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Corrosion of evaporators

Conference Paper · September 2006

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

CORROSION OF EVAPORATORS
Angela Wensley Dave Christie
Angela Wensley Engineering Inc. Bacon Donaldson Consulting Engineers
15397 Columbia Avenue 12271 Horseshoe Way
White Rock, BC, Canada V4B 1K1 Richmond, BC, Canada V7A 4V4
awensley@uniserve.com dchristie@acuren.com

ABSTRACT
________________________________________________

The results of corrosion inspections of black liquor evaporators and concentrators are presented. Case histories
include examples of the apparent sudden onset of rapid corrosion thinning of carbon steel evaporator shells. It is
increasingly apparent that carbon steel is no longer an acceptable material for construction of evaporators handing
black liquors of intermediate and higher solids content. Carbon steel has unstable passivity in black liquors of
intermediate solids content and can suddenly shift from passive to active conditions, resulting in high rates of active
corrosion. Austenitic stainless steels can experience both internal and external corrosion problems. Use of duplex
stainless steels is increasing in attempts to solve corrosion problems.
________________________________________________

INTRODUCTION

In 1974, during the 1st International Symposium on Corrosion in the Pulp and Paper Industry held in Chicago, Lloyd
Clay commented on some serious corrosion failures of carbon steel liquor boxes, baffles, umbrella, and the vapor
body of 3rd-effect evaporators [1]. Over 30 years later, pulp and paper mills are still reporting similar problems of
rapid corrosion thinning of carbon steel components in multiple-effect evaporators. Are we slow learners or is it
possible that the slow yet inexorable trends to increased sulfidity, production rates, and temperatures may be causing
carbon steel to suddenly become an unsatisfactory material of construction after many years of satisfactory service
in black liquors of intermediate solids content? In addition, with the trend to higher solids concentration, even
stainless steels are having corrosion problems.

This paper presents the results of inspections in multiple-effect evaporators and concentrators. It reiterates the
unstable active/passive behaviour of carbon steel in liquors of intermediate solids content and also shows some cases
of corrosion of stainless steels.

Evaporator Design

There are numerous different designs of evaporators and concentrators [2]. The two main design types that are used
extensively are:

1. Rising film long tube vertical (LTV) evaporators.


2. Falling film (FF) evaporators.

Sketches of both designs are on the following page, although there are many variations on these themes. In a rising-
film evaporator, the vapor body is at the top, while in a falling film evaporator the vapour body is in the upper
chamber of the bottom of the unit. In rising-film evaporators, the liquor flows up the tubes, impinges on the
underside of a deflector (typically called the umbrella), and collects in a pool around the tubesheet where it is passed
into the bottom of the next effect, while the vapour is passed into the heater shell of the next effect. In falling-film
evaporators, the liquor falling though the tubes collects in a pool at the bottom of the evaporator for either
recirculation or transfer to the next effect. Evaporator materials of construction have to withstand wet vapour,
splashing liquor, and immersion.

Evaporator black liquors contain both inorganic and organic compounds and range from weak (<20% solids), to
intermediate (20% to 35% solids), to strong (36% to 60% solids), to heavy (61% to 85% solids). Rising film
evaporators can deliver up to 50% solids while falling film evaporators can deliver up to 65% solids. Concentrators
are forced circulation evaporators or evaporator/crystallizers that are used to concentrate the liquor up to 85% solids.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Vapor
Separator
Vapor Body Vapor
Heater

Steam Product
Steam Vapor
Liquor
Heater
Vapor Body
Condensate
Entrainment
Separator Condensate
Liquor
Product
Box
Liquor
Feed Liquor
Recirculation Feed Liquor
Falling Film Evaporator Rising Film Evaporator

LITERATURE SURVEY

For equipment critical to the operation of a kraft mill, it is surprising how little has been published on the inspection
of evaporators. There have been several studies of corrosion in alkaline pulping liquors, including black liquors.

Literature on Evaporator Inspection

The earliest references dealt with the corrosion of carbon steel and recommended stainless steel for those locations
and effects where carbon steel experienced high rates of corrosion or corrosion failures [3 – 5]. In 1950, von Essen
[3] observed that corrosion of carbon steel in evaporators appeared to increase with sulfidity and with higher
concentrations of solids. Lankenau published two comprehensive papers on inspection experience with evaporators
[4, 5]. His recommendations for the use of type 304 stainless steel (for example, the use of type 304 stainless steel
for the first two effects and below the liquid line in the third effect) were widely adopted. There were also early
reports of corrosion of the weld seams during acid cleaning of stainless steel evaporator tubing [6, 7]. Type 304
stainless steel tubes were also found to be susceptible to stress corrosion cracking (SCC) from the outside,
prompting a recommendation to change to type 310 stainless steel tubes [8].

In the 1960's, brief summaries of corrosion problems in evaporators were published by Bowers and Yeske [9, 10].
In 1991, the problem of external SCC (ESCC) of type 304L stainless steel evaporator heads was reported by
Danielson and Risebrough [11]. The ESCC was so severe that the heads of the first three effects had to be replaced.
The recommendations they made for preventing ESCC of austenitic stainless steel heads (shot peening, epoxy
phenolic coating, and removal of insulation from the critical location) are still valid today. In 1992, Willis and
Murray [12] reported the corrosion failures of the longitudinal weld seams in type 304L and type 316L stainless
steel evaporator piping. The NACE T-5H-14 task group on Black Liquor Corrosion (now NACE Technology
Exchange Group 131X) has been a good source of information on corrosion problems in evaporators, particularly
the March 1993 meeting [13].

