SPE 87261

Optimisation of Carbon Steels for Sour Service

DR.CORNELIUS O. EMENIKE AND DR. FIKRY F. BOROUKY*, ZADCO

Copyright 2000, Society of Petroleum Engineers, Inc.

th
This paper was selected for presentation at the 9 Abu Dhabi International Petroleum Exhibition and
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ABSTRACT
Failures in sour environments are a major concern to oil
producing companies because these failures do not usually
involve material loss (wall thinning). These time – dependent
failures can release toxic gas (hydrogen sulphide) to the
environment. Of major concern is the exposure of facilities
designed for sweet service to wet hydrogen. Hence, this paper
reviews the theory of HIC. For new production facilities such
as Pipelines, free-water knock out ( FWKO) drum and
flare stack, material selection using the well-known
immersion test NACE TM0177/ NACE TM02 84 is
highlighted.
Structure – property relationship is of paramount
importance in design, hence
regression equations were used to establish the effect of
chemistry and microstructure on mechanical properties.
INTRODUCTION
Recent failures[1-6] of pipelines and flare stacks are a major
motivation for production of HIC- resistant steels. This
problem posed by hydrogen interaction with steel becomes
more pressing as the search for energy resources advances into
deeper gas and oil wells. The products from these wells have
high susceptibility to hydrogen sulphide ( H2S) and carbon
dioxide ( CO2 ) contamination. The use of water or steam
injection as an enhanced recovery technique worsens the
situation by raising the corrosivity of these ‘sour’
environments. This concern assumes a wider dimension if the
original design is for sweet environment.
There are two major theories of HIC. Firstly, the
pressure model pioneered by Zapffe and Sims[7] which
postulates that the entry of atomic and subsequent
accumulation of molecular hydrogen at traps promotes
cracking and subsequently, a hydrogen - induced decohesion
of the lattice was proposed by Troiano[8]. Much work has
identified non- metallic inclusions (NMI) as potential
nucleation sites for HIC, hence much emphasis is placed on
producing low sulphur (0.005%max) and low phosphorus (150
ppm max) steels. These steels are also regarded as killed clean
steels. HIC resistance of these steel is confirmed by carrying
out NACE tests TM 0177 / NACE TM 0284.

Recommendations were made for repair of equipment /
facilities that failed during the transition from sweet to sour
services. Eventually, a rule based form of expert (knowledge
based) system was used to formalize a number of
relationships. These rules are in the form of IF -THEN
relationships. A brief explanation of the expert system is
given as the basis of rule format.
Structure - Property relation of carbon steel is reviewed
because HIC resistance steels have to meet the requirements
of mechanical properties. A recent case of failure is
highlighted, with relevant recommendations. Eventually a
brief review of expert (knowledge based) system is carried out
with examples of applications.

Key Words: Sour service, sweet to sour transition, HIC,

Structure - property
Relationship, repair method, expert system.

