Petrotech-2010

31 October-3 November 2010, New Delhi, India

Paper ID : 20100856

New Materials And Technologies For Deepwater Development

Of Hydrocarbon Production

S.K.Velusshami* Dr. S.Kapoor, R.S.Mishra & R.Rai

Institute of Oil and Gas Production Technology, ONGC, Panvel – 410221, Navi Mumbai, India
Email : velusamy_k2000@yahoo.com

Abstract

The exploration of offshore gas/oil has been moving to deepwater fields as big reservoirs have been
found and technologies have improved. As the water depth becomes deeper and the reservoir is
located deeper underneath the seafloor, oil and gas products tend to have higher pressures and
temperatures than shallower reservoir products. The crude product usually contains large amounts of
water, wax, and asphalt. Dissolved carbon dioxide and sulfide may also corrode the pipe’s inner wall
surface. To prevent temperature drop during transportation, the pipeline may be insulated by means
of insulation coating, or employ a hot water circulation system or electrical heating system, or
designed as a pipe-in-pipe system .

The materials of choice must be corrosion-resistant, cost-effective, reliable and have the required
strength for the well conditions. As these conditions become more severe, material selection changes
from carbon steels to stainless, duplex, clad, flexible pipes, and composite materials.

The recent development of lean duplex UNS S32101, which is more corrosion resistant than 304, has
double the yield strength and can deliver substantial savings in both cost and weight. UNS S32101
also has good weldability, another advantage in the construction of flexible pipeline and umbilical
tubing in offshore projects. UNSS32003 lean duplex stainless introduced as a cheaper alternative to
the highnickel alloy 316L in both Subsea and topside applications. It is also considered ideal for
transport sweet to moderately sour oil and gas, and the alloy has been successfully applied in
deepwater flow lines. UNS S33207which is a new hyper duplex stainless steel has been developed
for use in umbilicals to explore fields at deeper sea depths. It has better corrosion resistance and
higher strength than super duplex stainless steel.

The available new materials and technologies discussed here will provide substantial support for
deepwater development, but continuing progress in these areas will undoubtedly be required.

Key words: stainless steel, Duplex, flow lines, flexible pipe, Umbilicals

Introduction:

Around the world, oil and gas development activities are increasing due to the growing demands for
energy. With the steady consumption of existing supplies, exploration and development have turned
to more hostile environments involving deep offshore wells, higher pressure and temperature
conditions, sour wells, and unconventional sources, such as oil sands. New Technology has
responded to industry demands with materials that meet the strength and corrosion resistance
necessary to survive the severe conditions associated with such production challenges.

The methodology adopted includes extensive literature survey on new metallurgy and technology for
different deepwater fields. This comprehensive detail includes series of literature survey executed for
new metallurgy for downhole equipment, pipelines as well as surface equipment used in deepwater oil
& gas production systems. Deepwater operations are highly technology sensitive, capital intensive
and high risk venture hence, for prolonged life proper selection of the material is adopted for different
field conditions in the design stage itself. Deep, sour-gas wells present great challenges to material
engineers. A host of corrosion resistant alloys (CRA) are providing respond to these challenges. The
Nickel, chromium, Molybdenum, vanadium system emerges as the premier CRA product to handle

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the most aggressive deep, sour-gas well environments. The engineered materials are one of the
solutions for tubular, risers, pipelines and umbilicals.

Lean duplex stainless steel is an ideal candidate for the high-pressure demands of offshore piping
systems that transport sweet to moderately sour oil and gas, and has been used for deepwater flow
lines.Titanium alloy components and risers offer considerable weight and corrosion resistance
advantages for long strings in deep wells and offshore locations. In this paper covers the selection of
new metallurgy for downhole equipment, pipelines, umbilical etc. and the application of suitable
technology for the development of deepwater fields.

Change in Materials of Construction

When it is observed that the existing material of construction is prone for corrosive attack, it is
normally decided to change the materials of construction and select alternate material to suit the
specific need. Generally the materials used in the hydrocarbon applications can be broadly grouped
as metals, non metals. Each variety of these materials has its specific applications and limitations. A
detailed study of process and operating conditions has to be carried out before selection of a new
material.

The new generation of Stainless Steels - Duplex stainless steels / Super Duplex Stainless steels by
and large resist almost all types of corrosion. The steel mills all over the world have been continuously
developing new materials with different metallurgies to resist almost any type of corrosion in the oil
and gas industry. While exotic materials like Titanium, Zirconium etc will operate in almost all
corrosive and high temperature environments, the initial cost is prohibitive to select materials unless
the equipment downtime is critical to the process and the facility. Detailed study of flow conditions,
corrosion mechanisms involved and the expected life of material is important before selecting a
specific metal for the application. It is all the time more important to understand that no single material
is cure for all the corrosion evils. A material which is good for stress corrosion cracking may fail due to
fatigue. Another material which can resist high temperature corrosion may fail due to pitting.