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Corrosion Testing of Carbon Steel in Black Liquors

The early literature on corrosion in black liquors dealt principally with the corrosion of carbon steel in laboratory
cooks. MacLean and Gardner [14] published an extraordinary work on the effect of wood extractives on corrosion
of carbon steel in black liquors where they identified a family of organic compounds, catechols, as corrosive to steel
under conditions of alkaline pulping. Mueller [15] determined that carbon steel shows active/passive corrosion
behavior in liquors produced in laboratory cooks and that mixtures of white and black liquors could be more
corrosive than either liquor by itself. Tonsi-Eldakar and McGlynn [16] investigated the organic compounds found in
black liquors and confirmed that catechols increased the anodic corrosion rate of carbon steel. In 1992, Kannan et al
[17] published work on the preparation of synthetic black liquors for corrosion testing. Kelly et al [18] exposed
coupons of carbon steels in black liquor tanks, and found that corrosion increased with increasing sulfide
concentration. Wensley [19, 20] reported on corrosion tests in weak, intermediate, and strong black liquors where
corrosion rates in all liquors were found to increase with increasing sulfidity, increasing solids content and
increasing temperature of the liquor. Troselius [21] showed that the corrosion rate of carbon steel in both the liquor
and vapor phases increases with the percent solids of the liquor. Singh et al [22] investigated corrosion in a mill
black liquors concentrated in the laboratory to produce test liquors having different percent solids from 15% to 70%.
They confirmed that the corrosion rate of carbon steel increased with the percent solids and with temperature, as
well as with the sulfide and the hydroxide content of the liquor.

Corrosion Testing of Stainless Steel in Black Liquors

In 1980, the Tappi Corrosion and Materials Engineering Committee published the results of corrosion coupon
exposures in evaporators [23] that confirmed that stainless steels had excellent resistance to corrosion, particularly in
the first effect where carbon steel was unsuitable. Coupon test results published by Ström [24] reiterated the
excellent corrosion resistance of austenitic stainless steels in mill black liquors and further showed that duplex
stainless steels had even better corrosion resistance. Wensley demonstrated that sensitized type 304 and type 304L
stainless steels were susceptible to intergranular attack in digester black liquors [25], that the corrosion resistance of
stainless steel in digester black liquors increased with increasing chromium content of the stainless steel [26], and
confirmed that type 304L austenitic stainless steel and type 2205 duplex stainless steel had excellent corrosion
resistance in weak, intermediate, and strong black liquors [19, 20]. Klarin and Kottila [27] exposed stainless steels
in approximately 60% solids black liquors in the laboratory and found that the corrosion rates of several different
stainless steels increased with increasing NaOH concentration. They also observed intergranular corrosion of
stainless steels in black liquors.

Klarin [28] exposed stainless steels in mill concentrator systems of approximately 70% solids content and found that
corrosion resistance improved significantly with chromium content of the stainless steel. Kottila [29] reported on
corrosion coupon tests in concentrator liquors up to 85% solids and at temperatures as high as 175ºC. Type 2205
duplex stainless steel had better corrosion resistance than austenitic stainless steels such as types 316, 304, and 6%
Mo superaustenitic stainless steels. Andreasson [30] reported similar results, as did Troselius [21]. Singh et al [22]
showed that the corrosion rates of stainless steels increased with both percent solids and temperature. Duplex
stainless steels had superior corrosion resistance to austenitic stainless steels, particularly at higher temperatures.

SCC of Stainless Steel in Black Liquors

Recently, it has become apparent that process-side (liquid, vapor, and under-deposit) SCC can be a problem with
both type 304L and 316L stainless steels in high-solids concentrators [31 – 33]. There have been a number of
papers published on SCC testing in black liquors. Kottila [29] produced SCC of austenitic stainless steel U-bend
specimens after 2 weeks in 180ºC black liquor but a type 2205 duplex stainless steel U-bend showed no SCC.
Troselius [21] found that the SCC susceptibility of austenitic stainless steels increased with sulfidity in synthetic
liquors containing 30% NaOH at 150ºC. Singh et al [22] performed slow strain rate testing and was able to produce
SCC of type 304 stainless steel at 170ºC in mixtures of softwood black liquor and white liquor. Leinonen [34]
produced SCC of type 2205 duplex stainless steel at 170ºC in simulated batch cooking liquor that contained 180 g/L
Na2S and 40 g/L OH¯.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

INSPECTION RESULTS

Internal inspections of evaporators are usually done visually, although other nondestructive testing may also be
performed. Examples of inspection results are discussed below, subdivided into the following subject areas:

1. Evaporator vapor bodies


2. Evaporator vapor ducts and outlets
3. Evaporator recirculation top heads
4. Evaporator tubesheets
5. Evaporator bottoms
6. Evaporator heater shells
7. Thermal spray coatings
8. Concentrators
9. External corrosion

Corrosion in Evaporator Vapor Bodies

Carbon steel in the vapor bodies of rising film evaporators typically experiences general corrosion although the
corrosion may be nonuniform, producing a rough or pitted surface. The locations of the most severe corrosion in the
vapor bodies vary from mill to mill, even with the same-design evaporators. In some evaporators the corrosion is
most severe in the splash and immersion zones while in other evaporators the corrosion is more severe in the vapour
zone. Figures 1 – 5 are examples of severe corrosion of carbon steel components in the vapour bodies of 2nd, 3rd,
and 4th effect rising film evaporators. Figure 1 shows corrosion through the exterior of the heating element that has
exposed the tubes. Figure 2 shows a preheater box whose welds have corroded preferentially with the result that the
box came loose from the tubesheet. Figures 3 and 4 show advanced corrosion of a barometric leg and drain pipe,
respectively. Figure 5 shows severe corrosion of an umbrella support.

