DILLINGER PRESSURE VESSEL COLLOQUIUM

Dillingen – 16/17 th september 2009

TOTAL Requirements for equipment

in severe wet H2S service.

Examples of equipment
made from Dillinger steel plates

Martin RICHEZ

Franck ZANONCELLI

Dillinger Pressure Vessel Colloquium – Dillingen – 16 & 17 September 2009

Requirement for vessels in severe wet H2S service 2/7

TOTAL Requirements for equipment

in severe wet H2S service.

Examples of equipment
made from Dillinger steel plates

1. Degradation of steel in wet H2S service

H2S is present in many refinery process streams. Wet H2S service is referred in a process stream
where both water in liquid phase and H2S are present.
Carbon steel is commonly use in this environment, but it can be subject to degradation depending
upon pH, H2S level, temperature, duration of exposure and nature of the material. Thickness loss
is usually not the main problem, but hydrogen is the major concern. NACE and EFC have
extensively studied this subject leading to different recommendations.
Hydrogen is involved in most corrosion mechanism, but H2S presents the specificity to lead to
high atomic hydrogen penetration in steel. This hydrogen tends to embritle the metal or to
recombine to form Hydrogen molecule in the steel inclusions. Hydrogen pressure can get very high
leading to high stresses.

There are two main types of degradation:

HIC (Hydrogen induced cracking). This is planar cracking that occurs in carbon and low alloy
steels when atomic hydrogen diffuses into the steel and then combines to form hydrogen at trap
sites. The driving force is the hydrogen pressure, helped by hydrogen embrittlement. No applied
stresses are required for cracks to appear. Susceptibility of steels to HIC is strongly dependent
upon cleanliness of the steel, and the size and shape of inclusions. These cracks are oriented in the
plan of the steel plate. They can be clearly identified when they form bulges at the plate surface.

SSC (Sulphide stress cracking). This is a form of hydrogen cracking due to the interaction of
hydrogen and stresses (residual or applied). Cracks are perpendicular to the stresses. Hardness is
known to increase susceptibility of the steel to SSC. NACE document MR 0103-2007 deals with
this subject.

Other degradations can appear which are combinations of HIC and SSC:

SWC (Stepwise Cracking). This term is used when closed hydrogen induced cracks (HIC),
developed at different depths in the steel are connected by small perpendicular cracks. Theses
cracks are due to hydrogen embrittlement and stresses induced by the bulging. Applied stresses can
also play a role.

SOHIC (Stress Oriented Induced Cracking). This term is used when staggered small cracks
formed approximately perpendicular to the principal stress (residual or applied), result in a “ladder
like” crack array linking some preexisting HIC cracks.

Dillinger Pressure Vessel Colloquium – Dillingen – 16 & 17 September 2009

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2. TOTAL practice for steel in severe wet H2S service

2.1 Severe wet H2S service
Severity of Wet H2S service depends on the H2S content and pH of water in contact with the
metal. During unit engineering, stream composition is provided by the process department. This
data is the basis for determining the service severity. However this data may not be fully available
and unusual or transient operations are often not considered. So any choice in H2S severity service
has to be confirmed by a specialist during the material selection review to take into account these
cases and company feed-back.

pH H2S ppm

10<H2S<50 50=H2S=2 000 2000<H2S=10000 H2S>10000

pH<5 Low High High High

5=pH=7.8 Low Moderate* Moderate* High

pH>7.8 Low* Moderate* High High

* High severity if CN- (cyanide) > 20ppm

When exposure to severe wet H2S service does not happen during normal operation but happens
during upset or transient operation, it is considered that only SSC may occur and the service is
considered as moderate.

2.2 Specification for plates

Carbon steel is commonly used in low, moderate and severe wet H2S service, with a 3 or 6 mm
corrosion allowance. In this case, steel components (plates, forged parts) and welding are subject to
stringent specifications.

For specific cases, when the environment is judged to be very corrosive, an internal liner made of a
corrosion resistant alloy may also be used (cladded plates or weldoverlay). In this case, there is no
specific requirement for the carbon steel base metal due to wet H2S service.

The objective of these specifications is to:

• reduce the hardness, by limiting residuals elements leading to high hardness phase
formation, and limiting the steel tensile stress,
• reduce susceptibility to HIC by limiting sulfur and by acting on the inclusion shape,
• limiting crack propagation by a low phosphorus and segregating element content.

All carbon steel materials shall be delivered fully killed and normalized.

The steel plates shall be fabricated from unalloyed carbon steels produced by an electric arc
furnace or oxygen furnace process. The steel shall be vacuum degassed, deoxidized and produced
to a fine grain structure, with a process leading low sulphur and phosphorus content.