New development in production tubing

Tubing for sour wells

The oil and gas industry in recent years has been moving toward more challenging reservoirs, they
can be high temperature and high pressure, high salinity, high contents of CO2 and H2S , low pH and
deep sea or arctic locations and this trend will continue in the future. One of the challenges for the
development of these fields is the selection of materials for the production tubing. Initially 95 ksi (One
thousand psi is abbreviated ksi ) specified minimum yield strength (SMYS) steels were developed,
followed by 110 ksi grades and partially then filled the gap between traditional martensitic stainless
steels and duplex stainless steels.The oil and gas industry has been pushing its technological limits in
new and more challenging areas and challenged the steel industry to develop materials that will push
the limits of the modified stainless steels to higher corrosion resistance and even higher strengths.
The steel industry has responded with new higher strength martensitic stainless steels that have 115
ksi or even 125 ksi SMYS. While the 95 ksi and 110 ksi grades have been widely studied and there is
plenty of field experience, the new higher strength grades have become available only recently and
more work is needed to understand their limits with respect to their resistance to localized corrosion
and environmental cracking1. The addition of alloying elements like Nickel and Molybdenum has been
the main factor for better corrosion resistance and higher strength.

Tubing for HP/HT Applications

Flow streams from high-pressure/high temperature (HP/HT) wells usually contain H2S, CO2, and
chlorides. Such wells with temperatures greater than 350°F require corrosion-resistant-alloy (CRA)
tubing/casing. Titanium alloys can provide for an alternative. A testing program was developed to
qualify Ti-6246 alloy for use in sour-gas oil fields. The alloy would be suitable for production tubing as
an alternative to nickel-based alloys and super duplex stainless steels, depending upon the
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application. This alloy, Ti-6Al-2Sn- 4Zr-6Mo, was selected for qualification testing . Adding
molybdenum gives the alloy exceptional corrosion resistance to chlorides and H2S. The titanium- alloy
pipe is comparable to nickel based alloys traditionally used for production tubing in corrosive and

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31 October-3 November 2010, New Delhi, India

highly sour wells. The titanium alloy shows excellent resistance to environmental stress cracking in
production, work over, and completion environments that may occur in severe HP/HT and deepwater
fields. Burst strength and connection performance also were documented. As with any CRA-material
selection, project-specific testing should be considered to define material performance with respect to
the environments and stresses assumed for the completion.

New materials in flexible pipe and umbilicals

Lean Duplex Grade in Flexible pipe & Riser

Technologies have developed to industry demands with materials that meet the strength and
corrosion resistance necessary to survive the severe conditions associated with production
challenges. AL 2003 (S32003) lean duplex stainless steel is a cost-effective alloy for both subsea and
top side applications where the corrosion resistance of 316L/317L is required or where the strength of
2205 duplex stainless steel maybe needed. AL 2003 is an ideal candidate for the high-pressure
demands of offshore piping systems that transport sweet to moderately sour oil and gas, and has
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successfully been used for deepwater flow lines for the offshore oil & gas industry . In strip and plate
product forms, AL 2003 lean duplex stainless steel has received NORSOK qualification under the
latest edition of Standard M-650.

Lean Duplex Stainless Steels (LDSS) have now been used or are being considered as substitutes for
several well-established materials, in various applications. When compared to Types 316L, 317L and
2205, S32003 contains significantly less of the key alloying ingredients Ni and Mo. As a result, the
attention of many has turned to LDSS as a replacement material for traditionally used stainless
grades. The technical advantages of S32003 LDSS for use in applications where it may be an
appropriate, cost-effective substitute for more costly, less capable stainless steels and alloying
elements of these steel grades are shown in Table 1.

Table 1- UNS S32003 LDSS as a substitute for type 316L

Grade UNS Cr Ni Mo N
Number
304 L S30403 18.2 8.1 0.1 0.06
316 L S31603 16.2 10.2 2.2 0.06
317 L S31703 18.2 11.2 3.2 0.06
S32003 S32003 21.5 3.7 1.8 0.17
2205 S32205 22.5 5.8 3.3 0.16

Unbonded flexible pipes are typically used offshore for risers connecting floating production units with
wellheads on the seabed and for flow lines resting on the seabed. The flexible pipes transport oil, gas,
water and other fluids used in oil and gas production. Flexible pipes are often used instead of rigid
pipes due to the ease of installation and superior fatigue properties.