Galvanic corrosion is also a problem. Figure 6 shows corrosion up to 5 mm deep into the carbon steel adjacent to
the stainless steel lining around the bottom part of the vapour dome in a 3rd effect rising film evaporator. This
groove was filled using type 309L stainless steel weld metal, although this repair was not a permanent solution to
the galvanic corrosion problem. Galvanic corrosion of carbon steel adjacent to stainless steel has been observed in
all effects where this condition exists.

Figure 7 shows grooving of the shell of a 3rd effect platen type falling film evaporator that had progressed to the
point where action had to be taken after 10 years of service. The damage occurred at a cold finger created by an
uninsulated stiffener ring on the outside of the vessel. Shell damage was minimal above and below the cold finger.
Similar damage was seen in the 4th and 5th effects in the same evaporator train. Weld buildup repairs were done to
restore the affected areas and the location was subsequently coated with thermal spray. The thermal spray coating
has performed well over the past 3 years of service and no further grooving has occurred.

SCC of carbon steel is occasionally found in evaporators. Figure 8 shows SCC in a weld for a sight glass nozzle in a
4th effect evaporator in what appears to be a weld repair. The cracking has been monitored for the past three years
and shows no signs of progressing. Similar SCC has been found in other evaporators and has also been associated
with weld repairs. In each case the cracking appears to be static in nature and no repairs have been carried out.

Figures 9 and 10 show intense corrosion of the carbon steel shell at the elevation of the entrainment separator (mist
eliminator) in the vapor body of a 3rd effect falling film evaporator. Holes cut in the stainless steel support to
accommodate the weld caps on vertical weld seams in the evaporator body evidently created conditions for local
high flow velocities of the liquor-laden vapor. Two separate perforations of the wall occurred. In addition, there was
also galvanic corrosion grooving around the wall adjacent to the stainless steel support.

Corrosion in Evaporator Vapor Ducts and Outlets

Some rising film evaporators have vapor separators in the top of the vapor body. The floors and walls of the vapor
separator can experience severe thinning to the extent that they require re-plating using type 304L stainless steel.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 11 shows corrosion at the inlet door to the vapour separator in a 3rd-effect evaporator. Figure 12 shows a re-
plated vapour separator floor in a 2nd-effect evaporator.

The area just inside the opening to the vapour duct can experience corrosion under conditions of high turbulence.
The vapour duct outer wall at the duct opening in a 3rd effect evaporator has required ongoing repairs over a number
of years. In 2003, the upper head of the vessel including the vapour duct was replaced using stainless steel to
address ongoing corrosion problems in the carbon steel unit.

Vapour outlet piping is typically fabricated from relatively light, typically 6 mm (¼") thick, carbon steel pipe and is
subject to velocity enhanced corrosion by entrained liquor carried in the vapour flow. After 6 years of service, the
piping from a 1st effect evaporator required repairs to address heavy thinning around the fabricated mitered joints
(Figure 13). Two years later, additional damage had accumulated to the point that further repairs were required.
The outlet piping was replaced in stainless steel and no further problems have occurred to date. Other effects in the
evaporator train experienced similar corrosion but at a lesser rate that decreased with vapour temperature. In these
effects, repairs have consisted of carbon steel weld buildup of washed out welds at miter joints. In more problematic
areas, stainless steel liners have been installed as required.

Corrosion in Evaporator Recirculation Top Heads

In a falling film evaporator, a leak occurred behind a loose stainless steel liner installed for splash protection above
the tubesheet (Figure 14). Upon removal of the liner, the leak was found to have occurred at a galvanic corrosion
groove adjacent to the stainless steel fillet weld between the stainless steel tubesheet and the carbon steel wall
(Figure 15). Intermittent grooves were also observed in the carbon steel wall approximately 1 cm above the
stainless steel fillet weld (Figure 16). The grooves adjacent to the stainless steel tubesheet were filled using type
309L stainless steel weld metal. The higher elevation grooves were built up using carbon steel. An attempt was
made to seal weld the stainless steel liner plates to prevent liquor from gaining access behind.

Corrosion of Evaporator Tubesheets

Carbon steel tubesheets can experience severe corrosion (Figure 17). Galvanic corrosion of carbon steel tubesheets
adjacent to the stainless steel tubes is also sometimes observed (Figure 18).

It is common for tubesheets to be constructed using stainless-clad plate. The upper and lower tubesheets in a 1st-
effect evaporator experienced heavy corrosion of the stainless steel cladding over 30 years of service. The stainless
layer of the tubesheets was evidently sensitized since lightly brushing the surface dislodged grains. Corrosion was
most advanced at areas of higher turbulence around the periphery of the upper tubesheet and opposite the liquor inlet
nozzles in the liquor body. The turbulence generated as vapour exited between the umbrella and tubesheet had
stripped the cladding from the edge of the tubesheet (Figure 19). Surprisingly, the carbon steel in this area did not
appear to have corroded appreciably, perhaps due to galvanic protection provided by the stainless steel. Part of the
tubesheet was built up using stainless steel weld metal. Corrosion of the tubesheet to steam chest weld and
structural welds in the stainless steel vapour body of the vessel was also observed (Figure 20). The welds were
roughly 3 mm (⅛") below flush, suggesting as much as 9 mm (⅜") total metal loss had occurred over 30 years of
service.

An epoxy coating was applied to the upper and lower tubesheets of the 3rd and 5th effects in an evaporator train to
control ditching damage adjacent to the tubes. The coating in the 3rd effect was in good condition after roughly
seven years service (Figure 21). In the 5th effect evaporator, the coating was less successful, possibly because
ditching was more advanced in this vessel before the coating was applied. After 4 years of service, the coating
showed evidence of failure with corrosion visible adjacent to tubes. At the last inspection (after 7 years of service),
numerous tubes in the lower tubesheet were leaking due to severe highly localized ditching (Figure 22).

