Paper No.

00691
CORROSION 2000
E X P E R I E N C E W I T H T I T A N I U M H E A T E X C H A N G E R S IN R E F I N E R Y S E R V I C E S

Deyuan Fan, William C. Fort, ili, Richard J. Horvath

Equilon Enterprises, LLC
P.O. Box 1380
Houston, Texas, 77251-1380 USA

ABSTRACT

Several experiences (successful and unsuccessful) with the use of titanium heat exchangers in refining
processes are summarized. These experiences primarily involve distillation column overhead condensers in
atmospheric crude distilling units, fluid catalytic cracking units, delayed coking units, and sour water strippers.
The causes of problems are discussed in relation to known limits of titanium corrosion resistance. Needs for
additional data are highlighted.

INTRODUCTION

Due to their superior corrosion resistance in many difficult environments, titanium and titanium alloys
have been successfully used in various petroleum refining and petrochemical manufacturing processes over many
years. Most applications are for water-cooled heat exchanger tube bundles, where grade 2 titanium is chosen to
resist aggressive conditions on the water side o-3). But there are many more applications involving shell and tube
heat exchan§ers, air coolers, piping, and pressure vessels where process side corrosion resistance is the primary
challenge ~4- ). Titanium's resistance to dilute HCI, NH4CI, NH4HS, and similar process environments has been
the primary reason for its use in our plants. Such conditions are found in a number of refining and petrochemical
processes.

The Shell/Texaco alliance companies (Equiion Enterprises LLC and Motiva Enterprises LLC) have a
large number of titanium bundles in refinery applications. Overall, most of the applications have been very
successful. However, as with any material, misapplication of titanium or operation of titanium equipment beyond
established process limits have resulted in premature failures, some with significant business impact. Some of the
experiences with titanium specific to Motiva's Delaware City Refinery have already been published t2,3). This
paper presents some illustrative case histories from other Shell/Texaco alliance refineries. The discussion is
organized around the type of refinery services. Some of the case histories describe failures. Despite these failures,
however, there are many not-so-interesting success stories.

CRUDE D I S T I L L A T I O N C O L U M N O V E R H E A D SERVICE

In petroleum refining, acidic conditions arise from chloride salts entering the refinery in crude oil. Even
after crude desalting, some of these salts still remain and can hydrolyze to HCI as the oil is heated in the crude
distilling unit (CDU) charge heater. The HCI gas goes to the overhead system of the atmospheric crude distilling

Copyright
©2000 by NACE International.Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Conferences Division, P.O. Box 218340, Houston, Texas 77218-8340. The material presented and the views expressed in this
paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in U.S.A.

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column, where it condenses with water to form hydrochloric acid. As with most refiners, we treat our CDU
atmospheric distilling column overhead systems with ammonia or amines to partially neutralize the acid to control
corrosion. The resulting ammonium or amine salts are also corrosive, though not nearly as corrosive as theun-
neutralized acid.

Most o f our early applications of titanium exchangers were in crude distillation column overhead service,
and overall they have been very successful. A few early failures served to define the limits of the commercially
pure titanium (grade 2) in this servicel~6). Since then, some titanium tube bundles have now been in service for
over 25 years. Titanium has provided reliability far superior to carbon steel in this service, specifically with
regard to the resistance to underdeposit pitting usually associated with salts such as ammonium and amine
chlorides. Decreased corrosion and fouling and improved heat transfer have been experienced with titanium tubes
bundles. As a result of the many favorable experiences in this service, new applications in this and other similar
services are increasing. Thus far, we have used Grades 2, 12, 7 and 16 titanium in refining crude distillation
column overhead service.

The experience gained to date has led us to formation of the practices outlined below to ensure continued
successful application in atmospheric crude distillation column overhead service. Underdeposit corrosion and
crevice corrosion concerns limit the use of certain grades of titanium at high temperatures.

