Sour Service: Meeting the Demands of the Gulf

Region’s Welded Pipe Manufacturers

David Quidort, Pierre Fize

ArcelorMittal Flat Carbon Europe, France
Summary

• Market context: H2S-richness in the Middle East’s oil and gas fields

• Supplying hot-rolled coil from European mills to world class

producers in the GCC

• The importance of sour resistant steel coils for the region’s

welded pipe market

• Current challenges in procurement of HIC resistant steel coils

1
Market Background

• Middle East energy OCTG and Line Pipe markets are large and will grow
through 2017
• Traditional ME annual consumption of large diameter line pipe is ~420 kt for HSAW and ~1,9
Mt for LSAW.
• Current project requirements suggest some 25 Mt of line pipe might be needed in the region
through to 2017.
• Drilling activity is strengthening across the region – Oman, Kuwait and Iraq are all hot spots
currently for increased OCTG demand.
• ME consumption of OCTG is ~600 kt/year for seamless and ~50 kt/year for welded.

• Changing demand requirements in the energy market are creating

opportunities for API steel coils suppliers to service this market
• Estimated API coil requirements from Middle East pipe producers is ~3 Mt/y.
• HSAW pipes are increasingly used for onshore gas line pipe applications. Spiral weld
technology has overcome technical/psychological barriers that previously limited customer
adoption.
• Sour grades account for apprx. 25% of HSAW pipe requirements and 82% of ERW.
• ERW/HSAW pipe producers source a significant part of sour steel coils from Europe, Japan
and India.

2
Sources – AM Sales and Marketing, Hatch Beddows, CRU, Companies reports
Hot Rolled Coils for Oil and Gas Linepipes
Mills and capabilities
With over 30 years experience in producing steels for oil and gas pipes, ArcelorMittal Flat
Carbon Europe supplies more than 450,000 tonnes of hot rolled coils each year to the
global oil and gas pipe industry.
 HIC-resistant steel production
Milestones
1996 2000 2001 2003 2007 2008 2011

Mafumeira Greencore CO2 Pipeline

X52 & X56MS-PSL2
Gauges 9.3 to 12.2 mm
10 kT ACIPCO (USA)
First HIC batch
Chevron (Nigeria) 20” CPW (Greece)
X52MS-PSL2 X70MS-PSL2 – 58 kt
X60MS-PSL2
Gauge 11.2 mm
Gauges 7 & 12.7mm
CO2 Pipeline (HFI)
Qualification by NPC
New vertical curved
(end user = ARAMCO)
Continuous Caster

Baku-Tbilisi-Ceyhan Al Shaybah & MPP

Turkish Pipe Consortium
Gauges 9 to 16 mm
First shipment of X65-HIC X65MS-PSL2 – 130 kt
Major HIC SAWH Project
for crude oil
Saudi ARAMCO
National Pipe Co.
X65MS-PSL2 – 35 kt
Gauges : 11.1 & 13.8 mm
Major HIC SAWH projects
Hydrogen Corrosion of Oil and Gas pipes

• These cracks are very difficult to

detect during routine in-line
inspection, thereby representing a
serious risk for the pipeline integrity.

• Sour environments differ significantly

in their aggressiveness to materials
depending on total system pressure,
partial pressures of H2S and CO2, pH
of the aqueous phase, temperature,
chloride ion concentration, etc.
What does all that mean to us?

HIC resistant steel

1. Selective chemistry
+
2. Premium steelmaking
and continuous casting
practices
+
3. Reliable thermo-
mechanical hot-rolling
process
Manufacturing HIC resistant steels

Hot metal pre-treatment station

• De-sulfurization of pig iron is

achieved by injecting of calcium
carbide in the torpedo car.

• Sulfur migrates into the slag.

CaC 2 + S = CaS + 2 C

• S level obtained after treatment:

S < 0,005%
Manufacturing HIC resistant steels

Steel Making in the Basic Oxygen Furnace

• Steel is made in the 330 Ton LD converter

having
• top oxygen blowing by lance and
• bottom oxygen blowing tuyeres

• Control of the slag chemistry for an optimal

de-phosphorization. P level obtained after
treatment:
P < 0,015%

• Slag-free tapping in the ladle using slag

stopper.