SCC was found in the upper and lower stainless-clad tubesheets in a 20 year old 2nd effect evaporator (Figure 23).
Cracking occurred along the upper tubesheet to steam chest welds and at liquor preheater box attachment welds at
both the upper and lower tubesheets. Exploratory grinding determined that the SCC was restricted to the stainless
layer at both tubesheets. No corrosion of the underlying carbon steel was noted and the cladding was still tightly

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

adhered. Weld repairs were carried out to cover the exposed carbon steel. Re-inspection of these areas over the past
2 years has shown that the cracking is dormant.

Carbon steel mechanical plugs are commonly used to isolate leaking tubes. Carbon steel plugs are often rapidly
attacked and the tube seal can fail. Numerous plugs in the liquor chamber of a 1st effect evaporator had receded
approximately 4 cm (1 ½") below the tubesheet (Figure 24). Some of the plugs had had dropped out. Corrosion
rates on the carbon steel plugs were roughly 3 mm/year (125 mils per year). Repairs involved using pieces of type
304 stainless steel plate to seal the previously plugged tubes.

Corrosion in Evaporator Bottoms

Significant flow-accelerated galvanic corrosion of the carbon steel wall was observed adjacent to the stainless steel
tubesheet in the liquor chamber at the bottom of a rising film evaporator (Figure 25). Corrosion testing confirmed
that the liquor was highly corrosive to carbon steel even under non-flow conditions at 139ºC (282ºF) giving a
corrosion rate of 1.2 mm/y (47 mpy). A new liquor chamber was constructed using type 2205 duplex stainless steel.

Severe corrosion of carbon steel can also occur in the immersion zone at the bottom of falling film evaporators,
particularly at nozzles. Figures 26 – 28 show perforations in the nozzles in the bottom of a 3rd effect falling film
evaporator. Stainless steel linings of the bottom cone and nozzles may cause galvanic corrosion of the carbon steel.
"Wormholing" has occurred behind stainless steel loose liners. Replacement of carbon steel nozzles was done using
type 304L stainless steel but this is likely only a temporary fix since new galvanic corrosion is liable to occur.

Corrosion in Evaporator Heater Shells

Heater shells experience vapor and condensate service. Carryover liquor in the vapor can cause severe corrosion of
heater shells. Heavy grooving of the heater shell below the vapour inlet was found in a 4th effect evaporator after
approximately 20 years of service (Figure 29). A carbon steel shell insert was installed to repair the damage. The
vapour inlet nozzles and a portion of the upper shell in the vessel had been previously replaced in stainless steel as a
result of heavy thinning. The grooving damage was due to liquor being carried over in the vapour flow draining
from the vapour inlet and running down the wall. Areas of the shell not immediately below the inlet were
unaffected. The carbon steel insert showed significant damage after only 3 years. This rapid onset of damage likely
reflects the fact that the vessel is being driven beyond the original design resulting in greater carryover. Similar
damage has occurred in the 2nd and 3rd effects in this evaporator train. Erosion corrosion of the vortex breaker at the
condensate outlet nozzle has been an ongoing issue in the 4th effect evaporator (Figure 30). Metal loss rates on this
component are as high as 3 mm (⅛") per year. The vortex breakers within other effects in the train have been found
with holes in some cases.

After approximately 30 years of service, the heater shell in a 2nd effect evaporator was perforated downstream of the
tangential vapour inlet (Figure 31). The internal baffle plates around the vapour inlet had thinned to failure and the
baffle plate around the tube bundle was heavily thinned. Liquor carryover appeared to be the root cause of failure.
In this case, however, damage was not restricted to high flow areas but also occurred in relatively quiet areas where
liquor pooled. The liquor drain nozzle near the inlet had suffered heavy pitting damage and was replaced; the
surrounding shell was heavily roughened by corrosion but no action was taken due to time constraints.

Thermal Spray Coatings

Thermal spray coatings have been used for corrosion protection since at least 1950 [3]. In most cases, the coatings
are effective and buy time before more expensive alternatives such as replacement are necessary. Surface
preparation is critical for the best performance from a thermal spray coating. There can also be corrosion problems
associated with the coatings.

Failure of thermal spray coating in the vapour body of a 3rd effect rising film evaporator has been a recurring
problem along seam welds and gives rise to accelerated corrosion of the welds (Figure 32). Portions of the thermal
spray coating have required repair or touch-up on a yearly basis. It appears that liquor can access the weld through
imperfections in the coating due to the roughness of the welds. When the liquor gets under the coating it
aggressively attacks the weld giving rise to corrosion losses of 6 mm (¼") or more per year in a highly localized

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

area. Repairs to restore the weld seam and thermal spray coating have not been successful unless the weld surface is
profiled to remove sharp edges and crevices. Welds that have been profiled and re-sprayed have given up to 4 years
service to date.

A thermal spray coating applied over flat plate will occasionally experience localized failure. Figure 33 shows a
perforation in the thermal spray coating on the vapour body shell of a 4th effect evaporator that gave rise to a void 12
mm (½") deep and 25 mm (1") long within a 2 year period. A perforation in the thermal spray coating on the
portion of the heater shell extending into the vapour body of a 4th effect evaporator led to holes in the heater shell
over the same 2 years of service. The thermal spray coating had been top coated with an organic seal coat that
developed extensive blistering within the first year of service. These blisters appeared to be precursors to failure of
the underlying thermal spray coating although only a few blisters gave rise to serious problems.

A vapour duct outer wall near the duct opening in a 3rd effect evaporator was thermal spray coated in an attempt to
control severe metal loss in this area. The thermal spray coating was unsuccessful in this area, lasting only a year
before significant degradation of the coating was noted (Figure 34).

