Micro-biological Induced Corrosion of Hot Oil heater tube

Malik.O.M*, Turi.M.H

(Petromaster, Al Khobar, KSA)

October, 2017

Abstract

The failed tube is from the Fin Fan Cooler System operated by the Farabi Petrochemical Company in
Jubail, Saudi Arabia. The cooler system is present in the Pacol Enhancement Process which is designed
to remove aromatic compounds from the C10 to C14 paraffin/Olefin product from the Pacol Process.
The unit is typically designed to remove about 80% of the aromatics that are normally present in the
Pacol product, with minimal loss of paraffins and Olefins. The PEP unit has two sections: the
adsorption section and the fractionation section. The adsorption section consists of six adsorbers loaded
with molecular sieve which remove the aromatics from the Pacolate. The fractionation section typically
consists of two columns which are used to recover the purge material and the desorbent.
Aromatics in the feed are adsorbed in the pores of the molecular sieve during the adsorption step. In
the adsorption step, aromatics are displaced from the molecular sieve by the desorbent (usually
benzene). Because the desorbent and the adsorbed aromatics boil at different temperatures, they can
be separated fractionation. In order to prevent the loss of paraffin/Olefin feed due to mixing with the
desorbed aromatics, a purge step is necessary. This study investigates the leakage of a condenser tube
from such system

1. INTODUCTION
The tube failure occurred on 1st Feb 2018, where a leak found at 501-EA-01A tube bundle. Bundle
was handed over to maintenance and leak test was carried out. 2 tubes found leak and were plugged.
Hydro test was carried out and found 5 new leak locations. After cleaning of two suspected rows and
16 tubes were found leak and plugged.

2. View from Floating header box

Figure 2 Schematic for thickness loss

MFL tests revealed that majority of the tubes in the outlet section, showed loss of thickness of varying
amount as depicted in the above schematics. The sample selected for the analysis, its thickness was
almost ae end. It was informed by the client that one of the tubes during inspection showed leakage. A
tube was selected for in-depth metallurgical analysis.

Figure 3 External appearances of the header and finned tubes headers observed during
inspection

2 TECHNICAL RESULTS

2.1 Visual Examination

The general appearance of the as-received sample can be seen in Figure 4. It can be seen that the
external surface is mostly covered by aluminium fins, some of which are externally distorted. The
central location of the tube sample reveals pin-hole leakage. The close up view of the pin-hole is
presented in figure 5. The external surface in the proximity of leakage shows uniform external
corrosion. The external surface is covered by light-brown deposit layer without severe corrosion signs.

Fig. 4: General view of the as-received sample

 X X”

Fig. 5: Close up view of the as-received sample

The pin-hole was observed to be circular and diametrically measured up to 2.5 mm. The opposite side
to the pin-hole presented some signs of localised corrosion also. However the extent of external
corrosion was not much severe. The tubes were sectioned longitudinally along the X-X” axis as
presented in figure 5. The internal surface is presented in figure 7 which shows different appearance
of the leak side and the opposite side. The pin-hole side revealed dark brown and strongly adherent
layer of corrosion products on the inside surface.

Multiple wide and shallow pits were also evident. Figure 8 (c) & (d) shows signs of localized corrosion
in forms of pits. These pits were observed to be of varying size and depth. The periphery of these pits
contained reddish-brown corrosion deposits. The pit morphology was cup-shaped and they were
concentrated to a localized area.

2.2 Metallographic Examination

Sections were cut at the locations shown in Figure 10 and identified as:
 Section T1 – transverse section 1 adjacent to leakage;
 Section T2 – transverse section 2 adjacent to leakage.

The sections were prepared in the conventional manner for examination under an optical microscope
in as-polished and etched conditions. The etchant was 3% Nital.
 T2 T1

Fig. 6: Locations for the micro samples

(a) (b)

Fig. 7: Mounted Samples (a) Section T1 (b) Section T2

Figure 7 (a & b) presents photomicrographs of the transverse sections in the un-etched condition that
show clear indication of corrosion pits. There was a gradual decrease in the tube thickness in the
vicinity of the corrosion pits. The pits were observed to be of varying morphology containing shallow
and elliptical pits. The thickness reduced to maximum wall thickness and resulted in the pin-hole.
 Shallow Pit Elliptical
Through thickness leak Pit

Internal Side Internal Side

(a) Transverse Section T1 (Magnification 200X)

Internal Side

Internal Side

(b) Transverse section (T2) (Magnification 200X)

