I Et 5250.00 114 940 JNL 901 C
I Et 5250.00 114 940 JNL 901 C
I Et 5250.00 114 940 JNL 901 C
Document revised by
PETROBRAS/DP&T/PRGE/ENG, according to PT-
PRGE/ENG-0392/2017, from Rev. C.
Material Specification
This document is the property of Jacobs and/or client and it is loaned with the restriction that the borrower undertakes that it shall not be
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TABLE OF CONTENTS
1.0 INTRODUCTION
1.1 GENERAL
1.2 ABBREVIATIONS
1.3 REFERENCED STANDARDS AND DOCUMENTS
2.0 FUNDAMENTALS OF MATERIAL SELECTION
2.1 GENERAL MATERIAL REQUIREMENTS
2.1.1 Basic Concepts
2.1.2 Carbon Steels
2.1.3 Stainless Steels
2.1.4 Non-ferro Metals
2.1.5 Materials for Environments Containing H2S
2.1.6 General Requirements for H2S Service
2.2 CORROSION BY WET SOUR GAS/SOUR WATER (WET H2S CORROSION)
2.3 HIGH TEMPERATURE HYDROGEN SULFIDE CORROSION
2.4 CORROSION BY LIQUID SULFUR
3.0 MATERIAL SELECTION
3.1 SULFUR RECOVERY UNIT
3.1.1 General
3.1.2 Material Selection for Piping
3.1.3 Material Selection For Equipment
3.2 UTILITIES
3.2.1 Material Selection for Equipment
3.2.2 Material Selection for Piping
1.0 INTRODUCTION
1.1 GENERAL
In this report the material selection for the Sulfur Recovery Unit is described, according
to standards of Jacobs Comprimo® Sulfur Solutions (JCSS). Furthermore, it explains
relevant corrosion concepts and standards, and links them to the material selection.
1.2 ABBREVIATIONS
3. American Petroleum Institute API Recommended Practice 945 (3rd ed., June 2003):
Avoiding Environmental Cracking in Amine Units; USA
5. NACE International Publication 8X194 Materials and fabrication practices for new
pressure vessels used in wet H2S refinery service, item No. 24179, June 1994.
Houston, USA
7. A working guide for carbon steel equipment in wet H2S service (developed largely
from oil refinery experience), EEMUA London UK, Publ. No. 179, 1996
8. NACE Corrosion 2004 conference paper no. 4649: An overview of NACE Intl.
Standard MR0103 and comparison with MR0175. Houston USA
It should be noted that a corrosive medium does not consist of one chemical substance,
for which a material could be selected from a table, list or brochure, but often is a
mixture of chemical substances. Furthermore, the chemical substances might react to
intermediate or final products, and sometimes by-products or waste products are
formed.
Some equipment cannot be manufactured from one grade of material, due to the
different functions of the components of the equipment.
Conditions outside normal working conditions have been taken into account, such as
temperature excursions during steaming-out or temperature run-away during upset
conditions. Localized types of corrosion that could have serious consequences, such as
stress corrosion cracking, pitting and crevice corrosion, have been carefully considered
with respect to material selection.
The materials selected in this report are specified according to ASTM standards, with
restrictions on carbon content, sulfur content and in cases prescription of heat
treatments. These minimum requirements are specified in the so called Additional
Material Requirement (AMR) sheets, which are appended to this report. AMR-sheets
shall apply where indicated, for all carbon steel used AMR-M1 is the minimum material
requirements to be applied.
If carbon steels other than the prescribed ASTM steels are used, these shall be killed
steels in the normalized condition and with a minimum specified tensile strength below
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 6 of 22
500N/mm2. The carbon content shall be less than 0.23% and the carbon equivalent CE
<= 0.43% (CE=C% + Mn%/6 + [Cr+Mo+V]%/5 + [Ni+ Cu]%/15). The weldability shall
be such that a maximum heat affected zone hardness of less than 248 HV10 is
ensured. The restriction on carbon content and sulfur content applies. Upgrading of
carbon steel to low alloy steel is subject to approval.