• Grade 2 titanium has been used reliably up to 250°F (121°C) for over 25 years in atmosphere crude
distillation column overheads when used in conjunction with injection o f neutralizers to control the pH.
Some failures have occurred when it was used above 250°F (121°C) in this service (4)
• Grade 2 titanium has also been used very successfully in fractionator overhead systems in other process units
such as fluid catalytic crackers, delayed cokers, and sour water strippers. The temperatures of applications in
these systems vary from 210°F (99°C) to 250°F (121°C).
• Grade 12 titanium has been used in atmospheric crude distilling column overhead condensers up to at least
340°F (171°C) in situations where formation o f solid, dry salt can be avoided. Proper water wash or selection
o f amine neutralizers is important in ensuring the successful use of titanium.
• Grade 16 titanium has only recently been introduced into refinery service. It is being used up to 350°F
(177°C). Sufficient experience to judge limits is not yet available.
• Tubesheets and tube bundle skeletal items (e.g. baffles, tie rods, etc.) should be made from suitable alloy
materials, not carbon steel, to optimize bundle life. Premature failures o f titanium tube bundles have resulted
from corrosion of carbon steel skeletal items. Besides titanium, materials such as Alloy 625, Alloy 825,
Alloy 20Cb-3, Alloy 400, and even Type 316 stainless steel have been used successfully for these parts in
certain applications.
• Use of the thinner wall titanium tubes, typically 20 ga. (0.035 in. [0.89 mm] wall thickness), requires closer
baffle spacing to prevent excessive tube vibration that can result in premature fatigue failures. Tubesheet
holes should be TEMA ~ close tolerance fit to facilitate tube roiling to obtain proper tube-to-tubesheet seal.
Because o f these important considerations, it is not a good practice to simplyretube an existing carbon steel
bundle with titanium tubes.
• In most cases, a proprietary neutralizing amine is injected, either with water or with another carrier, ahead of
the condensers to control the pH and protect the exchanger shell, associated piping, and overhead
accumulator. Injection of ammonia or amines that form high melting, solid chloride salts is not advised where
titanium condensers are used.

The following is a select list o f our titanium application experiences, including failure histories where
applicable.

Tubular Exchanger Manufacturers Association, 25 North Broadway Tarrytown, NY 10591, USA

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 Case 1 - Crude Distilling Unit

In 1972, grade 2 titanium tubes were first installed in the atmospheric crude distilling column overhead
vapor/cooling water condenser bundles operating at process temperatures less than 260°F (127°C). The titanium
tubes replaced carbon steel tubes that had a short life. The grade 2 titanium tubes have been in use for over 25
years, without any problems.

In 1973, grade 2 titanium tubes were installed in the hotter overhead/crude exchanger bundles in this
same overhead system. The atmospheric crude distilling column tops vapor at 336°F (167°C) enters the shell side,
and the crude feed at 70°F (21°C) enters the tube side. Leaks occurred in the titanium tube bundles within one
month after installation. The leaks were found to be highly isolated pits, often only one over a 20-ft (6-m) long
tube and usually in the hotter portion of the bundles. Figures la - lc show typical pits initiated from tube OD. All
of them were located on the top of the tubes. After 12 months in service and a total of 14 leaks, the tube bundles
were replaced.

The corrosion was attributed to pitting and/or underdeposit corrosion associated with ammonium chloride
salts. Scanning electron microscope (SEM) traces near the pits revealed elevated levels of chlorides (Figures 2
and 3) in addition to iron and sulfur. Analysis of the overhead sour water samples showed 60 to 80ppmw chloride
and 220 to 460 ppmw ammonium. Surface finish and iron contamination of the titanium tubes were also cited as
potential contributors to the observed failures~5'6~. Intermittent water washing was initiated to remove the NH4CI
deposits and keep the bundle clean. This approach apparently helped somewhat to prolong the bundle life, but
was not ultimately successful. Eventually, carbon steel tubes were reinstalled, but process changes in the early
1980's caused carbon steel bundle life to decrease to less than six months.