Steel shall be produced with thorough desulphurization, dephosphorization and deoxidizing

treatments. Calcium treatment shall be applied for inclusion shape control, except that it need not
be applied to plate with very low sulphur levels (below 0.002 %). The calcium content shall not
exceed 3 times the sulphur content.

Dillinger Pressure Vessel Colloquium – Dillingen – 16 & 17 September 2009

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The supplier shall exercise special care in the selection and supervision of the conditions of
fabrication and normalizing heat treatment, in order to eliminate heterogeneous structures, such as
pearlite structures in very pronounced bands and aggregates of bainite and
unannealed martensite.

Chemical analysis shall be in accordance with material norm/specification requirements.

Materials with a minimum specified tensile strength value greater than 415 MPa are not allowed
(according to the material norm or specification). Hardness shall be lower than 200 HB.

The chemical composition of carbon steel plates (heat analysis) shall be restricted as followed,
except where the material norm/specification is more restrictive:

Single Elements Maximum wt. %

Carbon (C) 0.18
Manganese (Mn) 1.20
Phosphorous (P) 0.010
Sulphur (S) 0.005
Silicon (Si) 0.40
Copper (Cu) 0.20
Nickel (Ni) 0.40
Chromium (Cr) 0.30
Molybdenum (Mo) 0.12
Vanadium (V) 0.015
Niobium (Nb) 0.015
Titanium (Ti) 0.02
Boron (B) 0.0005
Multiple Elements
Cr + Mo 0.30
Ni + Cu + Cr + Mo 0.70
Nb + V + Titanium (Ti) 0.12
V + Nb 0.03
Carbon Equivalent (Note 1) 0.38

Dillinger Pressure Vessel Colloquium – Dillingen – 16 & 17 September 2009

Requirement for vessels in severe wet H2S service 5/7

Note 1: Carbon Equivalent (CE) shall be calculated using the following formula:

Plates shall be subjected to an ultrasonic lamination check in accordance with EN 10160 Class S2
or ASTM A 578, level C, supplementary requirement S1.

2.3 Forged components and piping

The chemical composition (product analysis) shall be restricted as follows, except where the
material norm/specification is more restrictive:

Single Elements Maximum wt. %

Carbon (C) 0.21 / 0.20 (note 2)
Manganese (Mn) 1.05 (note 2)
Phosphorous (P) 0.025 (note 3)
Sulphur (S) 0.020 / 0.010 (note 2 – note 3)
Multiple elements Maximum wt. %
Vanadium (V) + Niobium (Nb) 0.20
Nb + V + Titanium (Ti) 0.12
Carbon Equivalent (Note 1) 0.43 / 0.40 (Note 2 – Note 3)
Nickel (Ni) 0.40

Note 1: Carbon Equivalent (CE) shall be calculated using the following formula:

Note 2: the higher limits are for forgings the lower ones for pipes.
Note 3: for forgings: Mn = 1.35 % max provided that P ≤ 0.015 %, and S ≤ 0.010 %

2.4 Specification for manufacturing

All pressure vessels in wet H2S Service shall be Post Weld Heat Treated in accordance with the
code requirements. 1 hour per 25 mm of thickness (minimum holding time of 1 hour) and 600°C
shall be applied as a minimum

Weld hardness testing of production welds shall be carried out in accordance with the NACE
International Publication 8X194 with a maximum value of 200 HB (hardness of 210 HV10 max.).
In heat affected zone (HAZ), higher values not exceeding 248 HV 10 are acceptable.

All accessible inside surfaces of welds of pressure retaining parts shall be 100 % inspected by
Wet Magnetic Fluorescent / Particle Test (WFMT) after PWHT.

For thickness > 40mm, a 100% radiography and ultrasonic examination is required before and after
PWHT.

2.5 Hydrogen induced cracking test.

The HIC test and crack evaluation shall be in accordance with NACE Standard TM0284. The test
is performed at pH = 3.

The test shall be performed per heat on the thickest plate in a simulated PWHT condition.

Dillinger Pressure Vessel Colloquium – Dillingen – 16 & 17 September 2009

Requirement for vessels in severe wet H2S service 6/7

The following acceptance criteria shall be met:

% (maximum)
CLR CTR CSR
Average 5 1.5 0.5
Single 10 2 0.7

Note:
• Average value. Arithmetical mean of the values obtained on the total number of studied
sections.
• Single value. Arithmetical mean of the values obtained on the 3 studied sections for each
specimen.

The maximum individual crack length on any section shall not exceed 5 mm.

3. Refining unit and area of concern

Many refining units are concerned by wet H2S service. H2S rarely comes from the crude itself,
most of it is provided by thermal degradation of the feed, catalytic cracking or
hydrodesulfurization.