The upper tubesheet in a 3rd effect evaporator was thermal spray coated in 1997 to control general corrosion of the
carbon steel. Inspection in 2001 found that the thermal spray coating was still relatively intact, but "undercutting" of
the carbon steel tubesheet was occurring beneath the thermal spray (Figure 35). Small holes in the metal spray
opened to large voids where the carbon steel was lost. The tubesheet wastage was so severe in many areas adjacent
to the tubes that the tubesheet was penetrated in some cases (Figure 36). It appears that liquor trapped under the
thermal spray was more aggressive than the bulk liquor. Weld repairs were carried out around ten tubes. Follow up
inspection in 2002 found that damage had progressed significantly and repairs were required around roughly one
hundred tubes

Approximately 8 years ago, a thermal spray coating was applied to the carbon steel upper tubesheet in a 4th effect
evaporator. The coating has been failing along the stainless steel tubesheet to steam chest weld and spalling is
moving gradually inward (Figure 37). Roughly 3 mm (⅛") of carbon steel thickness has been lost adjacent to the
stainless steel weld. Apart from this damage the coating is largely intact and has performed well in protecting the
bulk of the tubesheet.

Corrosion in Concentrators

Concentrators operate at higher temperatures and with higher solids content liquors, and are typically of solid or clad
stainless steel construction. Liquor concentrator vessels may be of three general designs:

• Upflow design using a tube bundle contained within the heater shell of the vessel, i.e. essentially a
"standard evaporator" that operates at higher temperature.
• Falling film design using either a tube bundle or flat platen elements.
• Vessels using external heaters where the liquor is heated outside the vessel and then pumped into the
concentrator where flashing occurs.

Corrosion problems have been experienced in all three types of concentrators.

Experience in Upflow Concentrators

The vapour body and lower dome in a rising film concentrator were fabricated using type 304 stainless steel roll clad
plate, as were the upper and lower tubesheets. All liquor piping and the tube bundle were also of type 304 stainless
steel metallurgy. During the inspection in 2001, it was noted that the surface of the clad plate in the vapour body
was rough and discoloured. Eddy current thickness testing found a minimum cladding thickness of 0.5 mm (0.022")
with the lowest values occurring at roughly the tubesheet elevation. The cladding had a minimum thickness of 2.3
mm (0.090") 6 feet above the tubesheet elevation. Significant perforations of the cladding were observed at the
tubesheet elevation 1 year later (Figure 38). The exposed carbon steel was corroded to a depth of approximately 3
mm (⅛"). Eddy current thickness testing carried out in the lower dome found no pattern to the distribution of metal
loss. Readings ranged from a low of 2.2 mm (0.049") to a high of 2.3 mm (0.091").

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Close examination of the affected surfaces found grain drop-out was occurring suggesting that the stainless steel
cladding was sensitized and was undergoing intergranular corrosion. Stainless steel piping and welds were not
affected nor were the heat affected zones around welds to the shell. It appeared the welding heat cycle served as a
"solution annealing treatment" and restored the corrosion resistance of the clad layer.

Follow-up eddy current thickness testing carried out between 2002 and 2004 determined that corrosion rates in low
turbulence areas in both the vapour body and the lower dome were typically 0.1 to 0.25 mm/y (5 to 10 mils per
year). Corrosion rates were much higher and exceeded 0.5 mm/y (20 mils per year) in high turbulence areas. In
both 2003 and 2004, through-wall perforations were found associated with the vapour outlet ducting (Figure 39).
Corrosion rates on the exposed carbon steel in these areas exceeded 12 mm (½") per year.

Repairs to the vessel were carried out by lining using 2205 duplex stainless steel. One course of over-plating at the
tubesheet elevation was carried out in 2002 followed by a second course in 2004 since corrosion of the roll clad
plate had continued. The duplex stainless steel has performed well to date and after 3 years of service no
appreciable corrosion of the plate can be detected although "frosting" of the seal welds has occurred.

The lower stainless-clad tubesheet was found to be severely damaged in 2004 (Figure 40). A hole through the 37
mm (1 ½") thick tubesheet plate occurred as the result of localized loss of the tubesheet stainless steel cladding. The
exposed carbon steel was then rapidly attacked and perforated (Figure 41). Experience in the upper dome has shown
that corrosion occurs at an extremely rapid rate once the carbon steel is exposed. The lower tubesheet was found to
be in good visual condition with no exposed carbon steel evident during inspection in 2003. Eddy current thickness
readings carried out on the lower dome shell in 2003 ranged from 1.3 mm to 1.8 mm (0.050" to 0.076"). Failure of
the tubesheet cladding was surprising since there was no significant change in the thickness readings from 2002. In
2005, the upper and lower tubesheets were replaced using solid duplex stainless steel.

Recently a number of mills have suffered thinning failures of tubing in high solid concentrators and liquor heaters
after 15 to 20 years of service. Eddy current inspection of the tube bundle was carried out in 2004 since this vessel
was of similar vintage and had experienced corrosion of the clad plate. A limited inspection found 25% of the tubes
were thinned from between 40% and 49% through-wall while the remaining tubes had wall thinning that ranged
from 20% to 29%.

Experience in a Falling Film Concentrator

Significant corrosion of weld heat affected zones in the piping has occurred in a falling film concentrator
constructed in the mid-1980's using type 304 stainless steel (Figure 42). The liquor distribution piping at the top of
the vessel, as well as condensate collection piping and NCG take-off piping in the lower end of the vessel have been
affected. Roughly half the wall thickness of the piping had been lost adjacent to welds rendering the piping
susceptible to fatigue cracking damage. The piping was replaced during a rebuild of the vessel in 2001. To date the
replacement components have not shown significant damage.

