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SPE 87261

Optimisation of Carbon Steels for Sour Service


Copyright 2000, Society of Petroleum Engineers, Inc.

This paper was selected for presentation at the 9 Abu Dhabi International Petroleum Exhibition and
Conference held in Abu Dhabi, U.A.E., 15-18 October 2000. Recent failures[1-6] of pipelines and flare stacks are a major
This paper was selected for presentation by the ADIPEC Program Committee following review of motivation for production of HIC- resistant steels. This
information contained in an abstract submitted by the author(s). Contents of the paper as presented,
have not been reviewed by the ADIPEC and are subject to correction by author(s). The material, as problem posed by hydrogen interaction with steel becomes
presented, does not necessarily reflect any position of the ADIPEC or its members. Permission to copy
is restricted to an abstract of not more than 300 words. Illustration must not be copied. The abstract
more pressing as the search for energy resources advances into
should contain conspicuous acknowledgment of where and by whom the paper was presented. Write deeper gas and oil wells. The products from these wells have
ADIPEC Coordinator, GEC, P.O. Box 5546, Abu Dhabi, UAE., Fax 009712-4446135
high susceptibility to hydrogen sulphide ( H2S) and carbon
dioxide ( CO2 ) contamination. The use of water or steam
ABSTRACT injection as an enhanced recovery technique worsens the
situation by raising the corrosivity of these ‘sour’
Failures in sour environments are a major concern to oil
environments. This concern assumes a wider dimension if the
producing companies because these failures do not usually
original design is for sweet environment.
involve material loss (wall thinning). These time – dependent
failures can release toxic gas (hydrogen sulphide) to the
There are two major theories of HIC. Firstly, the
environment. Of major concern is the exposure of facilities
pressure model pioneered by Zapffe and Sims[7] which
designed for sweet service to wet hydrogen. Hence, this paper
postulates that the entry of atomic and subsequent
reviews the theory of HIC. For new production facilities such
accumulation of molecular hydrogen at traps promotes
as Pipelines, free-water knock out ( FWKO) drum and
cracking and subsequently, a hydrogen - induced decohesion
flare stack, material selection using the well-known
immersion test NACE TM0177/ NACE TM02 84 is of the lattice was proposed by Troiano[8]. Much work has
highlighted. identified non- metallic inclusions (NMI) as potential
nucleation sites for HIC, hence much emphasis is placed on
Structure – property relationship is of paramount producing low sulphur (0.005%max) and low phosphorus (150
importance in design, hence ppm max) steels. These steels are also regarded as killed clean
regression equations were used to establish the effect of steels. HIC resistance of these steel is confirmed by carrying
chemistry and microstructure on mechanical properties. out NACE tests TM 0177 / NACE TM 0284.

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

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

Structure - property
Relationship, repair method, expert system.




These are screening tests for materials selection. There are The impact transition temperature can be described by :
two main tests for HIC assessment. These are detailed in
NACE TM – 01-77 which consists of 0.5% acetic acid and Impact transition temperature 0C =
5% sodium chloride. The other test is NACE TM 02 84 ( BP √−Nf ) + 2.2(Pearlite) –11.5d-1/2 -(5)
-19 + 44(Si) + 700 (√
Test ). This latter test is less stringent than the former.
Metallographic evaluations of the crack ratios are carried out The new trend is to have the carbon content to a maximum of
after 96 hour continuous immersion in an H2S saturated approximately 0.15% and make additions of Nb, V, T singly
solution. For NACE TM –01- 77, evidence of H2S saturation or in combination to produce high strength low alloy (HSLA)
is given by a change of pH from 2.4 to 3.5. For sour service, Steels. The upper limit of each microalloy is 0.1 %. Also by
NACE MR 0175 is also specified. using low S (0.005% max ) and P (0.015% max ), steels with
excellent strength, toughness, weldability, formability and
STRUCTURE – PROPERTY RELATIONSHIP HIC resistance are produced. Details are documented else
where [9-12].
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 EXPERT ( KNOWLEDGE BASED ) SYSTEM
appreciation that the ferrite grain size played a most important
role in controlling the properties of ferrite, in terms of both An expert system is a type of artificial intelligence ( A1 ). In
the yield stress and the ductile brittle transition temperature. its simplest form, an expert system utilizes knowledge and
inference procedures to solve problems that are usually dealt
The structure property relationships are based on two with by human expertise. The system is user – friendly.
(i) Hall–Petch equation : δy = δi + Kyd-1/2 ------------------- (1)
There are three main components of expert system.
(ii) Petch equation : β Tc = ln β - ln C -ln d-1/2 ---- (2) These are :-
Where δy is the yield stress
d is the grain size of the polygonal ferrite
This contains facts and data relevant to a specific application
and Tc is the impact transition temperature The inference engine uses it in the course of solving a
The equation relevant to plain low carbon - manganese steels
is: Database management. For optimum performance, an
integrated information system combines a database with an
Yield stress (MN/m2) expert system. Database design should focus attention to
15.4 [3.5 +2.1(Mn) = 5.4 (Si) + 23 (Nf) + 1.13 d– 1/2] content and format and contain relevant information. This
Where ( ) is the weight % of alloying element information / data will be useful for rule formulation.
and Nf is the “free” nitrogen content Included in this database are NACE TM 0177, NACE TM
0284 and structure-property relationship.
The tensile strength of low carbon steels comprising ferrite-
pearlite structures can be described by: THE INFERENCE ENGINE

