NACE Paper No.

MECCOCT18-12335

Risk Management of High Temperature Hydrogen Attack in Refineries

Jehad Al Aithan, Sayee P. Raghunathan, Hendrik J. Debruyn

Consulting Services Department
Saudi Aramco
Dhahran, 31311
Saudi Arabia

ABSTRACT

Duplex stainless steels (DSS) are widely used in the oil and gas industry and is one of the typical materials
choices for constructing the reactor effluent air cooler (REAC) of hydrocracker units. The high corrosion
resistance of duplex stainless steel ensures significantly more uptime than carbon steels and austenitic
stainless steels, while the mechanical strength allows for lighter constructions, more compact system
design and less welding. However, REACs constructed from DSS have experienced many failures in
very short service time. According to reviewed literature, most of these failures are associated with an
imbalance of weld joint phases (ferrite/austenite). In the presence of parameters such as high pressure
and ammonium bisulfide (NH4HS) sulfide stress cracking (SSC) can be promoted. Nevertheless, there
is still a debate in the industry about the main cause of these failures. This paper will examine the
attributed factors of the cracked DSS reactor effluent air coolers as well as other key elements such as
water wash, process parameters and flow regime through an in-depth literature review.

Key words: duplex stainless steel, reactor effluent cooler, materials selection

INTRODUCTION

Hydroprocessing in the refinery consists of hydrocracking and hydrotreating units that upgrade low value
oil into cleaner, high value fuel products and reduces sulfur, nitrogen and aromatics in the hydrocarbon
streams. With the growing demand for clean transportation fuels, flexibility in product yields, and a shift
toward low sulfur diesel, hydroprocessing has become an increasingly important refinery process. A block
diagram for a refinery is provided in figure below, showing the use of such hydroprocessing units.

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 Figure 1: Refinery Process Block Diagram

Hydrocracker units are used to produce maximum distillates of high-speed diesel, kerosene, naphtha
and liquefied petroleum gas (LPG). During the sulfur removal procedure in the hydrocracker reactors,
reactions occur at high temperature in the presence of hydrogen. After reactions, the process stream
containing hydrogen sulfide (H2S), ammonia (NH3) and hydrogen chloride (HCl) enters the recycle gas
and separation section including Reactor Effluent Air Coolers (REACs) and Hot/Cold High/Low Pressure
Separators and Absorbers. The reactor effluent air cooler (REAC) is one of the most important pieces of
equipment which cools the reactor effluent before separating the vapor (recycle gas) from the oil effluent
and the sour water.

Ammonium bisulfide forms in sour water systems where both ammonia and hydrogen sulfide are present.
Ammonium bisulfide causes severe flow-enhanced corrosion damage and also is responsible for under-
deposit corrosion attack. Flow-enhanced or erosion-corrosion can occur at impingement points such as
elbows or Tees, or downstream of flow disturbances such as welds or flow control valves. In low-flow
areas, under-deposit corrosion or interface corrosion with pitting in a line is also reported. Older REAC
designs used carbon steel, but these were based on low concentrations of ammonium bisulfide and
involved frequent and thorough inspections. It should be noted that many parameters such as flow
velocities, pH, temperature, partial pressures of H2S and NH3, and solution contaminants such as oxygen,
chlorides, and cyanides influence corrosion resistance in such systems. From industry wide surveys
carried out and various reports and papers there are some common conclusions:

a. Increasing the ammonium bisulfide (NH4HS) concentration in the aqueous phase increases
the corrosion of carbon steel and alloys.
b. Increasing fluid velocity increases the corrosion rate. The recommended maximum velocities
vary for carbon steels and alloys.

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 c. Wash water injection rate and water distribution are critical to control the NH4HS deposition
and aqueous solution concentrations.
d. Wash water quality can influence the corrosivity of the system.
e. Ammonium chloride (NH4Cl) salt can cause fouling and corrosion in units with chloride
present in the reactor effluent stream.