1. Stainless steel carcass

2. Polymer Fluid Barrier
3. Carbon steel Pressure Armour
4. C.S. Tensile Armour
5. Anti-wear/Friction Tapes
6. Polymerexteenal sheath

Figure - 1 cross section of Flexible pipe showing inner carcass layer

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The innermost layer, the carcass, is made from a stainless steel strip typical 316L (UNS S31603).
Stronger alternatives such as 22% chrome duplex (UNS S32205) and 25% chrome duplex (UNS
S32750) has been used for deep water applications in addition to fields with highly corrosive
production fluids. The resent developments in lean duplex stainless steel (UNS32101) grades have
provided an interesting alternative material with better mechanical properties, similar corrosion
resistance at a very competitive price compared to austenitic 316L grade. The cross section of flexible
pipe (carcass layer) is shown in figure-1.

Hyper Duplex Stainless Steel in Umbilicals

Umbilicals are used for controlling wellhead functions using hydraulic lines and can also be used for
chemical injection. Since the steel umbilical UNS S32750 was introduced to the market super duplex
stainless steels have been the most commonly used material. In recent years there has been a trend
to explore fields at deeper sea depths and longer umbilical are required. The newly developed hyper
duplex stainless steel, UNS S33207, has a 20% higher yield strength compared with UNS S32750.
UNS S33207 has high contents of Cr, Mo and N that results in a PRE above 50 according equation:
PRE= %Cr + 3.3%Mo + 16%N (% by weight).The higher strength in UNS S33207 makes it possible to
use thinner wall thickness and hence “think thin”. In order to increase the maximum service
temperature the corrosion properties has to be increased compared to super duplex stainless steels.
The UNS S33207 has better local corrosion resistance and also a higher maximum service
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temperature than super duplex stainless steels in an umbilical . (A typical flow line and pipeline of
deepwater field is shown in figure-2.)

Figure -2 A typical flow line and pipeline of deepwater field

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Titanium grades Ti-6A1-4V (UNS R56400), Ti-6A1-2Sn-4Zr-6Mo (UNS R56260), and 38-644 alloy
(UNS R58640) are increasingly used for vessels, pumps, piping, and deep well components where
the toughest environmental conditions make other materials unsuitable. Titanium alloy components
and risers offer considerable weight and corrosion resistance advantages for long strings in deep
wells and offshore locations. The super DSS & lean duplex materials which have been used for flow
lines in deepwater fields are shown in Table 2.0.

Table-2.0 New materials of flow lines and dosing pumps in deepwater fields

Supplier Project Description of flow line

A Phase 3 of Miskar gas field in Tunisia . UNS S32760(Super DSS) for 2 flow lines
Operator BG Tunisia Ltd. with external diameter of 273 mm and wall
thickness of 14.3mm

B Following system for Kikeh Field
Development project offshore Sabah,
Malaysia
C Alve field operator Statoil
UNS S32003 lean duplexes delivered to
Well stream International for flexible pipe
used in flow line
Rigid production flow line: 16 km long carbon
steel flow line with internal corrosion resistant
alloy cladding

Non-metallic unbonded flexible pipe for deepwater access

Flexible pipes are often used as dynamic risers that connect seabed flow lines to floating production
facilities. They are used as seabed flow lines where they are more cost-effective to install than rigid
steel pipe and in projects where the flow line may be recovered for reuse after a short field life.
Flexible pipes also are used as static and dynamic jumpers at the sea floor, on hybrid risers, or as
surface jumpers on deck.

The unbonded flexible pipe has developed as a new option that does not use metallic reinforcement.
Unlike metal pipe, the new Flexible Fiber Reinforced Pipe (FFRP) is highly resistant to the corrosive
properties of saltwater and other more aggressive chemicals such as the high H2S and CO2
concentrations being encountered more frequently in harsh offshore environments. The FFRP
connects wellheads, risers, flow lines, export pipelines, and well testing and intervention vessels to
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enable offshore oil and gas production in the most challenging environments . A new generation of
lightweight, noncorrosive flexible pipes has the potential to enable new field development scenarios in
deep and ultra-deepwater fields around the world.