• Alloys and fluxes are added to the heat as it

is tapped into the ladle.
Manufacturing HIC resistant steels

Ladle metallurgy
OB + De-S LANCE
• Steel is fully killed by Al and Si SAMPLING ADDITIONS
CORED WIRE
• Control of the slag chemistry and (SiCa, FeCa, Al)
desulfurization by top and bottom Argon
SEALED INERT
blowing. S level obtained after treatment: ATMOSPHERE

S < 0,002% (average 0,001%)

• Ferro alloy additions
• Inclusion shape control by SiCa cored wire
injection
• Treatment under controlled atmosphere:
low oxygen and hydrogen contents after
treatment: Ar

O2 < 0,003%
H2 < 0,002%
Manufacturing HIC resistant steels

Vacuum degassing

• “Vacuum degassing or alternative

processes to reduce the gas content of the
steel should be applied”.
°°°
• Fos-sur-Mer has also a Vacuum Degassing °°°°°
°° °°
° °
°
.....
°°°
°°°

facility (RH-degasser) of capacity ~1 Mt/y. °

°°°
°
°
• Vacuum degassing is used under wet °
°

atmospheric conditions to ensure low levels

in O2 and H2.
• Vacuum degassing is not the only way to
achieve low levels in O2 and H2.
• Vacuum degassing is also not sufficient to
guarantee HIC resistant steel.
 Manufacturing HIC resistant steels
Variation of sum of area fraction of MnS inclusions < 10 um with Ca/O ratio
9.E-06
Inclusion shape control
8.E-06

7.E-06

• In some standard specifications for pipelines 6.E-06

Area fraction MnS

intended for sour gas or oil transport, a Ca/S 5.E-06

ratio higher than 1,5 for heat with S level 4.E-06

greater than 0.0015 heats shall be selected. 3.E-06

2.E-06

• Too low Ca/S ratio results in the formation 1.E-06

of Manganese Sulfide MnS elongated 0.E+00

0 0.5 1 1.5 2 2.5 3
inclusions, whereas too high ratio results in Ca/O

the formation of CaS/CaO clusters.

• Both are detrimental to HIC resistance

• Control of the Ca/S ratio alone is not

sufficient to guarantee HIC resistant steel.

• Further addition of Ca (to comply with Ca/S

> 1,5) is not required when Ca/O > 1
Manufacturing HIC resistant steels

Continuous casting

• Use of split rolls in order to minimize

bulging and thus better segregation
control.
• Vertical-curved for enhanced inclusion
decantation. Vertical length ~2,7 m
• Slab thickness: 223 mm
• 1 sample is taken in the tundish and
analyzed for healt (ladle) analysis
• 100 % slabs are controlled by on-line
Eddy current
Slabs are continuously cast in 2 vertical-curved
• Dynamic Soft reduction in development casters with 2 strands:
for CC n°1. CC n°1 width <1800mm
CC n°2 width <2200 mm
Manufacturing HIC resistant steels

Optimum conditions shall be met prior to

casting of HIC-resistant steel

• Before the process: check of the proper

maintenance state of the CC

• During the process: a series of automations

and measurement devices operate on our
installations. The impact of all monitored
events is evaluated and an index is attributed
to each slab for its internal (cleanliness,
segregation) and surface quality.

• For every order, a minimum index level is

required. Each slab, which does not fulfill this
minimum level, will be automatically
downgraded from the order under
consideration.
Manufacturing HIC resistant steels
Hot Strip Rolling

84” Hot Strip Mill is equipped with:

• 3 reheating furnaces (walking beam type)
• 1 sizing press for width control
• 5 roughing stands (three 2-Hi, two 4-Hi)
• 7 stands 4-Hi finishing mill with Automatic
Gauge control, work roll bending and work roll
pair crossing systems.
• 180 m long run-out table with 2 laminar
cooling zones (2 x 50 m) and intense water
cooling 12,000 m3/h
• 4 down coilers equipped with hydraulic
wrappers and pinch roll and Automatic Jump
Control (DC n°4 & 5 for heavy gauges)
• Automatic Surface Inspection System
• Finishing temperature at target ±40
• Coiling temperature at target ±40
In-house HIC corrosion lab

• Sampling at edge, ¼ and ½ width for min 1

coil of each heat.
l = 100
mm
• HIC testing according to NACE TM0284-2003
– Test specimens are exposed during 96 h to the test L = 20
solution saturated with H2S gas. mm