* NOW AT ARAMCO, SAUDI ARABIA

2 CORNELIUS O. EMENIKE AND FIKRY F. BOROUKY
THE HIC IMMERSION TESTS.
These are screening tests for materials selection. There are
two main tests for HIC assessment. These are detailed in
NACE TM – 01-77 which consists of 0.5% acetic acid and
5% sodium chloride. The other test is NACE TM 02 84 ( BP
Test ). This latter test is less stringent than the former.
Metallographic evaluations of the crack ratios are carried out
after 96 hour continuous immersion in an H2S saturated
solution. For NACE TM –01- 77, evidence of H2S saturation
is given by a change of pH from 2.4 to 3.5. For sour service,
NACE MR 0175 is also specified.
STRUCTURE – PROPERTY RELATIONSHIP
HIC resistant steels have to meet the requirements of
mechanical properties, hence the necessity to carry out this
brief review. Perhaps the most important development was the
appreciation that the ferrite grain size played a most important
role in controlling the properties of ferrite, in terms of both
the yield stress and the ductile brittle transition temperature.
The structure property relationships are based on two
relationships:
(i) Hall–Petch equation : δy = δi + Kyd-1/2 ------------------- (1)
(ii) Petch equation : β Tc = ln β - ln C -ln d-1/2 ---- (2)
Where δy is the yield stress
d is the grain size of the polygonal ferrite
and Tc is the impact transition temperature
The equation relevant to plain low carbon - manganese steels
is:
Yield stress (MN/m2)
15.4 [3.5 +2.1(Mn) = 5.4 (Si) + 23 (Nf) + 1.13 d– 1/2]
Where ( ) is the weight % of alloying element
and Nf is the “free” nitrogen content
The tensile strength of low carbon steels comprising
pearlite structures can be described by:
TENSILE STRENGTH
Tensile strength (MN/m2) =
[15.4 19.1+1.8(Mn)+5.4(Si) +0.25(Pearlite)–0.5d-1/2 - (4) ]
Where (Pearlite) is the percentage pearlite in the structure. It
should be noted that both pearlite and grain refinement
contribute to the tensile strength.
SPE 87261
IMPACT TRANSITION TEMPERATURE
The impact transition temperature can be described by :
Impact transition temperature 0C =
√−Nf ) + 2.2(Pearlite) –11.5d-1/2 -(5)
-19 + 44(Si) + 700 (√
The new trend is to have the carbon content to a maximum of
approximately 0.15% and make additions of Nb, V, T singly
or in combination to produce high strength low alloy (HSLA)
Steels. The upper limit of each microalloy is 0.1 %. Also by
using low S (0.005% max ) and P (0.015% max ), steels with
excellent strength, toughness, weldability, formability and
HIC resistance are produced. Details are documented else
where [9-12].
EXPERT ( KNOWLEDGE BASED ) SYSTEM
An expert system is a type of artificial intelligence ( A1 ). In
its simplest form, an expert system utilizes knowledge and
inference procedures to solve problems that are usually dealt
with by human expertise. The system is user – friendly.
COMPONENTS OF EXPERT SYSTEM
There are three main components of expert system.
These are :-
THE KNOWLEDGE BASE.
This contains facts and data relevant to a specific application
The inference engine uses it in the course of solving a
problem.
Database management. For optimum performance, an
integrated information system combines a database with an
expert system. Database design should focus attention to
content and format and contain relevant information. This
information / data will be useful for rule formulation.
Included in this database are NACE TM 0177, NACE TM
0284 and structure-property relationship.
ferrite-
THE INFERENCE ENGINE
This is sometimes referred to as control logic. It
communicates with the user through the user interface and
makes logical deductions based on the rules. The goal of the
inference engine is to prove or disprove hypothesis in the
expert system domain of expertise.
INFERENCE CHAINS . In the ruled based method of
representation, an inference engine solves problem (s) by
either a forward chaining or backward chaining structure or a
sophisticated combination of these.
3 OPTIMISATION OF CARBON STEELS FOR SOUR SERVICE
FORWARD CHAINING / ANTECEDENT REASONING
/ DATA – DRIVEN STRUCTURE:
The inference engine starts with the antecedent in the rule base
and by interrogations and deductions, proves or disproves the
various hypotheses.
BACKWARD CHAINING / CONSEQUENT
REASONING /GOAL – DRIVEN STRUCTURE:
The inference engine starts with the hypothesis as a
consequent. It examines the rule base for rules with first
hypothesis as a consequent.
No conclusion has been drawn about the superiority of
one chaining structure over the other. However, each
application is dictated by the nature of the problem being
evaluated.
THE USER INTERFACE
This sets up the screens through which the user states the
problem to be solved and allows interaction with the rest of
the system. These screens may look like a simple menu or
resemble ordinary word processing, database or spread sheet
screens.
KNOWLEDGE REPRESENTATION
Knowledge is mainly represented in two ways. These are the
popular rule – based methods. Knowledge is also represented
by frame based methods.
RULE BASED METHOD.
Rules are the most popular technique for representing
knowledge.
Rules are usually expressed as IF –THEN statements and
are sometimes represented by arrows (→ ) to indicate the IF
and THEN portions. However, the arrow version will not be
applied in this paper. Only, the IF- THEN version will be
used in this paper.
FRAME - BASED METHOD
This consists of both frame and semantic nets. Frame – based
method of representation uses a network of nodes connected
by relations and organized into a hierarchy.
Details are given elsewhere [ 13 - 15 ]
Expert systems are executed by the use of expert system
(ES) shell, which incorporates the inference engine and
already has the basic rule format. Further developments may
make shells flexible and competitive.
SPE 87261
The advent of rule – programming languages (i.e.
artificial intelligence (A1 ) languages such ad LISP or
PROLOG ) has considerably simplified the production of
expert systems. In these languages the program contains
statements, or rules, concerning the nature and relationships of
items of knowledge. LISP or PROLOG is more flexible than
the tailor - made shell.
FAILURE OF FLARE STACK DUE TO TRANSITION
FROM SWEET TO SOUR FLUID
This flare stack was constructed in 1982. Up until 1998, it