In the mid-1980's, grade 12 titanium tube bundles were installed in this higher temperature
overhead/crude service. The grade 12 titanium tubes performed very well, but premature bundle failures occurred
because the carbon steel tubesheets, baffles, and tie rods corroded severely. These bundles were replaced with
grade 12 titanium tubes, alloy clad tubesheets, and solid alloy baffles and tie rods. In this very aggressive
overhead condensing environment, the grade 12 titanium has now served well for over 15 years.

Case 2 - Crude Distilling Unit

In 1994, grade 12 titanium bundles were installed in the atmospheric crude distillation column overhead
vapor/crude exchangers. These replaced carbon steel bundles that were failing at six-month intervals. Operating
temperatures were up to at least 332°F (167°C). These bundles have performed very well for over five years.

Case 3 - Crude Distilling Unit

Some grade 2 titanium tubes were installed in the bundles of carbon steel atmospheric crude distillation
column overhead/crude exchangers during 1981/82. The titanium tubes were placed in four rows around the outer
periphery of the bundles where carbon steel tubes had failed quickly due to erosion-corrosion associated with the
incoming mist-laden overhead vapor. The grade 2 titanium tubes have performed very well for about 18 years at
temperatures up to 250°F (121°C).

Case 4 - Crude Distilling Unit

Some grade 12 titanium tubes were installed in two of the carbon steel atmospheric crude distillation
column first stage overhead vapor/crude exchanger bundles in 1991. The titanium tubes were used in the top four
rows where carbon steel tubes had failed rapidly. Other tubes in the bundles remained as carbon steel. Extra
vibration dampening bars were installed between the baffles to provide additional support for the titanium tubes.
The titanium tubes performed very well at service temperatures up to 300°F (149°C). Severe corrosion of the
remaining carbon steel tubes prompted replacement of these bundles in 1993, and grade 12 titanium tubes were
again used in the top four rows.

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 In 1995, major process changes were made as part of a unit revamp project to facilitate the processing of a
new crude. The column overhead temperature was raised to 340°F (171°C). Multiple failures o f the carbon steel
tubes occurred between 1997 and 1999. Again, the titanium tubes in top four rows performed very well.

In 1999, these exchangers (total of six) were replaced with grade 16 titanium tube bundles with grade 7
titanium baffles and tie rods, Alloy 625 tubesheets, and Alloy 625 clad shells. Grade 16 titanium has been
reported to possess corrosion resistance superior to grade 12 and closely approaching grade 7 titanium o). These
exchangers are expected to perform very well.

In 1995, grade 2 titanium bundles were installed in two of the second stage overhead vapor/crude
exchangers in the overhead system as part of the unit revamp mentioned above. These exchangers experience
temperatures up to 250°F (121°C) and have performed satisfactorily to date.

Case 5 - Crude Distilling Unit

A grade 12 titanium bundle was installed in one o f the atmospheric crude distillation column first stage
overhead vapor/crude exchangers in 1992. This bundle operates up to 265°F (129°C). It replaced a carbon steel
bundle that was failing in three to four months due to amine chloride salt corrosion. The bundle was inspected
during the 1995 maintenance turnaround and was found to be in like-new condition. It is still in service to date
with no problems reported.

Case 6 - Crude Distilling Unit

Two grade 12 titanium bundles with Alloy 400 baffles were installed in the atmospheric crude distillation
column overhead/crude exchangers in 1994. These replaced carbon steel bundles that had failed every one to two
years, and had resulted in several unscheduled unit shutdowns. Crude oil was on the tube side, and atmospheric
crude distillation column overhead vapor was on the shell side. There were two exchangers in series and stacked
vertically. The atmospheric column overhead temperature entering the first (top) exchanger was 330°F (165°C).
The temperature in between the exchangers was approximately 295°F (146°C). Wash water carrying a proprietary
organic amine was injected between the two exchangers.

Inspection of both bundles in 1996 did not reveal any signs of corrosion, and they were described as in
like-new condition. However, leaks developed in 1998 in many of the tubes in the second (lower) exchanger.
Examination indicated that the tubes had failed by OD corrosion in areas where they were in contact with the
baffles, as shown in Figures 4 and 5. There was also some generalized OD pitting corrosion away from the
baffles, as shown in Figure 6. Hydriding o f the titanium was found in all of the corroded areas. Near the failed
areas, the hydriding had penetrated completely through the tube wall.