Experience in a Concentrator Using External Heaters

A concentrator of type 304 stainless steel construction with external heaters had been in service roughly 15 years
before corrosion problems became apparent. The only evidence of corrosion within the concentrator was "frosting"
of welds and weld heat affected zones on the shell and attachments. The concentrator was fed by two external
heaters. Both heater tube bundles were of type 304 stainless steel metallurgy. The heaters performed without
notable problems until 1999 when a number of tubes collapsed in service (Figure 43). At that time, mill personnel
thought it was the result of a steam pressure surge and no further action was taken. The heaters were inspected
again in 2000 and more collapsed tubes were found as well as tube cracking at the lower tubesheet (Figure 44).
Again the damage was attributed to operational problems and the unit was returned to service with no action taken.
Shortly after being brought back on line, a steam pressure surge occurred and both heaters were blinded off with
tubes collapsed over their entire length. Subsequent examination determined that the tubes were heavily thinned
from the liquor side

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

External Corrosion

Both carbon steel and austenitic stainless steel evaporators can experience severe corrosion beneath wet thermal
insulation. NACE has published guidelines on the prevention of external corrosion and cracking [35].

In 1990, a 4th effect evaporator dome separated from the vapor body and traveled 50 metres (150 feet) before
landing on the roof of a black liquor storage tank. Inspection of the heads of the other evaporators in the train
(Figure 45) revealed them to have severe general thinning on the outside of the head that reduced the thickness from
14 mm (9/16") to 3 mm (⅛"). The failure location was at the dome-to-flange weld (Figure 46) where the weld had
incomplete penetration and where a fatigue crack had initiated at a large slag pocket.

After approximately 17 years of service, ESCC was found under the thermal insulation on a type 304 stainless steel
evaporator flash tank. The ESCC occurred immediately above a carbon steel stiffener ring stitch welded to the shell
(Figure 47). Dye penetrant applied to the outside of the vessel was picked up on the inside indicating cracking had
propagated through the wall (Figure 48). "Temporary" repairs were made by installing stainless steel bands on the
outside and inside of the vessel and seal welding them. The repair was in service for 10 more years before the kraft
mill was decommissioned.

DISCUSSION

The examples presented in this paper are just a few of the corrosion problems that we have found. Corrosion testing
is currently ongoing to better understand why some carbon steel evaporators suddenly experience rapid corrosion
thinning after many years of problem-free service. Suspected culprits are increased sulfidity and increased
temperature. There are three possible corrosion states for carbon steel in evaporators:

1. Stable passivity.
2. Unstable passivity.
3. Active corrosion.

In weak black liquors, carbon steel appears to have stable passivity and consequently a very low corrosion rate.
Increased sulfidity and temperature do not appreciably change the passive corrosion rate.

In strong black liquors, carbon steel corrodes actively. If the corrosion rate is greater than 0.5 mm/y (20 mils per
year) carbon steel may be unsuitable as a material of construction, necessitating the use of stainless steel. Increased
sulfidity or temperature will increase the active corrosion rate of carbon steel, making an unsuitable material even
more unsuitable.

In intermediate black liquors, carbon steel has unstable passivity. Slight increases in sulfidity or temperature may be
sufficient to cause the corrosion state to change from passive to active. If a change from passive to active behavior
occurs, the result will be the sudden onset of rapid corrosion. This is likely the reason for much of the unexpectedly
rapid corrosion observed in 3rd, 4th, and even 5th effect evaporators.

Austenitic stainless steels are generally resistant to corrosion in evaporators unless they have become sensitized as
has been observed for clad plates, particularly in tubesheets. SCC can be a problem the high service temperatures
and solids contents characteristic of concentrators. ESCC may be a problem for evaporators, concentrators, and
flash tanks constructed using austenitic stainless steels. As in other locations in the kraft mill, the trend is to
construction using duplex stainless steels.

CONCLUSIONS

1. Carbon steel evaporator corrosion is mill-specific and even train-specific.


2. Carbon steel evaporators can experience corrosion just about everywhere: in the vapor dome, in vapor ducting,
on the tubesheets, in immersion service, and inside the heater element.
3. The corrosion of carbon steel is often galvanically accelerated by contact with stainless steel.
4. Thermal spray coating can protect against corrosion but careful surface protection and inspection are required.
5. Type 304L stainless steel can experience intergranular corrosion and SCC in evaporators.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