– pH after H2S saturation shall not exceed 3.3, and at

test end, it shall not exceed 4.0. (for solution A).
– Iodometric titration to measure H2S concentration in
the test solution

• Ultrasonic scanning of the specimen after

exposure: determination of CAR (crack area
ratio).
• Metallographic examination: location of
sample cuts at the highest UT indication
• HIC-test capacity: 3 x 50 samples per week
• SSCC testing available under request
Product feasibility range

HIC resistant acc. to NACE TM0284:2003

solution A (pH=3)
20 • Production: Fos-sur-Mer, France
16

• Make-to-order strategy after

14,3
technical study of client
12,7
specification

11
• Approval is required for each steel
X42 - X56 X60 X65 X70 X80 grade x dimension x tonnage
feasability demonstrated

under development; trials in progress

Out of current feasibility program

Examples of recent projects

20“ Greencore CO2 pipeline (USA)

• End User : Denbury Resources Inc.

• Customer : CPW, Greece
• Pipe : HFW

• Grade API X70MS PSL2 (sour service)

• Main dimension : 1598 x 11,2 mm
• Total tonnage : 58,000 mt
• Production plant : Fos-sur-Mer
• Deliveries : 10Q4 – 11Q4
 20“ Greencore CO2 pipeline
Steel chemistry

X70MS-PSL2 for Greencore CO2 project

(statistics from 253 heats)

12 18

16
10
14

8 12
% of heats

% of heats
10
6
8

4 6

4
2
2

0 0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31

25

5
75

1
25

5
75

2
25

5
75

3
25

5
75

4
25

5
75

5
0,

1,

2,

3,

4,
0,

0,

1,

1,

2,

2,

3,

3,

4,

4,
Suphur (ppm) Ca/S
 Examples of recent projects
Tensile properties
YS pipe YS coil UTS pipe UTS coil

1,2
Statistical datas from 30 heats SAWH X65MS 30" x 13,8 mm - Saudi Aramco MPP project
1

Cumulative frequency
0,8

• Steel coils are delivered

0,6
with an extra strength to
compensate for the 0,4

apparent loss in yield 0,2

strength between the as
delivered steel coil and 0
440 460 480 500 520 540 560 580 600 620

the manufactured pipe. 1,2 Yield and Tensile Strength (MPa)

Statistical datas from 101 heats
SAWH X65MS 30" x 11,1 mm - Saudi Aramco Shaybah project
1
Cumulative frequency

0,8

0,6

0,4

0,2

0
440 460 480 500 520 540 560 580 600 620
Yield and Tensile Strength (MPa)
 Baku-Tbilisi-Ceyhan (BTC) project

BTC crude oil pipeline 34”, 42” and 46” (1700 km)

• End User : BOTAŞ and BP

• Customer : MITSUI & Co. and Turkish Pipe Consortium (BMB, Ümran, Noksel)
• 578 km of SAWH line pipe for sour service
• Grade API5L X65 PSL2 sour
• Coil suppliers:
– NSC Oita
– JFE Mizushima
– Posco
– Arcelor
• Production: Fos-sur-Mer
• Coil width: 1500 – 1800 mm
• Thickness: 8 – 16 mm
• Total tonnage: 130,000 mt
• Deliveries: 2003
Baku-Tbilisi-Ceyhan (BTC) project
HIC-Testing

X65 HIC statistical results in NACE 0284 96 Solution A

(381 samples)
100%

95%
Cumulated Percentage

90%

CLR
85% CTR
CSR

80%
0% 2% 4% 6% 8% 10% 12% 14% 16% 18% 20%
Conclusions and current challenges

• Middle East energy OCTG and Line Pipe markets will grow and the
need for sour grades will is increasing

• ArcelorMittal is highly qualified and has a long history of supplying

premium HIC-resistant steel coils from to world-class pipe
manufacturers

• HFI Pipes are becoming a reference for CO2 transportation

• Yet, still some reluctance to use HFI and SAWH in sour

environments

• Initiating a JIP to characterize SAWH sour serviceability?

 Acknowledgments

Fos-sur-Mer Mill
• Pierre Mabelly
• Jean-Michel Gabriel
• Bruno Michel
• Denis Lebre
• Xavier Bano

OCAS R&D Center

• Muhammad Arafin
• Martin Liebeherr