The neutralizing amine used in this case is one that forms a high-melting point, solid chloride salt, similar
to NH4CI. Further investigation revealed that problems with flow control o f the wash water injected into the
overhead vapor resulted in an insufficient quantity o f wash water. The wash water carrier for the neutralizing
amine completely evaporated, and the temperature was too high to allow water to condense in the exchanger. As
a result, a highly corrosive "dry" amine chloride salt tended to accumulate at the crevices between the tubes and
baffles. At the elevated temperatures, titanium could not maintain its passivity, especially in the underdeposit or
crevice conditions present under the baffles. The result was corrosion and hydriding o f the tubes, concentrated
where they passed through the baffles.

There were no leaks found in the top exchanger bundle, therefore it was not inspected. Presumably, the
tubes did not corrode because there were no salt forming neutralizers present in the top exchanger.

Case 7 - Crude Distilling Unit

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 A grade 2 titanium exchanger bundle was installed in a second stage overhead condenser of the
atmospheric crude distillation column overhead in 1990. The hot accumulator upstream of the exchanger operates
at 275°F (135°C). Some mechanical damage during installation caused leakage in a few peripheral tubes. But,
overall, the bundle performed very well. In 1999, a second titanium bundle was installed in the exchanger
immediately downstream. The inlet temperature is approximately 250°F (121°C), and it is expected to perform
well.

Because of the favorable experience in this unit, eight overhead condensers in a second atmospheric crude
distilling unit in the same refinery were replaced with grade 2 titanium over the past several years. The overhead
temperature of this unit is approximately 285°F (141°C). All bundles have performed well to date.

Laboratory Test Results in Dry Ammonium and Amine Chloride Salts

We have conducted a number of laboratory experiments to determine corrosion of titanium alloys by

ammonium and various amine chloride salts. Tests were conducted in seal, high strength glass tubes under static
conditions. Pure amine chloride salts were made by reacting amine and hydrochloric acid and subsequently
purified by recrystallization. Figure 7 shows data on a select group of titanium alloys and Alloy 400 in a molten
amine chloride salt at 300°F (149°C). It was found that titanium alloys, including grade 7, 12 and 16, are highly
susceptible to corrosion when subject to "dry" amine salt conditions. Addition of small amounts of liquid phase
water (l%wt) was sufficient to passivate the titanium alloys. High temperatures tended to accelerate the active
dissolution rate. However, active behavior was detected in dry salt conditions as low as 250 °F (121 °C).

CONVERSION UNIT FRACTIONATOR OVERHEAD SERVICES

Conditions similar to those found in the atmospheric crude distilling column overhead are present in the overhead
systems of fractionation columns in other downstream refinery units, such as fluid catalytic cracking unit (FCCU)
and delayed coking unit (DCU). The FCCU and DCU fractionator overhead streams contain high levels of NH3
and H2S along with lesser concentrations of HCN, HCI, SO2, and CO2. Ammonium polysulfide or proprietary
filming amine inhibitors are sometimes injected to help with corrosion control in these overhead systems. We
have limited applications of titanium and titanium alloy tube bundles in these overhead condensing systems.

Case 8 - FCCU Fractionator Overhead Condenser

Grade 2 titanium tubes were installed in 1992 in the fractionator overhead/cooling water exchanger in a
new residue FCCU. This is a very large, vertical, shell-and-tube exchanger with one tubeside (process) pass, and
cooling water on the shellside. Water wash is continuously injected into the fractionator overhead vapor
immediately upstream of this exchanger to control ammonium chloride deposition. The water wash reduces the
fractionator vapor temperature from approximately 280°F (138°C) to 216°F (102°C). This lower temperature
permitted the selection of grade 2 rather than grade 12 titanium. Performance has been excellent.

Case 9 - DCU Fractionator Overhead Condenser

Grade 12 titanium tubes were installed in the overhead air cooler of a new DCU in 1996. The overhead
temperature is 285°F (141°C). The overhead condensate leaving the air cooler contains about 4%wt NH4HS and
cyanides up to 120 ppmw. The air cooler has been very reliable thus far.

