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Caustic cracking: Incidents in refineries

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CAUSTIC CRACKING:
INCIDENTS IN REFINERIES
Graham R. Lobley, Iyad A. Al-Buraiki, Abdelhak Kermad, Khalid M. Al-Nabulsi

Saudi Arabian Oil Company

SUMMARY: Caustic soda is used in several refinery processes, for example in crude distillation
units for chloride corrosion control and in some mercaptan removal units. Caustic cracking can
occur in carbon steel piping and equipment handling caustic and also in downstream equipment, if
caustic carryover occurs. Careful design and operation of caustic injection equipment is needed to
ensure adequate dispersion of diluted caustic before injection into the carbon steel crude charge
line of the crude distillation unit. For hot caustic service, appropriate materials selection and
process operation are essential. Three cases of caustic cracking are illustrated in: (i) non-stress
relieved carbon steel piping; (ii) austenitic stainless steel heat exchanger tubing; (iii) a UNS N08825
alloy caustic injection quill. The damage mechanism is identified via metallurgical failure analysis,
including metallography, fractography and microanalysis. Finally, recommendations are provided
to prevent recurrence of failure.

Keywords: caustic stress corrosion cracking, refineries, caustic injection and treatment, failure
analysis

1 INTRODUCTION
Environmental cracking or stress corrosion cracking (SCC) is a major damage mechanism within the oil industry. Sulfide
stress corrosion cracking (SSC) is often the principal form of cracking affecting both the upstream and downstream sectors.
Several other SCC damage modes can also operate in petroleum refining (1-3), notably chloride and polythionic stress
corrosion cracking of austenitic stainless steels and caustic stress corrosion cracking of carbon steels and austenitic stainless
steels (4). Stress relief or post weld heat treatment is an effective method of mitigating caustic cracking in carbon steels (2, 5).

1.1 Caustic stress corrosion cracking review

Caustic stress corrosion cracking (CSCC) has been a significant problem in non-stress relieved carbon steel equipment in some
gas plants and refineries. In a key review of CSCC in carbon steel equipment in company plants, McIntyre (6) noted that
cracking problems had been observed in several processes, particularly Merox (mercaptan oxidation) gas treating units. In the
early 1990s, CSCC was experienced where caustic is used to treat liquefied petroleum gases (LPG). Merox units at both
refineries and gas plants have been affected, with cracking incidents experienced in caustic prewash drums, caustic settlers,
extractor vessels, sand filters and associated piping. CSCC has also been reported in some fractionation sections, although
these are nominally free of caustic. In some cases, low levels of caustic have apparently carried into fractionation streams in
recycled butane. Caustic concentrated in crevices, and due to evaporation, causing CSCC in debutanizer reboilers. NACE RP
0403-2003 (5) is a recommended practice for avoiding CSCC, in carbon steel refinery equipment and piping. It includes a
caustic soda chart (Figure 1) that defines three areas (A, B and C) for material application as a function of increasing
temperature and caustic concentration. Area A identifies “safe” region for non stress relieved carbon steel, area B a region in
which stress relieved carbon steel is recommended, following welding and significant cold working and area C, at temperatures
above 110 ºC, where only nickel alloys are recommended for all caustic concentrations.
Though historically, CSCC problems have been primarily associated with carbon steel equipment (4, 5), more recently cases of
CSCC have also been encountered in some corrosion resistant alloys operating at higher temperatures. Cracking cases in 316H
austenitic stainless steel heat exchanger tubes and an Incoloy 825 caustic injection quill are also presented. Rebak (7) recently
reviewed industrial experience of CSCC in stainless steels and nickel-based alloys. In common with earlier references (8, 9),
regarding the effect of alloying elements, nickel levels exceeding 30% reportedly increased cracking resistance. A detrimental
effect upon cracking was also referenced when sulphide is present in caustic (6, 7). Thus, if caustic is contaminated, especially
with sulphide compounds, CSCC has been observed in Area A of the caustic soda chart (6). More specifically, oxidisable

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sulphur compounds increase the corrosion rate on Nickel 200, active species including hydrogen sulphide, mercaptans and
sodium sulphide (9).

