils before failing next to a weld.

There is poor fit-up and incomplete weld penetration with the result that the joint of the thicker pipe was offset from
the section that thinned. There was no apparent erosion of this edge, as shown in Figure 7. Figure 8 is a series of
SEM micrographs showing areas on both sides of the weld. The metal next to the rupture site displays intergranular
corrosion, similar to the failures already discussed. The adjacent piping which visually does not appear to be
corroding also shows signs of chemical attack when magnified. EDX results listed in Table III show the ruptured
pipe is a close match to 316L stainless steel. The thicker pipe matches 304L. Though there may be flow effects,
corrosion is the primary mechanism. It is even affecting 304L. The failure probably occurred near a weld because it
created localized turbulence that enhanced corrosion.
Chemistry thick reducer to thinned thick
Element reducer side pipe weld pipe pipe weld
Carbon, C% 0.027 0.022 0.002 0.031
Manganese, Mn% 1.94 1.81 1.8 1.21
Sulfur, S% 0.01 0.016 0.006 0.013
Silicon, Si% 0.43 0.47 0.47 0.58
Nickel, Ni% 8.23 11 10.5 10.4
Chromium, Cr% 18.1 17.9 17 19.1
Phosphorus, P% 0.023 0.019 0.027 0.017
Copper, Cu% 0.23 0.11 0.27 0.11
Molybdenum, Mo% 0.33 2.13 2.36 0.93
Closest match 304L 316L 316L 304
Table III EDX chemistry of 80% black liquor solids piping.

% Element Thicker Pipe Weld Matrix Ruptured Pipe
Chromium 19.37 18.87 17.84
Nickel 7.92 11.13 10.09
Molybdenum 0.53 1.63 1.84

Stress corrosion cracking, SCC, is also an issue for piping. Figure 9 shows an example of SCC of 316L long radius
5D bends in 73% liquor. This system was periodically steam cleaned to remove thick deposits. It appears that sulfur
plays a role in the cracking as it was one of the major elements in the deposit as identified by the EDX scan in
Figure 10. Chlorides were not detectable.

The pipe hardness is Rockwell C 35. In the annealed condition it is typically softer, in the upper Rockwell B range.
There is a variation in thickness around the circumference resulting in raised bands of material. This is not a result of
corrosion but cold work introduced during bending. Figures 12 14 show a variety of cracks observed on the inner
surface. Physical marks such as the bands, scratches or punches were often initiation sites for cracking. Figure 14 is
a micrograph showing branched cracking typical of SCC. At higher magnifications, the cracks are primarily
transgranular. Individual grains of austenite are filled with parallel deformation lines indicating severe cold work.
This piping was replaced with 304L that was fully solution annealed before going into service.

Concentrator Tube

304L concentrator tubes also experience corrosion and cracking. The time to failure has been from six months to
about ten years. Solids concentration varies but all are at least 70%. 2205 has been the replacement material for the
tubes that failed rapidly. So far, the service life has exceeded four years. The longer term failures have been replaced
in kind.

The examples here show several types of degradation. Some tubes are filled with spiral bars called enhancers or
turbulators. Their purpose is to increase the turbulence in the tube. The bars were made out of 316L. They rapidly
cracked and fell out of the tubes. The mills that have not replaced the enhancers have not seen a change in
concentrator performance. Figure 15 shows a cracked enhancer. SCC initiated along the sheared edge of the bar.
This is another example of cold work providing the stress component for initiating SCC. Additionally the tube
cracked along a diagonal line that followed the path of the enhancer. This is shown in Figure 16. Figure 17 is a
close-up photograph revealing fine branched cracking. Figure 18 is a micrograph showing that crack initiation
occurred on the OD. This is the steam side but there were reports of black liquor contamination due to carryover.
The ID is corroding. Figure 19 shows fine pitting. Figure 20 shows a diagonal line that marks where the enhancer
rested against the tube wall. It is actually a raised line of material. The stainless steel has thinned all around it.
Figure 21 in cross section shows this step. The smooth surface of the tube ID was examined with the SEM and again
the intergranular effect is seen in Figure 22.

The other example is from a concentrator in which the liquor flows on the outside of the tube elements. The liquor
solids are 71%. 304L tubes are joined to 2205 headers. At the location of greatest splashing 304L had thinned to
failure. Turbulence was a major influence on corrosion. The 2205 tubes shown in Figure 23 have etched welds.
Though there is some chemical effect no measurable thinning was detected. The replacement material for 304L was
2205.