S O U R W A T E R S T R I P P E R O V E R H E A D SERVICES

Refinery sour waters from hydroprocessing units, conversion units, and various other sources have to be
stripped in sour water strippers (SWS) to remove H2S and ammonia. The resulting SWS column condensed
overhead water can contain as much as 30-40%wt ammonium bisulfide along with chlorides, cyanides, and other

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 corrosive species. Titanium is one of the few materials with high resistance to concentrated ammonium bisulfide.
Titanium is used for overhead condenser bundles in sour water strippers when conditions are very aggressive.

Case ! 0 - Sour Water Stripper Overhead Condenser

In 1992, grade 2 titanium tubes were used to retube a shell-and-tube overhead condenser for a stripper
column treating sour water from the catalytic cracker gas plant. The original Alloy 800 tubes had experienced
through-wall pitting attack in seven years. The temperature o f the inlet vapor to the exchanger is approximately
221°F (105°C), and the condensate leaving the exchanger contains 9-1 !% ammonium bisulfide with a minor
amount of chlorides. No cyanides have been detected. The exchanger has not been inspected since the titanium
tubes were installed, but has performed well to date.

Case l I - Sour Water Stripper Overhead Condenser

In 1995, a grade 2 titanium air cooler (tubes and header boxes) was installed in a sour water stripper. The
stripper treats sour water from a coker, coker gas plant, gas oil hydrotreater, and several amine treating units. The
temperature of the inlet vapor to the air cooler is 245°F (118°C) maximum. The condensate leaving the air cooler
contains approximately 15% ammonium bisulfide, 30-35 ppm chlorides, and 30-50 ppm cyanides. The air cooler
has not been inspected to date but has not experienced any performance problems.

Case 12 - Sour Water Stripper Overhead Condenser

In 1996, a grade 2 titanium air cooler (tubes and header boxes) was installed in a new sour water stripper
as part of a new project. The stripper treats sour water from a delayed coker, a distillate hydrotreater, and a sulfur
recovery unit. The temperature of the inlet vapor to the exchanger is approximately 245°F (118°C). The
ammonium bisulfide concentration in the condensate leaving the air cooler is approximately 18%wt, with 80 to
100 ppmw cyanides. The air cooler has not been inspected to date but has not experienced any performance
problems.

OTHER APPLICATIONS

Throughout the years, titanium has been used in various other refining applications, mostly as tube
bundles in energy integration exchangers. Utilization o f grade 2 titanium has not been very successful in such
applications because of its temperature limitations. The following are some additional case histories, most
involving failures.

Case 13 - Straight Run Naphtha Hydrotreater Stabilizer Feed/Bottoms Exchanger

A grade 2 titanium tube bundle was installed in the feed/bottoms exchanger o f a stabilizer column in a
straight run naphtha hydrotreater in 1971. The stabilizer feed on the shell side is at temperatures up to 287°F
(142°C). The stabilizer bottoms on the tube side is at a temperature of 476°F (247°C). The tubes were inspected
after 25 months of service and were found to be at their original thickness. However, after another 10 months in
service the tubes failed by localized attack from both ID and OD, as shown in Figures 8-10. Crevice corrosion
was also found on the adjacent behind the hotter portion o f the tubesheet. The localized corrosion was attributed
to ammonium chloride salts at tube metal temperatures reaching 350-400°F (180-200°C). Installation of thermal
insulation on both sides o f the tubesheet apparently reduced the titanium tube metal temperature to a less
corrosive range; no further tube failures occurred in three years o f subsequent operation. The tube bundle was
eventually replaced with carbon steel.