• Since H2S is not usually present in the crude, H2S content is limited in crude distillation
unit. However some H2S is added from thermal cracking or cuts from other units (HDS,
Coker…) that are introduced into the feed to be reprocessed. Distillation overhead is
usually considered as a moderate wet H2S service. Some equipment, dedicated to off gas,
may be classified as severe.

• Hydrotreatment of light cuts like gasoline often lead to a limited amount of H2S. Low
temperature areas of the unit are often classified as moderate wet H2S service.

• Hydrodesulfuration units (that operate from 50 to 100 bars) or Hydrocracker units contain a
lot of H2S. Low temperature areas, where water can be present, are classified as severe.
Overhead of down stream separator and amine absorbers are considered as severe wet H2S
service.

• Thermal cracking units including Visbreaker, Coker, or catalytic cracking unit such as FCC
are also classified as severe wet H2S service on the cold light end cut (mainly LPG). On
these units cyanides can strongly increase degradation.

• In amine units (absorber or regeneration), all rich amines streams, and regenerator overhead
are considered as severe wet H2S service.

• Units downstream of Hydrotreatment units or amine absorbers, such as Reforming,

Alkylation, Isomerisation, Propylene units are not concerned by wet H2S service.

4. Recent examples of equipment fabricated from Dillinger

steel plates

Dillinger Pressure Vessel Colloquium – Dillingen – 16 & 17 September 2009

Requirement for vessels in severe wet H2S service 7/7

Dicrest steels have been developed by Dillinger Hutte GTS to be used in wet H2S service.
Dicrest 5 is the most elaborate of these steels. Its effective composition and characteristics are very
close to TOTAL requirements. These steels are also immediately available due to a permanent
stock maintained by Dillinger Hutte GTS.

These two advantages lead to the regular choice of Dicrest 5 for equipment made of thin to
medium thickness steel plates. This is the case in maintenance work where delivery is a primary
concern, but also for projects such as new units or major debottlenecking.

At this time a two stage water stripper is being built for the Feyzin refinery. This unit is dedicated
to remove separately H2S and ammonia from process water. In the first step H2S is removed in a
column operating at 10 bars, in a second step ammonia is removed in a second column operating at
0.5 bars.
Most of the equipment are in wet H2S service (moderate or severe). Dicrest 5 has been the material
chosen by most of the manufacturers with TOTAL agreement.

Unit Item Function H2S Operati Operating Thick. Steel

service ng pressure
temp.
Water 45 B 753 Condensate Severe 212°C 19 bars 15 mm A 516 Gr 60
Stripper drum Dicrest 5
Water 45 B 754 Condensate Severe 200°C 3 bars 15 mm A 516 Gr 60
Stripper drum Dicrest 5
Water 45 E 751 Feed/Effluent Severe 163°C 9.5 Chan. 13 mm A 516 Gr 60
Stripper 14.5 Tube 8 mm Dicrest 5
Water 45 E 752 Feed/Effluent Severe 200°C 9.1 Chan. 14 mm A 516 Gr 60
Stripper 13.8 Tub 8 mm Dicrest 5
Water 45 E 753 Reboiler Severe 200°C 9.1 Chan. 15 mm A 516 Gr 60
Stripper (Channel) 380°C 18.8 Tub. (Channel) Dicrest 5
Water 45 EA 754 Air cooler Moderate 136°C 7.8 bars 25 mm A 516 Gr 60
Stripper Dicrest 5
Water 45 EA 755 Air cooler Severe 109°C 1.5 bars 25 mm A 516 Gr 60
Stripper Dicrest 5
Water 45 EA756 Air cooler Moderate 84°C 3 bars 18 mm A 516 Gr 60
Stripper Stripped water Dicrest 5

For thick equipment, steel plates are usually not available on stock. In that case a special heat can
be performed in accordance with TOTAL requirements.

As an example, a cold high pressure separator (R-4206) for an HDS unit has been fabricated
recently from 65 mm thick steel plates, made by Dillinger Hütte.

5. Conclusion
TOTAL requirements for wet H2S service have been developed on the basis of professional
documents issued by NACE or EFC, with the help of steel manufacturers and TOTAL feed-back.
These requirements give satisfactory results since no failures have been encountered on recently
fabricated carbon steel equipment.

However, as for any complex recommendation, it is regularly updated to better suit the needs. For
example, the use of higher steel grade (grade 65 or 70) is under consideration and some adaptation
of the chemistry will be necessary in the near future.

Dillinger Pressure Vessel Colloquium – Dillingen – 16 & 17 September 2009