2 CASE 1: CARBON STEEL CRUDE LINE IN AN ATMOSPHERIC DISTILLATION UNIT

2.1 Summary
Caustic soda is injected into the crude charge line of refinery crude distillation units to control chloride corrosion in the crude
unit overhead system. In this particular plant configuration, caustic is injected downstream of the desalter (Figure 2).
Leakage in two carbon steel desalter line elbows downstream of the caustic injection point was attributed to CSCC, after about
22 years of service. No cracking was found in two more elbows examined from further downstream, closer to the preheat
exchangers. The root cause of the failure was attributed to a period of injection of excessively concentrated caustic extending
over two months. Recommendations to prevent recurrence included: (i) implement more effective controls to ensure injection
of correct strength caustic in future; (ii) upgrade the caustic injection system, including a crude slipstream, to improve caustic
premixing prior to injection into the crude stream; (iii) inspect the downstream preheat exchangers. Although the potential risk
of caustic cracking to piping and equipment (exchanger train) further downstream may be relatively low, a previous case at
another refinery resulted in both cracking of an elbow in the crude feed line and cracking within the crude preheat exchanger.
Five years ago, the crude line in case 1 was replaced up to the preheat exchangers with stress relieved carbon steel piping and
the caustic injection system was also upgraded. No further incidents have been reported since implementation of these
measures.

2.2 Background
Diluted caustic soda solution (3 to 5 ºBaumé or about 1.9 to 3.1 wt. % concentration) is injected from a Monel 400 alloy quill
to control overhead corrosion in the crude distillation unit, which is caused primarily by hydrochloric acid (HCl) corrosion.
After desalting, traces of salt are still entrained in the crude stream, which include some magnesium and calcium chlorides.
Readily hydrolysable magnesium and calcium chlorides produce hydrogen chloride at moderate reaction temperatures (above
about 160 – 250 ºC respectively) within the crude preheat train. The purpose of the dispersed caustic is to neutralise this HCl.
The exact mechanism is unclear, but some propose that caustic reacts directly with HCl as it is formed.
The crude temperature at the conventional caustic injection point is approximately 120 ºC. For approximately 2 months, a
higher strength caustic solution was accidentally injected (about 15 ºBaumé or 10.3 wt. % concentration). Crude line leakage
at two elbows was reported overnight, which eventually resulted in an emergency plant shutdown and a decision to replace the
complete line from the desalter to the preheat exchanger. Leaks were initially minor weeping type, but upon clamping one
elbow, the leak increased and the plant was shutdown. The failed elbows were submitted for metallurgical failure analysis.

2.3 Examination
Extensive cracking was confirmed adjacent to the two elbows’ girth welds. External surface cracking networks parallel to the
girth welds were confirmed with wet fluorescent magnetic particle inspection (WFMPI). Figure 3 shows two elbows as
received and Figure 4 shows the extensive cracking illustrated by laboratory-performed dye penetrant examination.
Microsections showed branched intergranular cracks in the weld heat affected zones and adjacent parent elbow material
(Figure 5). There was also localized metal loss downstream of the welds, which is attributed to increased erosion-corrosion at
these locally turbulent locations. Turbulence is triggered by both the direction change at the elbow and locally at the girth
welds, whose weld roots penetrate a few mm into the stream.

2.4 Discussion
The characteristic crack morphology — branched intergranular and filled with oxide corrosion products (Figure 5) —
supported a CSCC damage mechanism. A previous failure analysis of a carbon steel piping failure by CSCC showed high
sodium levels detected within a fine intergranular crack that was opened in the laboratory (Figure 6). This latter case is taken
from another refinery LPG Merox system (4). The interesting point in the current case is that the carbon steel is operating in
Area C of the caustic soda service chart (Figure 1), although one clause in the standard NACE RP0403-2003, paragraph 4.6,
suggests that low concentrations (below 5%) are normally acceptable. The key factors in reducing CSCC risk are reduction of
residual stresses by post weld heat treatment and improved caustic dispersion via better premixing using a crude slipstream in
the injection line.

3 CASE 2: 316 STAINLESS STEEL PREHEAT EXCHANGER TUBING IN A HYDROGEN PLANT

3.1 Summary
An emergency shutdown of a refinery hydrogen plant was caused by a heat exchanger leakage. The premature failures of type
316H austenitic stainless steel preheat exchanger tubes from a hydrogen unit were attributed CSCC. The primary root cause of
tube failures was caustic carryover from the amine treating unit. The tube material was consistent with its original
specification, SA 213 TP 316H, and no metallurgical anomalies were noted. The refinery was immediately recommended to
consult with process engineering to investigate and eliminate caustic carry-over to prevent cracking recurrence. Failure of this

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exchanger resulted in both appreciable repair costs and related revenue loss. Subsequent process engineering evaluation
revealed that the caustic coalescer in the amine treating unit was both undersized and further overwhelmed during periods of
higher hydrogen production demand.