As a general rule, carbon steels denoted as P no. 1 steels in ASME code section IX can
be used for process equipment and piping without base metal hardness control, except
where indicated otherwise.
Carbon steels used that are not listed as P no. 1 materials in ASME code Section IX
shall have a maximum base metal hardness of 22 HRC (or 237 HBW).
Hot formed P no. 1 material piping and fittings shall have a hardness not higher than 20
HRC (or 225 HBW).
Methods to ensure a weld hardness below the above mentioned limits are given in
NACE RP-0472.
Stress relieving heat treatment (after >5% cold deformation) shall be carried out in the
temperature range 595°C to 650°C.
Carbon steel internals (such as Vortex breakers, baffles) shall have a corrosion
allowance of 3 mm for both sides together.
Where austenitic stainless steels are recommended for services >50°C, appropriate
measures shall be taken to prevent external chloride stress corrosion cracking. Paints
to be used shall not contain any zinc. Alternatively, higher alloyed austenitic or
austenitic ferritic (duplex) stainless steels, with a higher resistance to this form of
cracking, can be used.
To minimize the risk of chloride stress corrosion cracking the chloride content shall be
limited to 50 ppm at 60oC for 300 series austenitic stainless steel when applied for sour
water environments with possibly low pH values (no amines present).
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 7 of 22
Aqueous solutions containing H2S can cause different forms of cracking (HIC, SOHIC)
in plate material containing laminar inclusions. To minimize the risk that plate materials
sensitive for these forms of cracking are used, HIC resistant plate material shall be
used where continuous wetting of the steel with H2S containing aqueous solutions is
expected. Jacobs has defined HIC resistant plate material with the Additional Material
Requirements (AMR) M3, see Attachment 1.
It shall be noted that the requirements of M3 are more stringent than M2 and that the
following is included for HIC resistant plate material.
Ultrasonically testing for laminations in accordance to EN 10160 (1999), level
S2/E2.
Carbon content 0.23%
C.E. 0.43%
Sulfur content of 0.002% and a phosphor content of 0.010%.
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 8 of 22
Alternatively, if the above mentioned chemical restrictions are not feasible, through-
thickness-tensile (t.t.t.) testing may be applied.
For plate with a thickness below 25 mm, the through-thickness-tensile (t.t.t.) test in
accordance with ASTM A 770 may be carried out on a plate with a thickness over 25
mm taken from the same heat of steel. If t.t.t. testing is applied, then the material shall
also be capable of passing the NACE TM-0284 test with test solution A with the
following requirements.
Normally, the initial corrosion rate of carbon steel in aqueous H2S containing solutions
(general corrosion) is high, but falls rapidly to low values when a protective scale (iron
sulfide) is formed on the steel surface. The corrosion rate is dependent upon pH and
other corrosive species in the medium. Also the flow velocity influences the corrosion
rate by disturbing the protective scale.
Sulfide stress corrosion cracking (SSCC) of steel is a corrosion process in which crack
initiation and propagation occurs due to the diffusion of atomic hydrogen into the steel.
Atomic hydrogen is formed when H2S reacts with Fe to form corrosion products. The
crack propagation is the result of mechanical (tensile) stresses and embrittlement by
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 9 of 22
hydrogen that entered the steel. This type of corrosion occurs typically in steel showing
a hardened microstructure.
High stresses and high hardnesses can be present in welds and heat-affected zones
(HAZ). These places are especially susceptible to SSCC.
As indicated above, hydrogen induced cracking (HIC) can occur in steel exposed to wet
H2S. This form of attack will typically occur in steel with relatively soft microstructures
and appears commonly as blisters and/or stepwise cracking. HIC is caused by atomic
hydrogen that diffuses into the steel and is trapped in internal defects, such as
laminations or non-metallic inclusions (like MnS), and recombines there to molecular
hydrogen (H2). As molecular hydrogen has a considerable greater volume than atomic
hydrogen, pressure is built up in the metal. The pressure of molecular hydrogen can
attain such high values that cracking and deformation of the steel occurs, forming
blisters and stepwise cracks. Finally, blisters might rupture.
To prevent hydrogen induced cracking, clean and homogeneous carbon steels without
plate type (elongated) non-metallic inclusions shall be used.