Tank

The last example is a product liquor flash tank at 70% solids. The liquor enters a tank via a tangential nozzle and hits
one section of the wall. Figure 24 shows the damaged plate where it was affected by liquor impingement. The area
had been covered with an additional 304L wear plate which was perforated. The shell had corroded to the point of
needing replacement. Similar to the other failures, the surface is shiny and polished with telltale intergranular
corrosion visible with the SEM (not shown). The corroded area was replaced with 2205 along with a 2205 wear
plate. Two years later a small area of this plate has lost half its thickness. The discoloration noted in Figure 25 is the
location of the thin section where the liquor splashes against the wall.
DISCUSSION

Stainless steel failures continue to occur in high solids black liquor service. The perception is that more failures will
occur as the solids concentration approach 80% however the experience is that corrosion is possible in heavy black
liquor at all solids concentrations of at least 70%. The failures can be rapid, on the order of weeks or months, and
catastrophic. Piping, concentrator tubes and tanks were provided as examples but other affected equipment not
discussed in detail here includes nozzles, meters and cast parts in ball valves. Table IV provides a larger sampling of
failures in high solids black liquor.

Most of the failures involve 316L. Though there is widespread knowledge that this material is not suitable for high
solids black liquor service, it is often selected for spur of the moment repairs. 304L has done well except in high
velocity, turbulent or splashing situations. It thins but not at the same rate and certainly provides much better service
than 316L. The one exception is CF8M, the cast equivalent of 316, for the body of ball valves. They are in
widespread use largely because of the expense of upgrading to a cast duplex. This is a situation where the inspection
frequency must be stepped up in anticipation of failure, with plans for more frequent change outs. Stellite liners have
improved the longevity of the valves making this an acceptable approach.

The upgrade for 304L has been 2205 and in all cases it has been an improvement though it is not immune to
corrosion. Lean duplex stainless steels such as 2101, 2304 or 2003 have been recommended as alternates to 2205,
however they are not readily available. Corrosion testing indicates they will do well in alkaline liquors(8). For any
stainless steel, austenitic or duplex, a corrosion allowance should be considered for use in high solids black liquor
service.

In all cases involving thinning, there is a flow affect from high velocity or turbulence. The failure mechanism
visually appears to be erosion corrosion. Metallographic examination shows that the metal is indeed corroding. Flow
assisted corrosion may be a better term describing the wastage. Turbulent liquor prevents passivity by continuously
removing oxides and exposing fresh metal to the corrosive environment.

Intergranular corrosion suggests that sodium hydroxide is a cause. In order to better understand the corrosion
mechanism, data from in-house liquor testing has been analyzed to determine specific corrodents. There is a
tendency for those mills that experience corrosion to have a higher sodium hydroxide concentration compared to
other mills without high solids failures. The mills having reported the most corrosion have made additions of caustic
to the black liquor. In one case caustic was added to neutralize acidic saltcake coming from the chlorine dioxide R8
process. In another case, alkali residuals were kept high to control digester corrosion. In both cases, adjustments to
caustic levels appeared to reduce corrosion, however at the same time material changes were made that also
improved equipment performance

Chlorides are variable. Some failures involve high chlorides relative to other mills that have low chlorides. The
affect of sulfur is difficult to assess but it may play a role in stress corrosion cracking as it was detected at high
levels in the deposits on cracked piping. Regardless of liquor chemistry, material selection has been the most
important factor in controlling corrosion.

CONCLUSIONS

Corrosion of stainless steel occurs in black liquor with as low as 70% solids.
The failure mechanism can be described as flow assisted corrosion. Design changes to reduce the flow affects
will reduce or eliminate corrosion.
Reducing stresses and deposition will improve resistance to stress corrosion cracking.
At least 18% chromium is required for corrosion resistance. Molybdenum is not a significant factor.
304L is sufficient for most applications. Duplex stainless steels are more resistant though not immune to
corrosion in high flow conditions.
Stainless steel in high solids black liquor service needs to be inspected for thinning and cracking on a regular
basis.

