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A Case Study on Caustic Corrosion in Refinery Piping

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721 THE INTERNATIONAL JOURNAL OF ENGINEERING AND INFORMATION TECHNOLOGY (IJEIT), VOL. 3, NO. 2,JUNE 2017

A Case Study on Caustic Corrosion in

Refinery Piping
Salem Ali Karrab
University of Misurata, Faculty of Engineering , Department of Materials Science & Engineering
[email protected]

Abstract— Caustic soda is received from supplier with When the spacers fall down /slip out during assembly and
concentration about 48% and stored at main storage tank by means of expansion and contraction during operation
and transferred intermittently to the refinery process unit's the bare tracer will gets pressed against the pipe causing
neutralization tanks at same concentration. Dilution is direct wall-to-wall contact and hot spots with steam
taking place at these tanks. In order to prevent caustic soda
tracing.
from freezing and /or crystallization (winterization) in
intermittent transferring piping, it was kept warm by means Carbon steel finds extensive application primarily
of steam tracing and insulation together. because of its low cost, reasonably good mechanical
Failure of carbon steel piping by caustic stress corrosion properties, and ease of fabrication [2]. Despite its limited
cracking (embrittlement) and caustic gouging has been a corrosion resistance; it is routinely used for most organic
recurring problem, several repairs attempts were made chemicals and neutral or basic aqueous solutions at
without success using patch plates and/or temporary moderate temperatures and frequently used in services
clamps. Some parts were totally replaced with schedule 80 with added thickness to assure the achievement of desired
piping but suffer failures within 12 months. service life [3].
Close observation of the corroded locations reveals severe
Exposure to high solution strength caustic can result in
grooving along the length of pipe at 3 & 9 o'clock positions
where steam tracing line is touching the pipes due to general corrosion of carbon steel above 79oC and very
braking of fixation clamps. high corrosion rates above 93oC [4]. Caustic corrosion
Several measures were recommended, these include can occur when the pH is raised excessively on a
avoidance of hot spots by steam tracing; avoidance of localized scale, where the protective oxides are no longer
temperature increase during idle condition and redesigning stable. Such undesirable pH excursions tend to occur in
the distribution piping in order to transfer caustic solution high temperature zones, where boiling has led to a
with concentration not more than (33%). localized caustic concentration [5]. The gouging is a type
of corrosion that occurs on a metallic surface in which a
Index Terms: Caustic soda, gouging, embrittlement, steam
hole, groove or indentation is created and results in
tracing, Umm Alnar Refinery
irregular wall thinning, the corrosion can proceed to
failure in a very short time. It is found under deposits in
heat exchangers, results from concentrated caustic left
I. INTRODUCTION behind after boiler water permeates the deposits and
ome process units utilize caustic solutions for evaporates [6].
S neutralizing or removal of sulfur compounds. The
liquid sodium hydroxide freezing point varies
Additionally, caustic can cause caustic embrittlement
of non-post weld heat treated carbon steel and of
depending on the concentration. A 50% by weight austenitic alloys including stainless steels and nickel
solution of sodium hydroxide begins to congeal and alloys [7]. It is a form of stress corrosion cracking
crystalize at temperatures as high as 10 – 12°C, so it characterized by surface-initiated cracks that propagate
should be stored above 15.5°C [1]. Stagnant diluted dramatically. Cracking can occur even at low caustic
caustic solution may become highly concentrated if water levels if a concentrating mechanism is present. In such
is allowed to evaporate, especially near hot surfaces, and cases, caustic concentrations of 50 to 100 ppm are
in dead legs. This is particularly true when using heat sufficient to cause cracking [4].
traced piping, and if handling system is only used Early cases of CSCC in CS were associated with
intermittently. Steam tracing and insulation were used riveted steam boilers, where cracks started in metal that
together to keep the transfer piping in a warm condition was highly stressed in tension. The majority of more
and prevent caustic soda from freezing. Steam traced recent industry cases are associated with non-stress-
piping prevented from touching the caustic piping by relieved welds, typically in the heat-affected zone (HAZ)
applying ceramic spacers. and adjacent base metal. Although rare, cracking can also
occur away from welds if high tensile stresses are present
[8]. Austenitic stainless steels may resist CSCC up to
Received 21 October 2016; revised 22 November 2016; accepted 7 93°C whereas at higher temperatures Nickel base alloys
December 2016. will be recommended.
Available online 8 December 2016. The so-called NACE caustic soda service chart
explained corrosion resistance of carbon steel, stainless
steel and nickel alloys in caustic solutions with respect to
www.ijeit.misuratau.edu.ly ISSN 2410-4256 Paper ID: EN039
 Salem Karrab/ A Case Study on Caustic Corrosion in Refinery Piping 128