6. External corrosion and SCC can also be problems with evaporators.

REFERENCES

1. Clay, L., Summary of Key Pulp and Paper Industry Corrosion Problems, Proc. of the 1st International
Symposium on Corrosion in the Pulp & Paper Industry, Chicago, pp. 7-8 (1974).
2. Venkatesh, V. and Nguyen, X.N., Evaporation and Concentration of Black Liquor, in Chemical Recovery in
the Alkaline Pulping Processes, 3rd Ed., co-editors R.P. Green and G. Hough, Tappi Press, Atlanta (1992).
3. Von Essen, C.-G., Corrosion Problems in Sulphate Paper Mills, Tappi J. Vol 33 No. 7, pp. 12A-32A (1950).
4. Lankenau, H.G., Engel, C.P., and Flores, A.R., Corrosion of Carbon and Stainless Steel Evaporators by Sulfate
Black Liquor, Proc. of the 1st International Symposium on Corrosion in the Pulp & Paper Industry, Chicago,
pp. 117-124 (1974).
5. Lankenau, H.G. and Bohnenberger, B., Service Experience of Materials for Pulping Spent Liquor Evaporators,
Proc. Tappi Eng. Conf., pp. 501-507 (1978).
6. Doughty, S.E., and Comerford, W.J., The Manufacture of Welded Stainless Steel Tubing for Maximum
Corrosion Resistance in Kraft Evaporators, Tappi J., Vo. 44 No. 9, pp. 609-613 (1961).
7. Collins, T.T., Acid Cleaning of Evaporators, Tappi J., Vo. 45 No. 9, pp. 692-702 (1962).
8. Chakrapani, D.G. and Czyzewski, H., Corrosion Problems in the Pulp and Paper Industry – A Few Case
Histories, Paper No. 19 presented at the NACE Corrosion/78 Conference, Houston (1978).
9. Bowers, D.F., Corrosion Problems in Kraft Liquor Systems, Paper No. 90 presented at the NACE
Corrosion/82 Conference, Houston (1982).
10. Yeske, R., Corrosion in Black Liquor Processing Equipment, ASM Metals Handbook, 9th Ed., Vol 13,
"Corrosion" pp. 1213-1214, ASM International, Metals Park, OH (1987).
11. Danielson, G. and Risebrough, N.R., External Stress Corrosion Cracking of Evaporator Tubes, Proc. Tappi
Eng. Conf., pp. 807-812 (1991).
12. Willis, J.D. and Murry, J.R., Corrosion Failure of Stainless Steel Evaporator Piping, Tappi J., Vol 75 No. 6 pp.
97-100 (1992).
13. Minutes of the Meeting of the NACE T-5H-14 Task Group on Black Liquor Corrosion, March 13, 1993.
14. MacLean, H. and Gardner, J.A.F., Heartwood Extractives in Digester Corrosion, Pulp and Paper Mag. Can.,
Vol 54 No. 11 pp. 125-130 (1953).
15. Mueller, W.A., Corrosion Studies of Carbon Steel in Alkaline Pulping Liquors by the Potential-Time and
Polarization-Curve Methods – Part II Mixtures of White with Oxidized or Nonoxidized Black Liquor, Tappi J.,
Vol 40 No. 3, pp. 129-140 (1957).
16. Tonsi-Eldakar, N. and McGlynn, K., Electrochemical Behavior of Iron in Alkaline Solutions Containing
Sodium Sulfide and Catechol, Paper No. 91 presented at the NACE Corrosion/82 Conference, Houston (1982).
17. Kannan, S., Bastek, P.D., and Kelly, R.G., Preliminary Studies on Preparation of Synthetic Black Liquors,
Paper No. 289 presented at the NACE Corrosion/92 Conference (1992).
18. Kelly, R.G., et al, Results of Corrosion Coupon Exposures of Ferrous Materials in Black Liquor, Tappi J. Vol
79 No. 11 pp. 148-154 (1996).
19. Wensley, A. and Champagne, P., Effect of Sulfidity on the Corrosivity of White, Green, and Black Liquors,
Paper No. 281 presented at the NACE Corrosion/99 Conference, San Antonio (1999).
20. Wensley, A., Corrosion in Alkaline Pulping Liquors, Paper No. 04248 presented at the NACE Corrosion 2004
Conference, New Orleans (2004).
21. Troselius, L., Corrosion in Evaporator Plants and Heavy Black Liquor Storage Tanks, Proc. of the 11th
International Symposium on Corrosion in the Pulp & Paper Industry, Charleston, Paper ISC0410 (2004).
22. Singh, PM., Mahmood, J., and Conde, P., Stress Corrosion Cracking and Corrosion Susceptibility of Duplex
Stainless Steels in Caustic Solutions, Paper No. 05196 presented at the NACE Corrosion 2005 Conference,
Houston (2005).
23. Anderson, D.B., Pulp and Paper Mill Corrosion Tests – Phase I, Part II, Proc. Tappi Eng. Conf., pp. 325-335
(1980).
24. Ström, S., Corrosion of Carbon Steels and Stainless Steels in Sulphate Black and Green Liquors, Proc. of the
7th International Symposium on Corrosion in the Pulp & Paper Industry, Orlando, pp. 105-110 (1992).
25. Wensley, A., Intergranular Attack of Stainless Steels in Kraft Digester Liquors, Paper No. 465 presented at the
NACE Corrosion/96 Conference, Denver (1996).
26. Wensley, A., Corrosion of Batch and Continuous Digesters, Proc. of the 8th International Symposium on
Corrosion in the Pulp & Paper Industry, Ottawa, pp. 27-37 (1998).

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

27. Klarin, A. and Kottila, M., Caustic Corrosion in Black Liquor Evaporators, Proc. Tappi Eng. Conf., pp. 299-
306 (1996).
28. Klarin, A., Corrosion Phenomena in Black Liquor Evaporators, Proc. of the 10th International Symposium on
Corrosion in the Pulp & Paper Industry, Helsinki, pp. 469-483 (2001).
29. Kottila, M. and Rauscher, J.W., Selecting the Proper Material for Black Liquor Concentrators, Proc. of the 10th
International Symposium on Corrosion in the Pulp & Paper Industry, Helsinki, pp. 485-495 (2001).
30. Andreasson, P., Corrosion Problems with Stainless Steels in Evaporator Plants, Proc. of the 10th International
Symposium on Corrosion in the Pulp & Paper Industry, Helsinki, pp. 497-508 (2001).
31. Reid, C., Stress Corrosion Cracking of Austenitic and Duplex Stainless Steels in the Kraft Pulp Mill, Proc.
Tappi Eng. Conf., Anaheim, pp. 1315-1337 (1999).
32. Bennett, D. and Reid, C., Unexpected Corrosion of Stainless Steel in High Solids Black Liquor Service, Tappi
Solutions Mag., pp. 57-58, Sept. 2002.
33. Klarin-Henricson, A., Corrosivity of Black Liquors from a Modern Digester to a High Solids Concentrator,
Proc. of the 11th International Symposium on Corrosion in the Pulp & Paper Industry, Charleston, Paper
ISC0409 (2004).
34. Leinonen, H., Corrosion Resistance of Duplex Stainless Steel and its Welds in Modern Kraft Cooking, Proc. of
the 11th International Symposium on Corrosion in the Pulp & Paper Industry, Charleston, Paper ISC0407
(2004).
35. NACE Standard RP0198-98, The Control of Corrosion Under Thermal Insulation and Fireproofing Materials –
A Systems Approach, NACE International, Houston (1998).