Case 14 - Sour Water Stripper Reboiler

Grade 2 titanium tubes were installed in a carbon steel shell o f a sour water stripper reboiler, replacing a
carbon steel bundle that was corroding at 85 mpy (2.2 mm/y). Superheated steam at 475°F (246°C) enters the

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 tubeside. Sour water at temperatures between 245-255°F (118-124°C) enters the shellside. After two years of
service the titanium tubes failed from attack by sour water. The failure mode was mostly intergranular cracking.
Moderate to severe general metal loss was also observed on the titanium tubes. The failure was attributed to the
presence of fluoride and chloride and elevated tube metal temperature. Fluoride in the sour water was believed to
have originated from hydrocracker catalyst.

Case 15 -Sour Water Stripper Feed/Bottoms Exchanger

Grade 2 titanium tubes were installed in one of four feed/bottoms exchangers in a sour water stripper in
1977. The shell of the exchanger was carbon steel. Sour water stripper bottoms enters the shellside at 215°F
(102°C), while the feed enters the tubeside at 160°F (71°C). Inspection of the exchanger after three years and ten
years of service showed that the tubes had no visible metal loss. However, leaks were discovered during a pre-
startup pressure test in 1991 (after 14 years of service). Several tubes were reported to have split under the testing
pressure. Further examination of these tubes revealed that they were "brittle". Hydriding of the titanium tubes as
a result of corrosion of the carbon steel shell was suspected to be the cause of the failure. The exchanger bundle
was replaced with carbon steel.

O X I D A T I O N AND P Y R O P H O R I C I T Y

Titanium in the form of metal powder is pyrophoric. So is heavily corroded titanium when corrosion
leaves a high surface area, sponge-like structure. We have experienced one incident involving ignition of
titanium. This occurred when the tubesheets were being cut off of a used titanium tube bundle. Apparently, the
cuttings ignited. This incident and industry reports prompted us to think carefully about fabrication and
maintenance activities so as to avoid running into additional pyrophoricity problems with titanium.

Case 16 - Catastrophic Oxidation of Condenser Tubes

This heat exchanger incident may not have involved pyrophoricity of the titanium itself, but it did involve
pyrophoricity of iron sulfide corrosion products in the exchanger. The exchanger in question was an atmospheric
crude distillation column overhead condenser in a crude distilling unit, with overhead vapor condensing on the
shell side. The exchanger contained grade 2 titanium tubes to resist corrosion by condensing HCi and ammonium
chloride salts. The shell and connecting piping were carbon steel. The exchanger in question was the second
from the top in a vertical stack of four condensers.

Corrosion of steel components in refinery systems containing hydrogen sulfide often results in the
formation and accumulation of iron sulfides in equipment during service. These sulfides can be pyrophoric,
oxidizing exothermally and eventually igniting when the equipment is taken out of service and exposed to air.
Precautions are normally taken, such as keeping the equipment wet enough that oxidation heat is removed by
evaporation, so that ignition cannot occur.

In this case, the bundles in the exchangers both upstream and downstream had been removed, but removal
of this bundle was delayed. During the delay, continued aspiration of the shells allowed the iron sulfides in the
bundle to dry out, begin to smolder, and then ignite. The empty exchanger shells on each side and interconnected
piping acted like a chimney providing draft, increasing the temperature until the titanium rapidly oxidized. The
high elevation of the exchanger made fire fighting difficult, and the fire burned for hours before it could be
extinguished. The result was destruction of the entire heat exchanger.

Subsequent examination of the bundle showed that the titanium tubes had been completely oxidized,
leaving only "husks" of titanium oxide, as shown in Figure 11. By contrast, carbon steel baffles and the carbon
steel exchanger shell were warped, but mostly still there. Further analysis convinced us that total oxidation of the
titanium tubes could have occurred without invoking titanium pyrophoricity. The lesson is that titanium can be
severely damaged by oxidation under conditions where materials not known for high oxidation resistance are
relatively little affected.

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 CONCLUSIONS

Knowledge about corrosion resistance of titanium and its alloys in various refining environments have been
mostly accumulated by trial-and-error. Although most applications have been successful and cost-effective, some
costly failures have occurred as a result of such practice. Understanding the limitations of titanium alloys in terms
of temperature and various corrosive conditions is very important to ensuring their continued successful use.