Fig. 8: Typical microstructures of the transverse sections in the un-etched condition

The micrographs for the etched samples are presented in figure 9 and 10 for the transverse section T1
and T2. The microstructure revealed typical phases of ferrite and pearlite. The internal surface of the
tube revealed wavy-nature and similar corrosion pits. The external surface was observed to be free
from any microstructural or corrosion degradation.
The corrosion pits were observed to be of varying morphologies and size also. The smallest pit was
measured to the value of 27µm as presented in figure 9 (f). The pits in the vicinity of the leak were
observed to be numerous causing the thickness loss and the eventual leakage of the tube. The gradual
loss in thickness and numerous corrosion pits provided the indication of presence of corrosive media
in the internal side of the tube.

Internal
Side

(a) Internal Side of the Transverse section T1 (b) Internal side - adjacent to image (a) showing
showing shallow pits (mag: x200) irregular surface (mag: X200)

(c) Internal side - further from image (b) showing (d) Internal side - further from image (c) showing loss
drastic change in thickness (mag:X200) in thickness and elliptical pit (mag:200)
(e) Location of maximum thickness reduction (a) (f) Location of maximum thickness reduction

(Mag: x200) (Mag: x400)

Fig. 09: Microstructures of the transverse section T1

(a) Bulk material microstructure (mag : x200) (b) Bulk material microstructure (mag : x400)
 Internal
Side

External
Side

(c) External side showing sharp surface (mag : x200) (d) Internal side showing wavy surface (mag : x200)

(e) Detail of thinned area (mag: X200) (d) full thickness loss (leak area) (mag: X200)

Fig. 10: Microstructures at external and internal surfaces in transverse section (T2)
 2.3 Hardness Testing
Hardness measurements were carried out using a Mitutoyo (Vickers) hardness testing machine,
with a 10kg load (HV10). Measurements were obtained for both tube samples ‘T1’ and ‘T2’ (Table
From the ASTM A-179 Standard Specification [Ref.3], the minimum Tensile Strength of SA-179 low
carbon steel (325MPa), is approximately equivalent to 100 HV (according to DIN 50 150
conversion tables). Thus hardness values for as-new material are required to be above 100 HV.
The maximum permitted hardness for as-new material (72 HRB) [Ref.3] is approximately 135 HV
(acc. to DIN 50 150). The results indicated that the service-exposed material was harder than
required by the specification.

Tube Hardness, HV10

Sample 1 2 3 4 Avg.

X 165 168 171 165 167

Y 164 159 158 157 160

Table 2: Results of Vickers hardness testing on tube samples

2.4 Chemical Analysis

The tube material (sample ‘X’) was analysed in order to check for conformance to ASTM A-179
specification requirements [3]. Chemical composition analysis was carried out using the Spectroscopy
technique; the results are shown in Table 3. It can be seen that the measured chemical composition
conformed to the specification requirements. No unusual (tramp) elements were detected.

Element C Cr Cu Mn S Ni Mo Nb Ni P Si
Sample X 0.07 0.13 0.04 0.61 <0.004 0.006 <0.01 0.002 <0.001 0.007 0.36
ASTM A179 0.035 0.035
0.06-0.18 - - 0.27-0.63 - - - - -
Specification max max

Table 3: Results of chemical analysis (wt.%)

 2.5 Scanning Electron Microscopy (SEM)

SEM and EDS analysis was conducted to evaluate the internal side’s Corrosion deposits / metal surface
which are adherent to the tube made from SA179 alloy.
SEM and EDS (JEOL) analyses were carried out on the internal side’s Corrosion deposits of the tube
at 20 KV with different magnification to obtain images with resolution range 100μm to 500nm. The
SEM have been taken at different locations to show the morphology of corrosion products and pitting
sites. EDS have been conducted using both area and line scan at different locations of corrosion
products and pitting sites. Also, EDS-Mapping have been performed to show distribution of the
elements over the scanned area.

The SEM show that the rust have different morphology with particle size range from 150 nm to 440
μm .also the Microstructure showed different gray level indicate that the depositions is composed from
different compounds (XRD needed to identify nature of the compounds). And there are pitting site on
the pipe surface.

Fig. 11: SEM show morphology of corrosion products

 3. DISCUSSION

There were corrosion pits of the internal surface, which identifies this as the bottom side of the tube.
These pits were observed to be of varying size and depth. The periphery of these pits contained reddish-
brown corrosion deposits. The pit morphology was cup-shaped and they were concentrated to a
localised area.