TENSILE STRENGTH This is sometimes referred to as control logic. It

communicates with the user through the user interface and
Tensile strength (MN/m2) = makes logical deductions based on the rules. The goal of the
[15.4 19.1+1.8(Mn)+5.4(Si) +0.25(Pearlite)–0.5d-1/2 - (4) ] inference engine is to prove or disprove hypothesis in the
expert system domain of expertise.
Where (Pearlite) is the percentage pearlite in the structure. It
should be noted that both pearlite and grain refinement INFERENCE CHAINS . In the ruled based method of
contribute to the tensile strength. representation, an inference engine solves problem (s) by
either a forward chaining or backward chaining structure or a
sophisticated combination of these.

FORWARD CHAINING / ANTECEDENT REASONING The advent of rule – programming languages (i.e.
/ DATA – DRIVEN STRUCTURE: artificial intelligence (A1 ) languages such ad LISP or
PROLOG ) has considerably simplified the production of
The inference engine starts with the antecedent in the rule base expert systems. In these languages the program contains
and by interrogations and deductions, proves or disproves the statements, or rules, concerning the nature and relationships of
various hypotheses. items of knowledge. LISP or PROLOG is more flexible than
the tailor - made shell.
The inference engine starts with the hypothesis as a
consequent. It examines the rule base for rules with first This flare stack was constructed in 1982. Up until 1998, it
hypothesis as a consequent. 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,
No conclusion has been drawn about the superiority of which contains eight per cent hydrogen sulphide.
one chaining structure over the other. However, each
application is dictated by the nature of the problem being MATERIAL OF CONSTRUCTION
The affected flare stack plates are ASTM A516 Grade 70
THE USER INTERFACE steel. This is typical steel used in pressure vessel
construction. At the time this steel was produced it was not
This sets up the screens through which the user states the common practice to use inclusion control or desulphurisation
problem to be solved and allows interaction with the rest of techniques to produce clean steels. Consequently, the sulphur
the system. These screens may look like a simple menu or and phosphorus contents of the steel are high up to 0.04% and
resemble ordinary word processing, database or spread sheet 0.035% respectively.
Sulphur combines with manganese to form round non-
KNOWLEDGE REPRESENTATION metallic inclusions (MnS) distributed in the steel lattice.
During rolling into plate form, these inclusions are deformed
Knowledge is mainly represented in two ways. These are the and broken up into stringers. These stringers tend to be
popular rule – based methods. Knowledge is also represented concentrated within the middle fifty per cent of the through
by frame based methods. thickness and lie parallel to the direction of rolling. This
promotes the anisotropy of mechanical properties.
Rules are the most popular technique for representing
knowledge. 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
Rules are usually expressed as IF –THEN statements and inspection of the flare stack plates indicated gross
are sometimes represented by arrows (→ ) to indicate the IF delamination at approximately mid – wall depth. internal
and THEN portions. However, the arrow version will not be inspection showed the presence of blisters on the stack’s
applied in this paper. Only, the IF- THEN version will be internal surface. The position of these blisters and the extent
used in this paper. of the delamination were mapped. Surface replica testing was
executed to determine if there were any surface breaking
FRAME - BASED METHOD cracks. The extent of surface corrosion on the internal
surfaces was recorded.
This consists of both frame and semantic nets. Frame – based
method of representation uses a network of nodes connected ASSESSMENT OF THE STACK
by relations and organized into a hierarchy.
Details are given elsewhere [ 13 - 15 ] The inspection results produced indicated gross delamination
in many of the plates in the affected area. There was physical
Expert systems are executed by the use of expert system evidence of blister growth on the inside surface of these plates.
(ES) shell, which incorporates the inference engine and Crack concentration was so great that ultrasonic inspection
already has the basic rule format. Further developments may could not differentiate between individual cracks.
make shells flexible and competitive. Radiography performed on one blister was successful in
detecting a crack growing from the edge of the blister