Sour water often will contain other corrosive components, such as: ammonia, carbon
dioxides and sometimes cyanides. Depending on the actual composition, pH and
temperature, a corrosive species might promote corrosion in one set of conditions
whereas it inhibits corrosion in other conditions. Consequently, the corrosion rate of
carbon steel in sour water will vary with composition, and the material selection has to
be performed using experience and careful interpretation of external information.
In our experience the above-mentioned data are not fully compatible with the corrosion
rate found in sulfur recovery units. The gas mixtures in sulfur recovery units contain
hydrogen sulfide, sulfur dioxide, carbon dioxide, water, nitrogen, hydrogen and carbon
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 10 of 22
The attack of steel by hydrogen sulfide is aggravated when hydrogen is present. It will
be less when species like SO2 and CO2 are present. Unfortunately, no corrosion rates
are published of typical SRU gas mixtures at high temperatures.
According to literature, the corrosivity of sulfur sharply increases when the sulfur is
aerated or when in contact with water. In our experience, the high corrosion rates of
steel in aerated sulfur are not found as long as condensation of water does not occur.
If condensation of moisture occurs, high corrosion rates are possible due to H2S in the
water, condensation of sulfurous acid or due to elemental sulfur in direct contact with
steel and water.
The conclusion is that carbon steel can be used for piping and equipment for transport,
storage and degasification of liquid sulfur as long as the forming of cold spots is
prevented, i.e. by careful application of thermal insulation.
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 11 of 22
During normal operations free water will not be formed in the Claus unit downstream of
the waste heat boiler, therefore sour conditions and risk of SSC or HIC do not exist. The
general requirements for carbon steel are applicable (see Section 2.1). Upstream of the
main burner, sour conditions might occur and materials for piping and equipment shall
meet the requirements of NACE MR-0103.
Minimum material requirements AMR as given for piping and equipment units shall be
met.
During normal operation no water will condense in these lines and consequently no
corrosion will take place, as the metal surface will have a temperature over the water
dew point. During upset conditions (e.g. no heating of the pipe wall) condensation may
occur, or possibly a slug of liquid could pass, which will be caught in the acid gas knock
out drum.
The piping in acid gas service shall be made of carbon steel with a corrosion allowance
of 3.0 mm to allow some attack during upset conditions. It is assumed that the gas from
the amine units may contain amine solvent. Therefore, minimum material requirements
as per AMR-M7 apply.
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 12 of 22
The piping material will be carbon steel with 1.0 mm corrosion allowance. Minimum
material requirements as per AMR-M1 apply.
All materials used for equipment in contact with H2S containing liquids shall meet the
general requirements as described in Section 2.1. Minimum material requirements are
given in the mentioned AMR-sheets in the appendix.
114-E-901/902/903/904 – 1st /2nd /3rd /4th Process Gas Reheater (HP Steam)
Shell side : A 516 - Gr. 55/60/65
Tube side : A 516 - Gr. 55/60/65
Tube sheet : A 516 - Gr. 55/60/65
Nozzles : A 106 A or B
Flanges : A 105
Tubes : AISI 321
Corrosion allowance
Shell side : 3.0 mm
Tube side : 1.5 mm (no corrosion allowance on tubes)
Tube sheet : 4.5 (3.0 + 1.5) mm
Minimum material requirements
Tube side/tubes : AMR-M1
Shell side : AMR-M1
Tubes : cancelled requirement C
3.2 UTILITIES
3.2.1 Material Selection for Equipment
No new equipment in the utility section.
Nitrogen Piping
Nitrogen is not corrosive and this piping shall be made of carbon steel with 1.0 mm
corrosion allowance. Minimum material requirements as per AMR-M1.
Condensate Piping
The piping shall be made of carbon steel with 1.0 mm corrosion allowance. Minimum
material requirements as per AMR-M1 apply.
Blowdown Piping
The piping shall be made of carbon steel with 1.0 mm corrosion allowance. Minimum
material requirements as per AMR-M1 apply.