Table IV Summary of stainless steel corrosion failures in high solids black liquor

Equipment Failure Mode Material Comments
Liquor solids meter corrosion 316L All corrosion is assisted by flow
Thin walled pulled Tee -
HSC piping
corrosion 316L Catastrophic rupture. The failure occurred approx. six
years after startup. The estimated corrosion rate is 20
mils per year.
Manual Ball Valve corrosion CF8M The 316 cast equivalent valve body failed after 6 years.
It was replaced in kind with an additional stellite lining.
The replacement has been in service for 6 years.
Liquor heater corrosion 316L/304L Failures occurred on the order of weeks. The nozzle
design was changed to reduce flow and now 304L is
satisfactory.
HSC piping corrosion 316 Carbon steel installed in Oct 02 failed within 2 years. It
was replaced with 316L with some sections failing in
less than 12 months. Pipe thinning led to rupture in the
most recent failure in spring 06.
Suction reducer - HSC
piping
corrosion 316 The pipe leaked. There have been other instances of
piping thinning including some 304L
HSC tubes/enhancers corr/cracking 304/316 304 tubes have thinned over 10 years. 304 is the
replacement material. Enhancers cracked and fell out
some years after startup. They were never replaced.
Concentrator tubes/
Enhancers
cracking 304/316 The enhancers are made out of 316. The tubes cracked
after 6 months. Thermal expansion issues contributed to
the failure. 2205 is the tube replacement material.
Tube element concentrator
tubes
corrosion 304 The failures occurred 2 years after startup. 2205 is the
replacement material. This has occurred at another
location resulting also in an upgrade to 2205. The
duplex stainless steel is performing well
Concentrator tubes/
Enhancers
cracking 304/316 Cracking occurred after 7 months. The new tubes are
made out of 2205.
Reducer cracking/corr 316L The pipe leaked after 6 - 8 months. 304L is the
replacement material.
Product Liquor Flash Tank corrosion 304L Corrosion occurred next to a tangential nozzle. The
thinned section was replaced with 2205 stainless steel
which is now thinning in a small area about 8 square.
HSC recirculation piping corrosion 316L Catastrophic rupture safety incident
REFERENCES

1. Klarin, Anja, Kottila, Mika, Caustic Corrosion in Black Liquor Evaporators, proceedings from the 1996
Engineering Conference, TAPPI.
2. Klarin, Anja, Corrosion Phenomena in Black Liquor Evaporators, Proceedings from the 10
th
International
Symposium on Corrosion in the Pulp and Paper Industry, Helsinki, 2001.
3.Kottilla, Mika, Rauscher, J ohn, Selecting the Proper Material for Black Liquor Concentrators, Proceedings from
the 10
th
International Symposium on Corrosion in the Pulp and Paper Industry, Helsinki, 2001.
4.Andreasson, Pernilla, Corrosion Problems with Stainless Steels in Evaporator Plants Proceedings from the 10
th

International Symposium on Corrosion in the Pulp and Paper Industry, Helsinki, 2001.
5. Bennett, Dave, Reid, Craig, Corrosion of Stainless Steel in High Solids Black Liquor Service, September 2002
Solutions, TAPPI.
6. Klarin-Henricson, Anja, Corrosivity of Black Liquor from a Modern Digester to A High Dry Solids
Concentrator, Proceedings from the 11
th
International Symposium on Corrosion in the Pulp and Paper Industry,
Charleston, SC, 2004.
7. Troselius, Lars, Corrosion in Evaporator Plants and Heavy Black Liquor Tanks, Proceedings from the 11
th

International Symposium on Corrosion in the Pulp and Paper Industry, Charleston, SC, 2004.
8. Singh, Preet, Institute of Paper Science and Technology at Georgia Tech, IPST report, 2006.









Figure 1: 72% solids, 1/4 316L stainless steel suction piping leaked after 9 years of service. The weld has not lost
any thickness. The surface appears to have been polished.







Figure 2: An SEM micrograph reveals intergranular corrosion.




Figure 3: Ruptured 70% heavy black liquor line.





Figure 4: A close-up of the rupture site shows grooving. The weld has not corroded to the same degree as the pipe.




Figure 5: The pipe matches the chemistry of 316L. The right SEM micrograph represents the pipe on the thinner
side of the weld. The left SEM micrograph is near the rupture on the thicker side. Both sides show intergranular
corrosion, a sign of caustic attack.









Figure 6: Catastrophic rupture of an 80% solids recirculation line from the concentrator to the flash tank

thinner 316L thicker 316L



Figure 7: The stainless steel thinned to 0.010 before failing. Note the step at the butt weld indicating poor fit-up
and incomplete penetration.