towards the internal stack surface. This would eventually Structural analysis of the flare sack was carried out to
become surface breaking and relieve the internal blister establish the structural integrity of the stack. Finite Element
pressure. analysis was employed. The result of this analysis confirmed
the fitness of the stack for continued operation. Details of the
Records indicate that when the steel was supplied it did analysis are beyond the scope of this paper.
not contain any defects of the nature observed. Mill
certificates showed percentage sulphur to be ten times higher Overall Recommendations for the infected Flare stack.
than that now normally considered as acceptable for sour - Drill into the flare stack blisters to relieve the internal
service exposure. 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
DETERIORATION PROCESS completed without delay.
- Investigate the condition of other flare stacks
This examines the mechanism and mechanistic steps of - Inspect the seal drum and knock out drum of the flare
hydrogen induced damage surface corrosion by wet hydrogen stack by ultrasonic
sulphide. - Should the other flare stacks show similar damage,
inspect the seal drums associated with them
‘This leads to the production of atomic hydrogen on the - Establish a key point monitoring programme for all
corroding surface. Monatomic hydrogen can be adsorbed on to equipment exposed to wet sour service.
the steel surface and then pass through the steel lattice - Implement operational health and safety procedures to
interstitially due to its small atomic size. monitor hydrogen sulphide.
- Continue to operate the flare stack when other
2 H+ + 2 e - → 2 Hads recommendations are implemented
- Determine wind speed cycles of gust winds and relate to
The monatomic hydrogen diffuses through the steel and fatigue survival.
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 RULE FORMULATION

Hads + Hads → H2 (gas). A typical feature of an expert system is the presence of

dependency relationships among attributes, which can be
This molecular hydrogen can not pass through the steel transformed into a hierarchy of rules.
lattice. In the body of the steel are typically MnS “ stringers’
which are formed during the steel making and rolling HIC RULES
processes. As more hydrogen becomes trapped at these sites,
the internal pressure builds up. This creates internal stresses IF hydrogen sulphide = present
that cause the inclusions to form small ( typically 1-2 mm ) AND moisture = present
cracks between them. This is the step wise cracking that is AND steel = not- clean
very typical of this type of damage. THEN HIC = probable

As the corrosion proceeds, the internal cracking CLEAN STEEL RULES

continues due to the increasing pressure formed by the build
up of gas. These hydrogen-induced cracks ( HIC) can IF sulphur concentration = specification
eventually join to form an internal void or delamination AND Phosphorus analysis = specification
within the central body of the plate. This void is generally at THEN steel = Clean.
the mid thickness and lies parallel to the plate surface. The
hydrogen gas pressure can reach pressures as high as 3000psi. IF Non – metallic inclusion (NMI) = globular
It is completely independent of the working pressure at the
corroding surface. This pressure causes the steel to yield AND the area fraction of NMI = low
locally and results in blisters at one or other of the plate AND the mean length of NMI = low
surfaces. It was observed that hydrogen induced damage was AND projected length of NMI = low
restricted to the first 15m of the flare stack. This may be AND orientation dependence of NMI parameters = low
attributed to uphill diffusion, diffusion across hydrogen THEN HIC resistance = high.
gradient, dislocation-hydrogen interaction and tendency to
diminishing wetness at the higher altitude of the flare stack. HIC (immersion) test rule
IF steel is for sour environment

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).
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

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.


(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