The central location of the tube sample reveals pin-hole leakage. The pin-hole side revealed dark brown
and strongly adherent layer of corrosion products on the inside surface. The stagnant condition and
the presence of these fresh deposits can be attributed to the hydro-jetting that was performed for
cleaning the tube internals.

Metallography showed the depth of the pits. The smallest pit was measured to the value of 27µm.
Metallography also showed that the pits at the external surface have regular pits with varying size and
dept. The pits at the external surface have ‘jagged’ edges, whereas the internal surface pits are more
rounded in appearance and increase in size beneath the surface. The morphology of the pits at the
external surface is indicative of acid attack, whereas the shape of the pits at the internal surface shows
that Microbiologically Influenced Corrosion (MIC) played a role in the damage. The analysis showed
that they primarily exhibited high Sulfates levels, but there were indications of Chlorides and this
shows that MIC was involved

There was a gradual decrease in the tube thickness in the vicinity of the corrosion pits. The pits were
observed to be of varying morphology containing shallow and elliptical pits. The thickness reduced to
maximum wall thickness and resulted in the pin-hole. The pits in the vicinity of the leak were observed
to be numerous causing the thickness loss and the eventual leakage of the tube. The gradual loss in
thickness and numerous corrosion pits provided the indication of presence of corrosive media in the
internal side of the tube.

To understand the nature of pits, SEM and EDS analysis was conducted, to evaluate the internal side’s
Corrosion deposits / metal surface. EDS have been conducted using both area and line scan at different
locations of corrosion products and pitting sites. Also, EDS-Mapping have been performed to show
distribution of the elements over the scanned area. SEM show that the rust have different morphology
with particle size range from 150 nm to 440 μm. Also the Microstructure showed different gray level
indicate that the depositions is composed from different compounds. The conducted EDX analysis
showed that the rusty scale was mainly iron oxide with small amount of other elements Like Cl, K, Ca,
P, S, Si, and Al which existed inhomogeneous in different depositions that might be precipitate form
the carried fluid .
 4. ROOT CAUSE OF FAILURE

Damage mechanism and root cause of failure

Corrosion occurred on the inner surface of the air cooler tubes due to the presence of water,
dissolved acids in process stream at temperature 78 °C in the exit from the column. The presence
of sulfates in corrosion products indicates that sulfuric acid also contributed to corrosion and due
to Sulfate-Reducing Bacteria, this lead microbiological induced corrosion in the system.

MIC is usually found in aqueous environments or services where water is always or sometimes
present, especially where stagnant or low-flow conditions allow and/or promote the growth of
microorganisms. Damage is often characterized by cup-shaped pits within pits in carbon steel.
There are several reason and one of them is the pH range of 0 to 12, and temperatures from –17°C
to 113°C. In this failure analysis, the pH was noted 5.13 and different organisms thrive on different
nutrients including inorganic substances for example sulfates or chlorides and inorganic substances
(e.g., hydrocarbons, organic acids). From the photographs provided by the client, there is huge
deposits, fouling and chunks which must be disturbing the flow and water stagnancy is a possibility
which could be a reason for MIC.

5. RECOMMENDATIONS

1. Low velocities can promote corrosion. Maintain flow velocities to above minimum levels
and minimize low flow or stagnant zones. Ultrasonic flow meters cab be used to monitor
the velocity.

2. Accelerated corrosion can also result from dead spots or stagnant areas. This stagnant areas
are a good source for MIC. A detailed Process Study need to be carried to find a source of
sulfates and chlorides, which will help to implement a suitable system and avoid
reoccurrence of such failures in the future.

3. It is recommended to avoid the chlorides/ sulphates as well as to maintain the pH to

acceptable level.

4. Effective mitigation of established organisms requires complete removal of deposits and

organisms using a combination of pigging, blasting, chemical cleaning and biocide
treatment.
5. It may also be a possibility that client arrange for Condition Assessment or Remaining Life
Assessment to know the life and condition of the operated tubes.
 6. Materials upgrading can be an option for such corrosion issues and can consider duplex
stainless steel or nickel base alloys (Inconel 625).

6. REFERENCES

1. Javaherdashti R (2008) microbiologically influenced corrosion: an engineering insight. Springer,

London.
2. ASTM A-179 Standard.
3. ASM Handbook (1987) Vol 13: Corrosion. ASM International, USA.
4. Critchley M, Javaherdashti R (2005) Materials, micro-organiss and microbial corrosion – A review.
Corrosion and Materials 30(3):8–11.