New Clad pipe Technology

Corrosion & Resistance

Traditional carbon steel line pipes made of High-Strength, Low-Alloy (HSLA) steels exhibit corrosion
rates of approximately 0.2 mm/yr under environmental conditions such as 10 bar of CO2 at 60 C,
whereas Corrosion Resistant Alloy (CRA) materials exhibit 0.005 mm/yr or less under the same
conditions. This means, given a 30 yr pipeline lifetime, that a 6mm wall thickness loss would occur for
HSLA steel, whereas CRA would lose less than 0.15 mm.The increase in corrosive environments has
led to an increased demand for CRAs. This is largely driven by the recent trend for exploitation of
fields containing higher proportions of chloride ions, H2S and CO2. In the past, carbon steel pipe
material has been used, but corrosion mitigation measures are expensive and difficult to maintain at
the required level to ensure minimal or no corrosion.

CRAs include austenitic and matensitic stainless steels, nickel-based and titanium-based alloys. The
choice of CRA will depend on the application Materials with 11% or higher chromium are required for
corrosion resistance. For most offshore applications, CRAs on their own do not provide sufficient
strength to resist hydrostatic collapse for the depths considered, or the level of strain induced during
pipe lay. Therefore, CRAs are used as the inner sleeve to a higher strength outer casing.

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Clad innovation & Optimal weld

Clad line pipe is a structure in which the CRA is metallurgically bonded to the higher-strength carbon
steel material during the plate rolling process, diameters (more than 16 inch) are limited. Corus has
developed a process to manufacture metallurgically bonded clad pipe using what it calls the UOE
method, where the material is formed into a “U”, and then an “O”, shape before being expanded “E” to
the final dimensions. Using UOE, the company has determined a production route for the
manufacture of CRA line pipe6.This enables them to supply large quantities with the same
dimensional and mechanical tolerances as offshore -grade carbon steel.

The most advantageous weld methods of Submerged Arc Welding (SAW) and Metal Inert Gas (MIG)
procedures are used for this process. A defect free SAW weld and excellent mechanical properties
were achieved. As a result of this development work, the company has established a production
process to manufacture metallurgically bonded clad pipes through a volume based UOE pipe mill in
outside diameters between 406.5 and 1,067 mm for deepwater production operations..

Conclusions

The conclusion to be drawn from this study can be summarized as follows:

1. The understanding of the corrosion mechanism is very important before considering various
material options for the applications. However, it should be clearly understood that no particular
material is the cure for all the evils of corrosion.
2. The selection of materials like low carbon, stainless, duplex, titanium, clad (alloy inner wall + low
carbon outer wall), flexible pipes, and composite materials depends on conveyed fluid properties:
pressure, temperature, and corrosive components of deepwater fields.
3. The duplex grades are used as inner tubing (or carcass) of flexible pipe and umbilicals. Lean
duplex UNS S32003 has been used in unbonded flexible pipe in the Kikeh field offshore
Malaysia, and has been found to outperform 316L.
4. The hyper duplex UNS S33207 has been used for umbilical at extreme water depths and it shows
superior localized corrosion resistance compared to super duplex stainless steels.
5. The titanium- alloy pipe is comparable to nickel based alloys traditionally used for production tubing
in corrosive and highly sour wells. The titanium alloy shows excellent resistance to environmental
stress cracking in production, work over, and completion environments that may occur in severe
HP/HT and deepwater fields.
6. The new clad pipe manufactured under UOE technology method which can withstand hydrostatic
collapse pressure and corrosion resistance and is used for deepwater production operations.

Acknowledgements

Authors duly recognise the work & other details cited in the paper to delve the issue on New Materials
and Technologies for Deepwater Development of Hydrocarbon Production.

References

1. High Strength Modified Martensitic Stainless Steel Production Tubing for Sour Wells Ardjan
Kopliku BP America Inc. Houston, TX 77079NACECorrosion Conference Paper No: 09082.
2. Ultra deepHP/HTCompletions: B. Maldonado, A. Arrazola, and B. Morton, Baker Oil Tools,
prepared for the 2006 Offshore Technology Conference, Houston, 1–4 May.
3. AL 2003 LDSS (UNS S32003) as a Substitute for Type 316L- John J. Dunn and David S.
Bergstrom, ATI Allegheny Ludlum, USA(Presented at the Stainless Steel World 2006
Conference Houston, Texas - November 14, 2006.)
4. Hyper duplex stainless steel for deep Subsea applications- Guocai Chai R&D Center PA
Tube, Sandvik Materials Technology, Sandviken, Sweden Stainless steel world, March2009.
5. Non-metallic unbonded flexible pipe for deepwater access - by Mike Bryant and Matt Lutz
Deep Flex Inc. E&P Mag June 2009.
6. Clad line pipe overcomes corrosion losses - By Martin Connelly,Corus Tubes,UK, World oil
April 2009.