was used for flaring sweet gas only. It was used on at least two
occasions for a period of about three months to flare gas,
which contains eight per cent hydrogen sulphide.
MATERIAL OF CONSTRUCTION
The affected flare stack plates are ASTM A516 Grade 70
steel. This is typical steel used in pressure vessel
construction. At the time this steel was produced it was not
common practice to use inclusion control or desulphurisation
techniques to produce clean steels. Consequently, the sulphur
and phosphorus contents of the steel are high up to 0.04% and
0.035% respectively.
Sulphur combines with manganese to form round non-
metallic inclusions (MnS) distributed in the steel lattice.
During rolling into plate form, these inclusions are deformed
and broken up into stringers. These stringers tend to be
concentrated within the middle fifty per cent of the through
thickness and lie parallel to the direction of rolling. This
promotes the anisotropy of mechanical properties.
INSPECTION RESULT
A leak in the inlet pipe led to the discovery of a large amount
of iron sulphide sludge at the base of the stack. Ultrasonic
inspection of the flare stack plates indicated gross
delamination at approximately mid – wall depth. internal
inspection showed the presence of blisters on the stack’s
internal surface. The position of these blisters and the extent
of the delamination were mapped. Surface replica testing was
executed to determine if there were any surface breaking
cracks. The extent of surface corrosion on the internal
surfaces was recorded.
ASSESSMENT OF THE STACK
The inspection results produced indicated gross delamination
in many of the plates in the affected area. There was physical
evidence of blister growth on the inside surface of these plates.
Crack concentration was so great that ultrasonic inspection
could not differentiate between individual cracks.
Radiography performed on one blister was successful in
detecting a crack growing from the edge of the blister
4 CORNELIUS O. EMENIKE AND FIKRY F. BOROUKY
towards the internal stack surface. This would eventually
become surface breaking and relieve the internal blister
pressure.
Records indicate that when the steel was supplied it did
not contain any defects of the nature observed. Mill
certificates showed percentage sulphur to be ten times higher
than that now normally considered as acceptable for sour
service exposure.
DETERIORATION PROCESS
This examines the mechanism and mechanistic steps of
hydrogen induced damage surface corrosion by wet hydrogen
sulphide.
‘This leads to the production of atomic hydrogen on the
corroding surface. Monatomic hydrogen can be adsorbed on to
the steel surface and then pass through the steel lattice
interstitially due to its small atomic size.
2 H+ + 2 e - → 2 Hads
The monatomic hydrogen diffuses through the steel and
becomes trapped at non- metallic sites (e.g. inclusions) within
the steel. Hydrogen atoms then combine at inclusion sites to
form molecular hydrogen in gaseous form
Hads + Hads → H2 (gas).
This molecular hydrogen can not pass through the steel
lattice. In the body of the steel are typically MnS “ stringers’
which are formed during the steel making and rolling
processes. As more hydrogen becomes trapped at these sites,
the internal pressure builds up. This creates internal stresses
that cause the inclusions to form small ( typically 1-2 mm )
cracks between them. This is the step wise cracking that is
very typical of this type of damage.
As the corrosion proceeds, the internal cracking
continues due to the increasing pressure formed by the build
up of gas. These hydrogen-induced cracks ( HIC) can
eventually join to form an internal void or delamination
within the central body of the plate. This void is generally at
the mid thickness and lies parallel to the plate surface. The
hydrogen gas pressure can reach pressures as high as 3000psi.
It is completely independent of the working pressure at the
corroding surface. This pressure causes the steel to yield
locally and results in blisters at one or other of the plate
surfaces. It was observed that hydrogen induced damage was
restricted to the first 15m of the flare stack. This may be
attributed to uphill diffusion, diffusion across hydrogen
gradient, dislocation-hydrogen interaction and tendency to
diminishing wetness at the higher altitude of the flare stack.
SPE 87261
Structural analysis of the flare sack was carried out to
establish the structural integrity of the stack. Finite Element
analysis was employed. The result of this analysis confirmed
the fitness of the stack for continued operation. Details of the
analysis are beyond the scope of this paper.
Overall Recommendations for the infected Flare stack.
- Drill into the flare stack blisters to relieve the internal
pressure. This was implemented. Coat the inside of the
stack over the affected first 15m, with a high quality
high build glass flake epoxy coating. This was
completed without delay.
- Investigate the condition of other flare stacks
- Inspect the seal drum and knock out drum of the flare
stack by ultrasonic
- Should the other flare stacks show similar damage,
inspect the seal drums associated with them
- Establish a key point monitoring programme for all
equipment exposed to wet sour service.
- Implement operational health and safety procedures to
monitor hydrogen sulphide.
- Continue to operate the flare stack when other
recommendations are implemented
- Determine wind speed cycles of gust winds and relate to
fatigue survival.
RULE FORMULATION
A typical feature of an expert system is the presence of
dependency relationships among attributes, which can be
transformed into a hierarchy of rules.
HIC RULES
IF hydrogen sulphide = present
AND moisture = present
AND steel = not- clean
THEN HIC = probable
CLEAN STEEL RULES
IF sulphur concentration = specification
AND Phosphorus analysis = specification
THEN steel = Clean.
IF Non – metallic inclusion (NMI) = globular
AND the area fraction of NMI = low
AND the mean length of NMI = low
AND projected length of NMI = low
AND orientation dependence of NMI parameters = low
THEN HIC resistance = high.
HIC (immersion) test rule
IF steel is for sour environment
5 OPTIMISATION OF CARBON STEELS FOR SOUR SERVICE SPE 87261