3.2 Background
Hydrogen production uses a steam reforming process to produce hydrogen from LPG feed. Hydrogen is used to upgrade
heavier oil fractions, in processes such as hydrocracking and hydrotreating (or hydrodesulphurising). In this particular
refinery, the hydrogen is used for hydrodesulphurising, primarily to remove sulphur and nitrogen impurities from gasoil. The
hydrogen plant pre-heat exchanger experienced tube leaks following hydrotests during a major plant turnaround. The total
number of plugged tubes was 33% of the total, significantly exceeding the industry norm of 10%. In the previous six years, the
shell and tube preheat exchanger was reported to have provided satisfactory service. This exchanger was then replaced in kind.
After only 10 weeks of service, the hydrogen plant experienced an unplanned shutdown, due to leaking tubes in the newly
replaced exchanger. A second case of cracking was also subjected to detailed metallurgical evaluation. Two sets of tubes
were examined that leaked after just 13 and 22 weeks of service respectively.
The shell side normal operating temperatures are 100 ºC inlet and 380 ºC outlet. The tube side inlet temperature is 420 ºC and
outlet is 350 ºC. The shell side stream is LPG feed, the tube side stream is converted gas from the hydrogen reformer (mainly
hydrogen). The LPG feed has been sweetened and washed with caustic in the amine treating plant. The caustic settles in two
stages: during the caustic wash stage, then any remaining caustic settles in the LPG coalescer.

3.3 Examination
Several removed heat exchanger tubes were examined. Stereomicroscopy revealed multiple primarily transverse cracks on the
outer surfaces of the tubes (Figure 7), which were concentrated close to the roll expanded tube ends. Using fluorescent dye
penetrant testing, extensive cracking networks were apparent. Positive material identification with an optical emission
analyzer indicated that the chemical composition of the tubes complied with SA 213 TP 316H specification.
Metallography of tube cross-sections indicated that cracking originated at the tube outer diameter (shell side), initially in an
intergranular mode, with subsequent propagation in a brittle transgranular mode, with crack branching (Figure 8).
Microhardness on microsections indicated an average hardness value of 197 HV. Both microstructure and hardness indicate
that the stainless steel had been solution annealed, though some subsequent cold working due to tube roll expansion was also
indicated from dimensional measurements.
Fractography and microanalysis was performed using the scanning electron microscopy (SEM). The intergranular cracking
was extremely brittle in appearance (Figure 9). Tight secondary cracks were opened for further evaluation. Analysis of
corrosion products inside the cracks was carried out using energy dispersive spectroscopy (EDS), which confirmed substantial
sodium levels (33.8 wt. % or 54.0 atomic %) in the first case, strongly indicative of ingress of caustic species. An opened
crack in the second case also revealed significant sodium levels (13.9 wt. % or 28.2 atomic %) and no chloride was detected in
either case.

3.4 Discussion
EDS microanalysis confirmed moderate to high sodium levels on the opened crack faces of two cases (13.9 to 33.8 wt.%). In
summary, the characteristic crack morphology and substantial sodium levels inside the tight cracks supports a CSCC damage
mechanism.
A process engineering review subsequently revealed that the coalescer, whose function is to separate any caustic droplets from
the LPG feed, was significantly undersized. Additionally, operations were sometimes processing an extra 40% of LPG during
periods of high hydrogen demand. These two factors overwhelmed the coalescer, resulting in carryover to the stainless
exchanger.
Provided that caustic carry-over is curtailed, the exchanger tubes can be replaced with in-kind material, i.e. stainless steel type
316H. Upgrading the metallurgy of the tubes was not recommended, since the root cause of the damage was attributed to
process excursions and not material unsuitability. Cracking and isocorrosion charts for 316 and 304 stainless steel (8) suggest
that caustic cracking becomes a risk above about 130 ºC at 30 % caustic concentration, whereas for about 3 % caustic
concentration the apparent caustic cracking boundary is over 200 ºC. The caustic levels measured in cracks and the operating
temperature range of the tubes puts the stainless steel tubes in the cracking range.
It has been reported that commercial grade 50% caustic soda solutions may contain 50 ppm chlorides (9) and since the
cracking mode is very similar, some argue that unreported chloride impurities are responsible for the cracking. Although crack
morphology and fractography are very similar for both caustic and chloride stress corrosion cracking, some significance is
attached to microanalyses of opened tight cracks in the present case. High levels of sodium were confirmed within tight cracks
and no chloride was detected, so CSCC was implicated as the damage mode. Although there may be some interaction between
caustic and chloride, classic chloride cracking is promoted by acid conditions and suppressed by high pH whereas caustic
cracking requires high pH. With around 28 to 54 atomic percent sodium detected inside opened tight cracks, very high pH
conditions are inferred at the propagating crack tips.