CSCC, based on temperature and concentration caustic on 1/2" steam tracing piping. Steam tracing was found
[9]. online even without caustic transfer (intermittent).
This paper intends to review process parameters,
inspection findings and failure histories experienced in
caustic piping of Um Al-Nar refinery in Abu Dhabi, and
find possible causes of the failure and recommend
remedial measures to avoid reoccurrences in future.

II. BACKGROUND
Caustic soda is received from supplier with
concentration about 48% & Chloride content of 125
PPM and stored at main storage tank (4008F) in unit 40
and transferred intermittently to refinery process units
neutralization tanks (1103-L, 1358L, 1501L &2011F) at
same concentration. Refer to figure 1 and table 1, dilution
is taking place at these tanks as per end user requirement. Figure 2a. Caustic Gouging

Figure1. Layout of Existing Feed and Distribution Caustic Piping to All

Refinery Units

Table 1. Refinery UNIT'S Daily Caustic Consumption

Design Periods of Figure 2b. Caustic Embrittlement (CSCC)
Concentration
Unit consumption caustic
level
L/D transfer
Once in 15
Unit11 3% 3600 III. DISCUSSION
days
Unit 13 20% 240 Once per shift
Once in 15 As per caustic service chart in Figure 3, Caustic
Unit 15 30% 1200
days solutions can be handled and stored safely with carbon
Unit 17 3% 1754 Once in 5 days steel equipment at temperature approximately 65 oC
Unit 17 10% 3571 Once in 5 days
Unit 40 48% 434 Once in 3 days
However, for caustic service above 65°C, carbon steel
must be post weld heat treated to avoid CSCC at welds
and properly fitted none metallic spacers or better using
Caustic leakage due to failure of carbon steel piping by
pre-insulated tracer, that will eliminate hot spots since
caustic corrosion has been a recurring problem in refinery
tubing is continually isolated along its length.
caustic transfer and distribution piping with different
During summer days metallic piping temperature can
sizes (¾"- 4"). Several repairs attempts were made
sometimes exceed 70°C, due to solar energy, particularly
without success using batch plates and/or temporary
if the system is stagnant with steam tracing, the
clamps. Some parts were totally replaced with schedule
temperature will go higher and caustic corrosion/cracking
80 piping but suffer failures within 12 months.
can be expected. In order to prevent increasing caustic
Subsequent detailed visual inspection revealed that
concentration by higher temperature, it has been warned
failures of caustic piping took the form of caustic gouging
against leaving even lower concentrations of caustic
and caustic stress corrosion cracking CSCC (caustic
solutions in heat traced piping during intermittent
embrittlement), as illustrated in figures 2a&b. The
injection. This can be achieved by water flushing the
affected area were mainly elbows, weld joints and heat
system after every use using preferably steam condensate
affected zones (HAZ). The severe corrosion concentrates
water. As per proposed new dilution skid at unit 40,
at 3 & 9 o'clock positions, it is more severe at 3 o clock
figure 4, the transfer of high concentrated caustic for long
position where steam tracing line is touching compared
distance will be eliminated and this in turn will avoid
with 9 o'clock position, particularly where fixation
material degradation and personnel injury.
clamps (spacers) were broken. Non-frequent failures were
The lowest recorded refinery climate temperature in
also noticed in non-insulated and none traced pipes.
winter at night time was around 6°C and freezing
Pipe skin temperature is measured at some locations
temperature of liquid 50% caustic is around 10 – 12°C
and found approx. = 55 °C on 2" caustic pipe and 87°C
www.ijeit.misuratau.edu.ly ISSN 2410-4256 Paper ID: EN039
 721 THE INTERNATIONAL JOURNAL OF ENGINEERING AND INFORMATION TECHNOLOGY (IJEIT), VOL. 3, NO. 2,JUNE 2017

