Paper No.

CPI15

Hydrogen Blistering in Stabilizer Overhead LPG Condenser of Naphtha

Splitter Facility
Swapnil Zodape
Indian Oil Corporation Limited, Guwahati Refinery, India
Email: zodapesj@indianoil.in

Manoj Kumar
Indian Oil Corporation Limited, Guwahati Refinery, India

Saugata Sahu
Indian Oil Corporation Limited, Guwahati Refinery, India

ABSTRACT

Low-strength carbon steels are widely used in refining industries for manufacturing pressurized
components such as pipes and pressure vessels. Hydrogen blistering is a common form of
hydrogen damage which can occur in components when a wet H2S environment is present.
Equipment operating in sour environment contain H2S are prone to deterioration by wet H2S
damage mechanisms when particular process variables gets established within the prevailing
operating conditions. Blistering and subsequent hydrogen induced cracking damage are strongly
affected by the presence of inclusions and laminations that provide sites for the diffusing hydrogen
to accumulate. The current study assesses the root causes of hydrogen blistering in a Stabilizer
LPG overhead condenser of naphtha splitter facility. The paper discusses in detail the inspection
findings, observations, prevailing process conditions for damage and remediation action plans to
prevent further accordance and growth of hydrogen blisters.

Keywords: Hydrogen blistering, Wet H2S, Diffusion, Sour water

NIGIS * CORCON 2017 * Sept. 17 – 20, 2017 * Mumbai

Copyright 2017 by NIGIS. The material presented and the views expressed in this paper are solely those of the author(s) and do not necessarily by NIGIS.
INTRODUCTION

Hydrogen damage is a degradation mechanism active in the oil and gas industry where carbon steel
is used for pressure vessels and piping that are in contact with wet H2S environments. Hydrogen
blisters may form as internal or external surface bulges, or within the wall thickness of a pipe or
pressure vessel. Blistering phenomenon occurs predominantly in low strength alloys when atomic
hydrogen diffuses to internal defects such as laminations or nonmetallic inclusions. The hydrogen
atoms combine to form hydrogen molecules that are too large to diffuse out and thus the pressure
builds up to the point at which local deformation occurs and thereby forms a blister. Hydrogen
blisters can form at different depths starting from the surface of the steel, in the middle of the plate
thickness or near welds.

This paper discusses in detail the observations of hydrogen blistering that were observed during a
shutdown in an IOCL refinery. Observations of hydrogen blistering were noticed on the heat
exchanger shell id and external surface of a stabilizer LPG overhead condenser in the naphtha
splitter facility. As per design, the stabilizer overhead system is designed with four condensers. The
condensed product is taken into the stabilizer reflux drum. The problem of blistering identified in the
shut down was due to the high level of H2S in the feed that was processed for short duration of four
months as an operational requirement and to meet the market demand.

When refinery equipment and piping are exposed to wet hydrogen sulfide, hydrogen atoms are
produced by surface corrosion of the steel. In the presence of hydrogen sulfide, the recombination
reaction of hydrogen atoms to the molecular hydrogen is retarded, consequently allowing, hydrogen
atoms to diffuse into the steel. These atoms can move rapidly either by diffusion or by transportation
through defects and are trapped at sensitive metallurgical defects such as the interface between
non-metallic inclusions and steel matrix. Cracking can occur if the critical amount of hydrogen
necessary for crack initiation is exceeded.

Table 1: Design Condition and Material of Construction

Design temperature in °C (Shell) 165 °C

Design pressure kg/cm2 (g) 10.3 kg/cm2
Material of construction - Shell SA 515 Gr. 60
Material of Construction – Tube Admiralty Brass
Process fluid-Shell LPG
Process fluid-Tube Cooling water

PROCESS IN BRIEF:

The purpose of the stabilizer column is to stabilize and remove the volatile components like propane,
butane and light fraction from naphtha, Figure 1. The feed from pre-topping column is caustic
washed before entering the feed surge drum. The feed before entering the stabilizer column is
heated to 124° C in feed bottom exchangers. The column overhead vapors are condensed in a
condenser and the condensed product is taken into stabilizer reflux drum.

NIGIS * CORCON 2017 * 17-20 September * Mumbai, India

Copyright 2017 by NIGIS. The material presented and the views expressed in this paper are solely those of the author(s) and do not necessarily by NIGIS.
 Figure 1: Process Flow Diagram

VISUAL EXAMINATION:

Visual examination revealed hydrogen blisters on the heat exchanger shell id and external surface
of all the overhead condensers. The hydrogen blistering was randomly distributed and the quantity
of blistering varied in nature for different exchangers. The diameter of the blisters observed varied
from 2 mm to 4 mm in diameter. Thickness measurements were done at all the blister locations and
shell plate where the surface appeared to be smooth. Thickness measured at the blister location
was 3.7 mm where it is suspected to have lamination or internal rolling defects.