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 1. Corrosion through the side of the heater shell in a 3rd effect evaporator.

Figure 2. Preheater box that has come loose from the tubesheet in a 4th effect evaporator.
The welds were preferentially attacked.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 3. Corroded barometric leg in a 3rd effect evaporator.

Figure 4. Corroded drain pipe in a fourth effect evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 5. Corroded umbrella support in a 4th effect evaporator.

Figure 6. Galvanic corrosion of the carbon steel wall adjacent to the stainless steel lining
in a 2nd effect evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 7. Grooving of the shell of a 3rd effect evaporator at a "cold finger."

Figure 8. SCC of a carbon steel weld repair at a sight glass in a 4th effect evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 9. Severe erosion-corrosion and perforation of the carbon steel shell above a hole
in the support for the mist eliminator.

Figure 10. Corrosion of the shell below a hole in the support for the mist eliminator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 11. Corrosion of the door into the vapor separator in a 3rd effect evaporator.

Figure 12. New type 304L stainless steel floor in the vapor separator in a 2nd effect
evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 13. Erosion-corrosion has produced "rivulets" in the vapor outlet piping from a 1st
effect evaporator.

Figure 14. Top head in a 3rd effect falling film evaporator showing two rows of stainless
steel loose liner plates above the tubesheet.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 15. Severe galvanic corrosion and perforation of the carbon steel wall in the top
head of a 3rd effect falling film evaporator.

Figure 16. Grooving of the carbon steel wall 1 cm above the tubesheet in the top head of a
3rd effect falling film evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 17. Severe corrosion of the carbon steel tubesheet in a 3rd effect evaporator.

Figure 18. Galvanic corrosion of a carbon steel tubesheet adjacent to the stainless steel
tubes in a 3rd effect evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 19. Corrosion of the stainless steel clad tubesheet in a 1st effect evaporator. Carbon
steel is exposed around the edge.

Figure 20. Preferential corrosion of the tubesheet-to-steam chest weld in a 1st effect
evaporator. The tube sheet had been built up using stainless steel.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 21. Epoxy coating in good condition on the lower tubesheet of a 3rd effect
evaporator.

Figure 22. Epoxy coating on the lower tubesheet of a 5th effect evaporator. Failure of the
coating around the tubes has led to galvanically-driven ditching and leaks.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 23. SCC of the stainless-clad tubesheet in a 2nd effect evaporator.

Figure 24. Corrosion of a carbon steel tube plug in a 1st effect evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 25. Erosion-accelerated galvanic corrosion of the carbon steel liquor chamber below
a stainless steel tubesheet. A window was cut to confirm the thinning.

Figure 26. Corrosion perforation of the interior projection of the liquor inlet in the bottom
head of a 3rd effect falling film evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 27. Exterior view of a leak in the bottom recirculation nozzle in a 3rd effect falling
film evaporator.

Figure 28. Interior view of a leak in the bottom recirculation nozzle in a 3rd effect falling
film evaporator. The nozzle-to-cone weld was stainless steel.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 29. Heavy grooving of the heater shell below the vapor inlet in a 4th effect
evaporator.

Figure 30. Erosion-corrosion of the condensate outlet vortex breaker in a 4th effect
evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 31. View through a window cut into the heater shell of a 2nd effect evaporator
showing thinning and failure of the inlet baffles downstream of the vapor inlet.

Figure 32. Failure of the thermal spray coating on a vertical weld seam in the vapor body of
the 3rd effect rising film evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 33. Perforation of the thermal spray coating and the heater shell inside the vapor
body of a 4th effect evaporator.

Figure 34. Deterioration of a thermal spray coating on a vapor duct outer wall at the duct
opening in a 3rd effect evaporator after only 1 year.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 35. Failure of a thermal spray coating on the tubesheet of a 3rd effect evaporator
after 4 tears.

Figure 36. Closer view of severe ditching around the tubes where the thermal spray coating
on the tubesheet had failed around the tubes in a 3rd effect evaporator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 37. Failure of the thermal spray coating at the tubesheet-to-steam chest weld after 8
years.

Figure 38. Corrosion perforation of the stainless-clad vapor body in a rising film
concentrator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 39. Shell of a rising film concentrator perforated beneath the vapor outlet nozzle.

Figure 40. Failure of the stainless-clad bottom tubesheet adjacent to the tubes in a rising
film concentrator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 41 Excavation of the stainless steel cladding from around a tube in a rising film
concentrator revealing a large void in the underlying carbon steel tubesheet with
two perforations of the tubesheet.

Figure 42. Attack of the heat affected zones of the welds in a liquor distribution pipe in the
top of a falling film concentrator.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 43. Collapse of tubes in an external liquor heater tube bundle for a concentrator.
The thinning occurred from the process side.

Figure 44. Cracking of tubes in an external liquor heater as the result of severe thinning
from the liquor side.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 45. Severe corrosion found beneath wet thermal insulation on a carbon steel
evaporator top dome.

Figure 46. Top of a 4th effect evaporator after the departure of the top dome.

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Paper Presented at the TAPPI Engineering, Environmental, and Pulping Conference, Philadelphia, 2005.

Figure 47. ESCC of a type 304 stainless steel above an external stiffening ring on an
evaporator flash tank.

Figure 48. Penetrant testing on the inside of the evaporator flash tank showing that the
ESCC had propagated completely through the stainless steel wall.

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