Figure 8: The ruptured pipe matches the chemistry of 316L. The right SEM micrograph displaying some
intergranular attack is from an area next to the perforation. The pipe on the other side of the weld matches 304L. The
left SEM micrograph shows that this side is also corroding.

316L 304L



Figure 9: Cracked long radius bends. The ID is coated with a thick, uniform deposit.











Figure 10: An EDX scan shows the deposit contains sodium, oxygen and sulfur. Chlorides are not present at
detectable levels.




Figure 11: Extensive ID cracking was observed once the deposits were removed. There was no thinning of the pipe.






Figure 12: Cold working during bending created raised bands of metal. This photograph shows a crack running
across one of these bands.

R Ra ai is se ed db ba an nd d



Figure 13: Many crack patterns were observed. This is an example of star cracking that initiated at what appeared to
be punch marks.











Figure 14: Metallography shows branched stress corrosion cracking. The cracking is primarily transgranular.
Parallel deformation bands within austenite grains indicate severe cold work.

50X 500X



Figure 15: The 316L spiral enhancer bar inside the concentrator tube has cracked. The tube material is 304L.

















Figure 16: External cracks of a concentrator tube follow a diagonal line where the enhancer rested against the tube
ID.




Figure 17: Fine stress corrosion cracking is seen on the tube OD









Figure 18: Stress corrosion cracking initiates from the OD.

46X



Figure 19: Concentrator tubes also corrode. Here is an example of fine pitting.










Figure 20: The entire surface has thinned leaving a raised diagonal line where the enhancer rested against the ID,
offering some protection against corrosion.




Figure 21: A metallographic cross section shows the ledge that formed under the enhancer.










Figure 22: An SEM micrograph of the corroded tube shows intergranular corrosion.

92X



Figure 23: 2205 duplex stainless steel tubes have etched welds.





Figure 24: The wear plate of a 304L liquor tank thinned and perforated due to liquor impingement.




Figure 25: The replacement wear plate made out of 2205 is also thinning as seen by the discoloration where the
liquor hits the tank wall.