THEN specification = NACE TM0177 (5) A. M. Kurdi, M.S. Abougfeefa and A.K. Deeney; Oil &
IF initial pH = okay Gas J. 1993, 91(30), 76-84
AND final pH = specification (6) K.M. Morsi and A.A. Key, Oil and Gas J, 1993, 91
AND hydrogen sulphide concentration = high (43), 76-79
AND test duration = 96 hours (7) C.A. Zapffe and C.E. Sims, Trans, AIME, 1941, 145 .
THEN test solution = saturated 225.
(8) A.R. Troiano, Trans ASM, 1960, 52, 54
Crack ratios (9) C.O. Emenike, Corros. Prev. Control, 1998, 35(3),
IF CLR (%) = specification 63-69.
AND CTR (%) = low (10) C.O. Emenike, and J.C. Billington; mater. Sci Technol.
And CSR (%) = low 1989. 5 (5). 450
THEN accept material. (11) C.O. Emenike and J.C. Billington: ibid, 1989 5 (6).
566
Stress corrosion cracking (12) C.O. Emenike: JMAT. SCI.L, 1990, 9, 24.
IF steels is for wet hydrogen sulphide service (13) C.O. Emenike, Materials & Design,1993, 14(6),
THEN specification = NACE MR0175 331
(14) C.O.Emenike, 1995, [Artificial Intelligence (A1)
IF hardness > HRC 22 approach to the Corrosion of HSLA pipeline steels in
OR hardness > HBN 220 sour oil. Fields] presented to chinese metals society,
THEN steel is out of specification. Beijing, China.
(15) D.A. Waterman, A Guide to Expert systems, 1986,
IF steel is out of specification Addison - Wesley, Reading MA, 25-94.
AND micro hardness is conducted
THEN carry out post weld heat treatment (PWHT)

IF welding = mandatory
AND CE (%) = specification
AND PCM (%) = within range
THEN specification = ASME section 9/ ASW D1. 1 / API
1104.

Repair rules
IF hydrogen blisters = present
THEN puncture with small size-drills
IF blisters = puncture
THEN coat internally with glass flake epoxy.
IF structural integrity = suspect
THEN carry out structural analysis.

Concluding remarks
The application of expert system in sour corrosion is
illustrated in this paper.

REFERENCES

(1) E.M. Moore and J.A. Warga, Materials Perf; 1976,

15(6), 17-23
(2) G.J.Biefer, ibid, 1982, 21 (6), 19
(3) B.E. Wilde, C.D.Kim and E.H. Phelps, corrosion, 1980,
36(11), 625
(4) G.T. Benyon and H.M. Yamauchi, 1987: Sour service
in oil, gas and petrochemical industries, Proc. Conf.
CAPCIS –UMIST and IBC Technical Services,
London, Paper 2