[1], therefore insulation alone can be fair enough to

maintain a minimum of 16°C temperature without
crystallization.
IV. CONCLUSION AND
RECOMMENDATIONS
 The failure of carbon steel piping is most likely to
be due to caustic cracking and caustic gouging at
weld joints, elbows and supports.
 Since the caustic is transferred intermittently
from utility storage to other units dilution skids,
where the piping is left idle with local
temperature increase by steam tracing. This may
in turn concentrate the left caustic and accelerate
attack especially in summer time.
 Carbon steel can be still used in distribution
piping to handle caustic solutions with
concentrations below 35% and at temperature up
to 75oC with proper stress relieving and properly
fixed non-metallic spacers or better using pre-
insulated tracer.
Figure 3. NACE Caustic Soda Service Chart [9].
 To avoid caustic stagnation condition during idle
times it might be advisable to water flush the
transfer lines after every use using preferably
steam condensate water and by implementing the
modification of proposed dilution pit at unit 40.
 Steam tracing maybe avoided in concentrated
caustic supply piping, since insulation alone can
maintain a minimum of 16°C temperature
without crystallization.

REFERENCES
[1] T. P. HOU, "Manufacture of Soda Ash," 2nd Ed. N.Y., Reinhold
Publishing Corp., 1942. From Industrial Engineering Chemistry,
Vol. 46, No 11, p. 2401. Figure 4. Layout of Modified Feed and Distribution Caustic Piping
[2] S. L. Chawla and R. K. Gupta, "Materials Selection for Corrosion to All Refinery Units
Control,". Materials Park, Ohio, ASM International, 1993.
[3] D. W. Green and H. R. Perry, "Perry's Chemical Engineers
Handbook," 8th Ed. , McGraw-Hill, 2008.
[4] American Petroleum Institute, Damage Mechanisms Affecting
BIOGRAPHIES
Fixed Equipment in the Refining Industry-1st ed., API- RP 571,
2003. Salem Ali Karrab was born in Misurata. Libya
[5] Roberge, P. R., Handbook of Corrosion Engineering. New York: in 1963. He received the BSc degree in
McGraw-Hill, 2000. Metallurgical engineering from University of
[6] Corrosion Control in the Refining Industry, NACE Course Book, Tripoli, in 1987, and the MSc. Degree in
NACE International, Houston, TX, July 2011. corrosion engineering from University of
[7] A. Al-Omari, A. Al-Zahrani, G. Lobley, R. Tems, and O. Dias, Manchester "UMIST" in 1998 and PhD degree
NACE International Corrosion Conference and Expo Corrosion in corrosion engineering from University of
"Refinery Caustic Injection Systems: Design, Operation, and Case Assiut, Egypt in 2013. He also holds
Studies" pp.4933, 2008. International Diploma in Safety Management from British Safety
[8] National Association of Corrosion Engineers – Recommended Council in 2000. He has 17 years experience in inspection and corrosion
Practice - Avoiding Caustic Stress Corrosion Cracking of Carbon in refinery and petrochemical industries with RASCO and ADNOC. He
Steel Refinery Equipment and Piping, NACE RP-0403-2003. is currently a lecturer in Materials Science at Misurata University since
[9] National Association of Corrosion Engineers, Corrosion Data 2006. His main areas of research interests include failure analysis,
Survey - Metals Section, 6th ed. NACE 37519-85, Houston, TX, corrosion & control, surface engineering and industrial safety and
2000. environmental protection.
[10] R. Baboian, "Corrosion Engineer’s Reference Book," 3rd ed.
editor, National Association of Corrosion Engineers (NACE),
Houston, TX: NACE, 2002.

www.ijeit.misuratau.edu.ly ISSN 2410-4256 Paper ID: EN039

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