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Caustic cracking of a 304 stainless steel bypass line has been reported in a steam methane reforming plant (10). In this case,
the cracking was attributed to potassium hydroxide that originated from a potassium-promoted reformer catalyst. All surfaces
downstream of the reformer showed significant potassium levels. The transgranular cracking was oxide-filled and very high
levels of potassium were noted in the EDS spectra from the fracture surface and no chloride was present within the cracks.
Thecurrent failure case is different in that it is upstream of the hydrogen reformer.

4 CASE 3: CAUSTIC CORROSION AND CRACKING ON INCOLOY 825 CAUSTIC INJECTION QUILL

4.1 Summary
A caustic injection quill made from Incoloy 825 (UNS N08825) failed prematurely by caustic corrosion and cracking. This
alloy evidently cannot handle caustic at the high temperature injection location, when in contact with high temperature crude
oil (290 ºC). Premature failure of the quill occurred after 11 months’ service, primarily as a result of excessive caustic
corrosion.

4.2 Background
An alternate location for caustic injection in crude transfer lines is upstream of the crude heater, where crude temperatures are
around 290 ºC. Though more risky, the motivation for injecting caustic at higher temperatures is to avoid fouling issues
sometimes encountered in preheat exchangers. Quills are traditionally made from Monel 400 alloy (UNS N04400). However,
since the crude is sour (high H2S levels), some sulphur corrosion of the Monel was also suspected as a possibility. So, an
injection quill made from Incoloy 825 (UNS N08825) was fabricated and installed. Although this Ni-based alloy nominally
contains 42% Ni, it failed prematurely by rapid caustic corrosion and cracking after just eleven months’ service.

4.3 Examination
Visual inspection showed significant wastage especially at the outer diameter of the quill tip, where it was exposed to the
highest temperatures within the stream (Figure 10). The quill tube was welded to the flange without stress relief. Although
this was a lower temperature exposure region (caustic premixed with crude slipstream around 200 ºC), significant transgranular
stress corrosion cracking was also observed (Figures 11, 12) in both the tube and flange material. In each case, cracking
initiated from the caustic stream side. The average rate of wall thinning at the quill tip was equivalent to about 154 mpy.

4.4 Discussion
Ni-base alloys, such as Incoloy 825, reportedly show appreciable caustic corrosion resistance (9), falling between stainless
steels and the higher Ni-alloys such as Alloy 600, though the specific data presented only included testing Incoloy 825 up to 66
ºC in 10% caustic concentration. However, Incoloy 800 (UNS 08800) showed a corrosion rate of 0.3 mpy in 73% caustic at
114 ºC, whereas the corrosion rate of Monel 400 was 0.5 mpy under the same conditions.
Rondelli (11) reported that CSCC resistance increases significantly with alloys above about 30% Ni, following testing at 200
ºC and 250 ºC, though Ni had a negative influence in the 10 to under 30% range. Both U-bend and slow strain rate (SSR) test
methods were used. Duplex stainless steels showed superior CSCC resistance compared to regular austenitic grades such as
316 stainless. 316 did not crack at 200 ºC but always cracked at 250 ºC. U-bend tested austenitic stainless steels showed
intergranular cracking, whereas with the tougher SSR tests, transgranular cracking was reported. Subsequent studies (12, 13)
reported the detrimental effect of sulphide ions in promoting CSCC in stainless steels at 200 ºC. When sulphide ions were
present, only transgranular cracking was reported in some alloys, whereas in the SSR tests without sulphide, mixed mode crack
propagation (intergranular and transgranular) occurred. A hydrogen damage mechanism was claimed by the suggested role of
the sulphide ions, which inhibit recombination of atomic to molecular hydrogen (12). The atomic hydrogen enters the lattice
and embrittles the alloys. The CSCC susceptibility of four higher austenitic alloys was studied at 200 ºC (13), including Alloy
825 (UNS N08825). This study also confirmed that CSCC increased markedly in the presence of sulphide ions, using a base
solution of 300g/l NaOH, with additions of 20g/l Na2S.9H2O.
In the present case, replacement quills using a closed-end, side-hole design were installed in Monel 400 alloy. The two quills
in parallel crude lines have been in service for over six years, without incident. The quills are periodically X-rayed in situ and
recently slight side hole enlargement was reported on one quill.