Corrosion of Stainless Steel in High
Solids Black Liquor
Margaret Gorog
TAPPI Engineering Conference October 2007
Background
Published experimental results
NaOH causes grain boundary corrosion.
Chromium improves corrosion resistance.
No gain with molybdenum.
304L is more resistant than 316L
Releases of sulfurous gases increase the risk of
SCC
316L stainless steel piping, thick, leaked
after 9 years of service. The weld is intact.
73% Suction Reducer
Notice the
intergranular
etching.
Thinning is caused
by corrosion.
73% Suction Reducer
50X
200X
Comparing stainless steel compositions
reducer to piper weld
thin pipe
thick pipe weld
73% Suction Reducer
316L equivalents thinned
corroded some attack
73% Suction Reducer
Chemistry thick reducer to thinned thick
Element reducer side pipe weld pipe pipe weld
Carbon, C% 0.027 0.022 0.002 0.031
Manganese, Mn% 1.94 1.81 1.8 1.21
Sulfur, S% 0.01 0.016 0.006 0.013
Silicon, Si% 0.43 0.47 0.47 0.58
Nickel, Ni% 8.23 11 10.5 10.4
Chromium, Cr% 18.1 17.9 17 19.1
Phosphorus, P% 0.023 0.019 0.027 0.017
Copper, Cu% 0.23 0.11 0.27 0.11
Molybdenum, Mo% 0.33 2.13 2.36 0.93
closest match 304L 316L 316L 304
Details of the rupture site
0.140 0.075 0.015 0.330
0.275 0.015 0.365
70% Recirculation Line
SEM examination of the ID reveals
intergranular corrosion
Thicker Ruptured
70% Recirculation Line
316 Fingerprint
Note the chromium content
1.97 2.31 2.22 Molybdenum
9.67 11.22 12.65 Nickel
17.10 19.61 18.30 Chromium
Ruptured Weld Thicker % Element
70% Recirculation Line
80% Recirculation Line
Remnants of a catastrophic rupture
Note the step at the butt weld
80% Recirculation Line
Intergranular corrosion
near the rupture
Corrosion of 304
pipe
316 304
80% Recirculation Line
1.84 1.63 0.53 Molybdenum
10.09 11.13 7.92 Nickel
17.84 18.87 19.37 Chromium
Ruptured Weld Thicker % Element
Note the chromium content
304 Fingerprint
80% Recirculation Line
6 316L piping, 6 years old
240 - 270 F
Periodically cleaned with
400 F steam
5D bends crack
Some pump vibration
73%, High Solids Concentrator Piping
A thick deposit coats the ID of the cracked pipe
73%, High Solids Concentrator Piping
The deposit contains mainly
sodium, oxygen and sulfur.
73%, High Solids Concentrator Piping
73%, High Solids Concentrator Piping
Wall grooving creates a variation in thickness
Average hardness is Rockwell C33.6
Pipe 1 Pipe 2 Pipe 3 Pipe 4
No. (in) (in) (in) (in)
1 0.213 0.155 0.259 0.256
2 0.202 0.146 0.224 0.197
3 0.228 0.165 0.228 0.209
4 0.169 0.171 0.196 0.197
5 0.166 0.154 0.195 0.170
6 0.158 0.175 0.185 0.203
7 0.144 0.150 0.175 0.158
8 0.147 0.133 0.154 0.162
9 0.144 0.139 0.161 0.165
10 0.155 0.130 0.192 0.174
11 0.165 0.134 0.185 0.199
12 0.169 0.130 0.194 0.180
After cleaning cracking is readily observed
Grooving and raised forming bands indicate
severe cold work
73%, High Solids Concentrator Piping
Cold work
deformation
bands
500X
50X
Stress Corrosion
Cracking
73%, High Solids Concentrator Piping
Examples of enhancer cracking, tube OD
cracking, ID pitting, and ID thinning.
70%, Concentrator Tube Corrosion and Cracking
The material is 316L
Metal spirals
enhance liquor
turbulence
Enhancer Cracking
Stress corrosion cracking
184X
Enhancer Cracking
Diagonal cracking follows the enhancer line
Concentrator Tube Cracking
A close-up shows branched cracking on the OD
Concentrator Tube Cracking
SCC initiates from the OD
Concentrator Tube Cracking
46X
ID pitting
Concentrator Tube Pitting
A thin section of the tube collapsed upon removal
Concentrator Tube Thinning
A diagonal line formed under the enhancer
spiral as tube metal next to it thinned.
Concentrator Tube Thinning
Corrosion next
to the turbulator
bar
The metal
under the bar is
protected from
corrosion.
92X
Concentrator Tube Thinning
Intergranular
corrosion
caustic attack
304L tubes are
corroding from
the ID
Concentrator Tube Thinning
Weld etching
71%, Tube Element Concentrator
70% Flash Tank
Thinning due to liquor impingement
Original plate Intergranular corrosion
70% Flash Tank
1000X
Wear plate Intergranular corrosion
70% Flash Tank
500X
70% Flash Tank
Thinning of 2205 duplex stainless steel
%Solids 70 80; Temperature > 230 F;
All flow related
Summary
Equipment Failure Mode Metal Fix
Product liquor flash tank Corrosion 304L 2205
BL heater pipe reducer Corr/Cracking 316L 304L
Ring header piping Corrosion 316L 2205
HSC tubes Corr/Cracking 304L 304L/2205
HSC spiral enhancers Cracking 316L Removed
Element concentrator tube Corrosion 304L 2205
Liquor Heater Corrosion 316L/304L 304L/design
HSC valves (cast) Corrosion CF8M CF8M
HSC piping Corr/Cracking 316L/304L 304L
Liquor Solids Meter Corrosion 316L Alloy 20
Discussion
Stainless steel failures continue to occur in
high solids black liquor service
Every failure has occurred in a region of high
velocity or turbulence.
Sodium hydroxide concentration in the liquor
is consistently high.
Stress corrosion cracking is also an issue.
Discussion continued
316L is not recommended for HSBL service
304L is suitable for applications that dont
involve high velocities, splashing and
turbulence
2205, 2304, 2101 duplex stainless steels have
improved resistance but are more expensive
and less available.
Consider a corrosion allowance for 304L and
even 2205.
Conclusions
Stainless steel corrosion occurs in black
liquor with as low as 70% solids.
The failure mechanism is flow assisted
corrosion.
Reducing stresses and deposition will improve
resistance to stress corrosion cracking.
Conclusions Continued
At least 18% chromium is required for
corrosion resistance.
304L is sufficient for most applications.
Duplex stainless steels are more resistant
though not immune to corrosion in high flow
conditions.
Questions?