Additional work is necessary to understand the limitations of titanium alloys in the wide range of
conditions encountered in refining processes, especially in CDU, SWS, FCCU and DCU overhead systems. The
ability to relate corrosion resistance to operating conditions such as type of amine, presence of ammonia, chloride
concentration, water content, and temperature is needed in order to confidently use titanium alloys.

REFERENCES
!. R. L. Jacobs and J. A. McMaster, "Titanium Tubing for Refinery Heat Exchangers Service," NACE
CORROSION/72, Paper #17

2. J. A. McMaster, "Titanium - Economical Corrosion Control Tool for Petroleum Refineries," NACE
CORROSION/77, Paper #102

3. J. A. McMaster, P. N. Blauvelt, and D. Rowan, "Titanium - Proven Performance in Hydrocarbon

Processing," CORROSION/2000, Paper #684

4. L.C. Covington and W. M. Parris, "Investigation of Titanium Tube Failures at Shell Oil Company, Martinez,
California ," Technical Report No. 49, TIMET, June 1975.

5. 1. A. Franson and L. C. Covington, "Application of Titanium to Oil Refinery Environments", API Mid-Year
Meeting in Chicago, Illinois, 1977

6. TIMET, "Titanium for Refinery Use," Technical Bulletin RT-2, March 1984.

7. W.J. Neill, "Experience with Titanium Tubing in Oil Refinery Heat Exchangers," NACE CORROSION/79,
Paper #31

8. K. Suzuki and Nakamoto, "Experience with Titanium Heat Exchangers in Oil Refineries," Materials
Performance, June 1981.

9. R.W. Schutz & R.L. Porter, "Lower Cost Ruthenium-Enhance Titanium Alloys for Severe Chemical
Service", Reactive Metals in Corrosive Applications Conference, September 12-16, 1999, Sunriver, Oregon.

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 (a)
(b)

Figure 1. Isolated Underdeposit Pits in Grade 2 Titanium

Tubes from an CDU Atmospheric Tower
Overhead Condenser (Case 1)

(c)

Figure 2. Deposits at Edge of a Pit in a Grade 2 Titanium

Figure 3. Electron Microscope Chloride Scan of Deposits at
Tube from an CDU Atmospheric Tower Overhead Edge of Pit in a Grade 2 Titanium, CDU
Condenser (Case I, 100X) Atmospheric Tower Overhead Condenser (Case I,
100X)

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 Figure 4. Corrosion Penetration Of A Grade 12 Titanium Figure 5. Corrosion Of Grade 12 Titanium Tubes Near The
Tube Under A Baffle In A CDU Atmospheric Baffle In A CDU Atmospheric Tower Overhead
Tower Overhead Condenser. (Case 6) Condenser. (Case 6, 1.2X)

10000

I000

Q.
g lOO
1
~ 10

o
U
0.1

0.01
Alloy 400 TI 7 Ti 16 T112
• Dry(100% salt) [] W e t ( l % H20) I

Figure 6. Pitting Corrosion of the Grade 12 titanium CDU Figure 7. Corrosion Of Titanium Alloys And Alloy 400 In
Atmospheric Tower Condenser Tube At Locations A Liquid Amine Chloride Salt At 300°F (149°C)
Away From The Baffles. (Case 6, 20X)

Figure 8. Perforation Resulting from Tubeside Corrosion of Figure 9. Extrernaly Corroded and Fractured Grade 2
A Grade 2 Titanium Tube In A Naphtha Hydro- Titanium Tube In A Naphtha Hydrotreater
treater Stabilizer Feed-to-Bottom Exchanger Stabilizer Feed-to-Bottom Exchanger (Case 13,
(Case 13, 1.4X) 1.4X)

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Figure 10. Internal Surface Corrosion of a Grade 2 Titanium Figure 11. Completely Oxidized Grade 2 Tubes From A
Tube from a Naphtha Hydrotreater Stabilizer CDU Atmospheric Tower Overhead Condenser
Feed-to-Bottom Exchanger (Case 13, 3X) In Which Pyrophoric Iron Sulfides Ignited.
(2.5X)

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