5 CONCLUSIONS
Effective mitigation of CSCC can be achieved in several ways, related primarily to materials and process-related issues as
follows:
Material:
Material selection is very important and stress relief heat treatment reduces cracking risk in carbon steels. Reduction of
residual tensile stresses adjacent to welds dramatically reduces risk of caustic cracking. For handling caustic at high
temperatures, higher Ni alloys are required and Monel 400 is a reliable field-proven alloy for injection quills in refinery

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services. Alloy 625 (UNS N06625) has also been used as an injection quill material by some refiners. Alloy 625 is reportedly
practically unaffected by caustic to about 320 ºC (8).
Process Environment:
Unexpected caustic carryover can cause repetitive cracking problems and must be eliminated if stainless steels are used for
exchanger tubes operating at high temperatures. Equipment such as caustic coalescers must be properly sized and maintained.
Stress relieved carbon steel crude lines give good service when low strength caustic is properly dispersed into the crude stream
by good injection system design and operation.

6 ILLUSTRATIONS

Overhead

Conventional injection
location

1st Preheat Desalter 2nd Preheat Heater

Train Train
Injection Upstream Atm. Column
of Heater

Figure 1: caustic soda service chart Figure 2: caustic injection locations in crude line

Figure 3: elbows as received Figure 4: cracking parallel to weld

Figure 6: intergranular cracking of LPG Merox carbon

Figure 5: branched intergranular cracking, x60
steel piping elbow, x1500

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Figure 8: 316H exchanger tube cracking, x200. Crack

Figure 7: 316H exchanger tube cracking
origin at tube outer diameter (top)

Figure 9: 316H transgranular fracture, x2000 Figure 10: Incoloy 825 injection quill

Figure 12: Incoloy 825 flange cracking, crack origin at

Figure 11: Incoloy 825 flange cracking, x750
tube side, x200

7 REFERENCES
1. NACE MR0175-2002: Sulfide Stress Cracking Resistant Materials for Oilfield Equipment
2. NACE RP0472: Methods and Controls to Prevent In-Service Environmental Cracking of Carbon Steel Weldments in
Corrosive Petroleum Refining Environments.
3. API RP 571: Damage Mechanisms Affecting Fixed Equipment in the Refining Industry-First Edition (2003)
4. G. R. Lobley, NACE-IOC Corrosion Odyssey, Session 3, Paper 2, Stress Corrosion Cracking in Refinery & Utility
Plants, Edinburgh, September 2001.
5. NACE RP0403-2003: Recommended Practice - Avoiding Caustic Stress Corrosion Cracking of Carbon Steel Refinery
Equipment and Piping

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6. D. R. McIntyre, A Review of Caustic Stress Corrosion Cracking and Its Occurrence in Saudi Aramco Plants,
Proceedings of the Materials Engineering and Corrosion Control Technical Exchange Meeting, Saudi Arabian Oil
Company, Dhahran, December 3 – 5, 1994
7. R. B. Rebak, Industrial Experience on the Caustic Cracking of Stainless Steels and Nickel Alloys – a Review, Paper
06501, CORROSION 2006
8. C. M. Schillmoller, Alloy Selection for Caustic Soda Service, NiDI Technical Publication 10 019, 1988
9. Corrosion Resistance of Nickel and Nickel-Containing Alloys in Caustic Soda and Other Alkalies, NiDI Technical
Publication 281, 1973
10. S. W. Dean, Caustic Cracking from Potassium Hydroxide in Syngas, Materials Performance, January 1999, 73 – 76.
11. G. Rondelli, B. Vicentini, M. F. Brunella,, A Cigada, Effect of Alloy Element Contents on Caustic Stress Corrosion
Cracking of Several Stainless Steels, Werkstoffe und Korrosion 44, 57-61, 1993.
12. G. Rondelli, B. Vicentini, E. Sivieri, Stress Corrosion Cracking of Stainless Steels in High Temperature Caustic
Solutions, Corrosion Science, vol. 39, no. 6, pp. 1037-1049, 1997.
13. G. Rondelli, B. Vicentini, Susceptibility of Highly Alloyed Austenitic Stainless Steels to Caustic Stress Corrosion
Cracking, Materials and Corrosion, 53, 813 (2002).

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