PHOTOGRAPHS:

Figure 2 and 3: Blister on shell ID Figure 4: Blister after puncture

ASSESSMENT:

Thickness scanning for blister mapping and for health assessment of the complete heat exchanger
shell was done. The size of the individual blister was measured and recorded for all the exchanger
stabilizer condenser shells. Randomly, some blisters were ground smooth and checked with the dye
penetrant test (DP) for any initiation of the crack. No surface cracks were observed. No cracking or
interconnecting blisters were noticed visually and in the DP test after grinding. Hardness is one of
NIGIS * CORCON 2017 * 17-20 September * Mumbai, India
Copyright 2017 by NIGIS. The material presented and the views expressed in this paper are solely those of the author(s) and do not necessarily by NIGIS.
the contributing factor for the susceptibility of the cracking. Hence, hardness of the base metal and
welds were checked and hardnesses were found between 150-170BHN. As per API 571, carbon
steel used in H2S service hardness is not a critical factor for blister nucleation and growth;
nevertheless, hardness tests were conducted for confirmation regarding the material verification and
reliability point of view.

THE INFLUENCE OF PROCESS VARIABLES

Process variables exert a strong influence on the occurrence of wet hydrogen damage. Knowledge
of these influences can assist in the planning of a survey where greater inspection effort can be
concentrated in areas likely to be susceptible to attack. The quality of the material used for
manufacturing is also equally important if the process parameters comply with the hydrogen
damage requirements.

Generally, wet hydrogen attack does not occur in neutral environments (pH ~ 7.0). Acidic
environments are preferred and a common region for this damage is at pH levels below 4.0 with
H2S present. If both H2S and cyanide are present, hydrogen blistering form of damage can occur if
the pH is in the basic range. H2S levels above 50 ppm are normally required for attack. In the
present case, the H2S levels were in the range of 1000 ppm. Most of the wet-Hydrogen attack
classes occur at operational temperatures between ambient and 150 °C.

DISCUSSION:

 As per the past history of the stabilizer overhead condenser no observations of blistering
were recorded on the id side of the exchanger shell. Due to operational requirements, high H2S feed
was processed for short duration of 4-6 months which caused blistering in the overhead condensers.
The operating temperature range and operating conditions made hydrogen damage phenomenon to
be very conducive.
 As per the existing facility and infrastructure, provision of caustic wash is provided for
neutralization of the H2S in the feed. The existing caustic wash facility and strength of the solution
used was not sufficient to neutralize the high H2S in the feed.
 The boot water pH in the reflux vessel was not monitored which could have reflected the
carryover of the H2S stream in the stabilizer downstream.
 The quality of the steel used is an important factor even though the hydrogen is formed due
to the corrosion. As the refinery is old there might be chances of material defects like elongated
non-metallic inclusions or laminations in the steel that could have aggravated the hydrogen damage.
 As a spare shell was not available immediately, any possible destructive testing for detailed
metallographic analysis was not done.

ACTIONS TAKEN AND WAY FORWARD:

 To avoid further damage to shell and as an immediate measure, all blisters were punctured
using a 2 mm dia. drill. The release of the gas will not allow the existing blisters to grow further
which otherwise could lead to cracking.

NIGIS * CORCON 2017 * 17-20 September * Mumbai, India

Copyright 2017 by NIGIS. The material presented and the views expressed in this paper are solely those of the author(s) and do not necessarily by NIGIS.
 The existing facility of caustic dosing was reviewed and an increase in caustic strength was
recommended when high H2S feed is processed.
 To take care of corrosion, provision for specialized corrosion inhibitor like polysulfide dosing
provision in the existing system is under review.
 All the stabilizer overhead condenser shells are planned for replacement in the near future
with carbon steel NACE Material - killed steel normalized condition.

ACKNOWLEDGEMENTS

The authors would like to thank Guwahati Refinery, Indian Oil Corporation for their support and
providing an opportunity for presenting this Technical Paper at CORCON 2017.

NIGIS * CORCON 2017 * 17-20 September * Mumbai, India

Copyright 2017 by NIGIS. The material presented and the views expressed in this paper are solely those of the author(s) and do not necessarily by NIGIS.