ATTACHMENT 1
The additional material requirements AMR are the minimum requirements for chemical
composition, hardness and heat treatment condition for carbon and low alloy steels that
are different from those approved by NACE MR0103-2005. These steels should also
comply with the requirements stated in Section 2.1 of this report.
AMR Number M1
Material Carbon and low alloy steel
For all product forms : More stringent requirements as per applicable material standards or
per applicable design codes are always governing.
Hardness limit : N.A.
Cold deformation >5% : Stress relieving heat treatment to be applied after deformation.
(temperature range 595°C-650°C, hold 1 hr per inch thickness)
Hot deformation : Normalizing heat treatment to be applied after deformation.
Carbon equivalent : N.A.
PWHT : N.A.
Bolting material
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 20 of 22
AMR Number M2
Material Carbon and low alloy steel
For all product forms : More stringent requirements as per applicable material standards or
as per applicable design codes are always governing.
Hardness limits : Base material 22HRC, HAZ (WPQ) 248 HV; weld deposit 200HB.
Base material hardness requirements are only for not P no.1 material.
Cold deformation >5% : Stress relieving heat treatment to be applied after deformation.
(temperature range 595°C-650°C, hold 1 hr per inch thickness)
Hot deformation : Normalizing heat treatment to be applied after deformation.
%Mn %Cr %Mo %V %Ni %Cu
Carbon equivalent : CE %C
6 5 15
PWHT : N.A.
Bolting material
Project No. : CE904600 Material Specification
Client : PETROBRAS I-ET-5250.00-114-940-JNL-901
Site Location : Regap Refinery, Minas Gerais State, Brazil Rev. C
Project Name : Sulfur Recovery Unit (U-114) Page 21 of 22
AMR Number M3
Material Carbon and low alloy steel
For all product forms : More stringent requirements as per applicable material standards or
as per applicable design codes are always governing.
Hardness limits : Base material 22HRC, HAZ (WPQ) 248 HV; weld deposit 200HB.
Base material hardness requirements are only for not P no.1 material.
Cold deformation >5% : Stress relieving heat treatment to be applied after deformation.
(temperature range 595°C-650°C, 1 hr per inch thickness)
Hot deformation : Normalizing heat treatment to be applied after deformation.
%Mn %Cr %Mo %V %Ni %Cu
Carbon equivalent : CE %C
6 5 15
PWHT : N.A.
Valve trim material All valve materials shall comply with the
requirements of NACE Standards MR-0103
AMR Number M7
Material Carbon and low alloy steel
For all product forms : More stringent requirements as per applicable material standards or
as per applicable design codes are always governing.
Hardness limits : Base material 22HRC, HAZ (WPQ) 248 HV; weld material 200HB.
Base material hardness requirements are only for not P no.1 material.
Cold deformation >5% : Stress relieving heat treatment to be applied after deformation.
(temperature range 595°C-650°C, 1 hr per inch thickness)
Hot deformation : Normalizing heat treatment to be applied after deformation.
%Mn %Cr %Mo %V %Ni %Cu
Carbon equivalent : CE %C
6 5 15
PWHT : Post weld heat treatment applicable
(temperature range 595°C-650°C, 1 hr per inch thickness, holding
time 1 hr minimum).
Pipe material Carbon content 0.23% Hot finished (T>850°C) or normalized.
CE 0.43% Additional requirements for plate are
Sulfur content 0.010% applicable in case of longitudinal welded
2
pipe. Max. tensile strength 585 N/mm
Plate to be normalized.
Fitting material Carbon content 0.23% Additional requirements for plate are
If plate material is used, CE 0.43% applicable in case of fittings fabricated
see plate material for Sulfur content 0.010% from plate. Normalized.
2
requirements Actual tensile strength Max. 585 N/mm
Plate material Carbon content 0.23% Ultrasonic examination acc. to EN 10160
CE 0.43% (1999) level S2/E2.
2
Sulfur content 0.002% Actual tensile strength Max. 585 N/mm
Phosphorus 0.010% Normalized
Forgings Carbon content 0.23%
CE 0.43%
Valve trim material All valve materials shall comply with the
requirements of NACE Standards MR-0103