Unexpected high corrosion rates have sometimes also been found in Saudi Aramco hydrocracking units
using carbon steel components. For example, between late 1993 and 1995, corrosion rates ranging
between 2.5 to 4 mm/yr necessitated urgent repairs to critical parts of hydrocracker reactor effluent air
coolers (REAC) in one of the refineries. Such systems contain corrosive agents plus flammable hydrogen
and naphtha and high concentrations of toxic hydrogen sulfide at very high pressure and the
consequences of failure are significant. Corrosion leaks in such high-pressure systems carrying
flammable and toxic gas can result in fires. A typical major hydrocracker fire can cost up to $50 million.
In addition to the risk of fire, a corrosion leak that shuts down the system results in a loss of approximately
$0.5 million per day. As a result, for newly constructed refineries, with sour and high Nitrogen feeds,
carbon steel materials have been routinely substituted by corrosion resistant alloys. Materials currently
in use in REAC systems include carbon steel, type 400 series stainless steels, type 300 series austenitic
stainless steels, duplex alloys 3RE60 and 2205, alloy 800, alloy 825 and alloy C-276. Alloy 400 has also
been used in some units.

Duplex stainless steels are used in these systems because of their significant cost advantage. These
steels combine benefits of the corrosion resistance of austenitic stainless steels and strength of ferritic
steels, thus leading to weight saving as well. However, about ten cases of Duplex Stainless Steels REAC
failures (see Table 1) have been reported around the world, in some cases leading to fire and explosion.
Most DSS REAC failures were attributed to weld quality issue however, many other factors can contribute
to these failures. Some of these are discussed by Turner. 1

Table 1: Summary of the Duplex Stainless Steel REAC Failures

Case Date Failure Cause

Sulfide stress cracking or hydrogen embrittlement of multiple tube-to tubesheet welds
1 1/2002
shortly after start-up. Some welds were confirmed to have high ferrite.
Cracked weld at REAC outlet-cracking within the weld deposit. Weld hardness and
2 11/2003
ferrite met requirement. About 1.25 inch of pipe spring back at failure.
32-inch long fracture with 37.5-inch total crack length in a header box weld resulting in
3 3/2005 an explosion and fire. Cracking occurred along the weld fusion line. Some evidence of
high ferrite and high hardness found in weld deposit and HAZ.
Multiple REAC outlet header and outlet piping weld cracks, some within weld deposits
4 6/2006
and some along weld fusion line. High ferrite identified at weld internal surfaces.
Header box leaked during hydrotest following repairs to cracked tube to- tubesheet
5 10/2009
welds. Cracked along weld fusion line. High ferrite in HAZ was found.
Leak in pipe to nozzle weld at REAC outlet. Crack occurred along weld fusion line with
6 9/2010
some areas of high ferrite identified.
Multiple tube-to-tubesheet leaks during hydrotest after cleaning a turnaround. REAC
7 3/2012
was built in 2004 following API TR 938-C guidelines.
Header box welds failed after 2.5 years of service, leading to a significant fire. Plate
8 2014 materials confirmed to meet UNS32205. Failure attributed to weld root porosity, weld
root corrosion and brittle fusion line fracture.

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 PROCESS OVERVIEW

Hydroprocessing units use hydrogen at elevated temperatures and pressures along with a suitable
catalyst to improve the quality of the feedstock. Since this involves the removal of objectionable elements
such as nitrogen and sulfur present in the hydrocarbon feed. Common to all units is the production of
H2S and NH3 from the reaction between hydrogen and the nitrogen and sulfur.

Generally, “heavier” feedstocks require the most severe processing (i.e., higher temperature and
pressure) and contain higher concentrations of sulfur and nitrogen that produce the highest
concentrations of H2S and NH3. Several other reactions can also occur, including the conversion of any
chlorides in the feed to HCl. Chlorides can be present as a contaminant in the hydrogen stream or in
organic and inorganic form in the hydrocarbon feed stream. Sulfur is converted to hydrogen sulfide (H2S),
nitrogen is converted to ammonia (NH3) and organic chlorides are converted to hydrogen chloride (HCl).
The formation of H2S, NH3, and HCl are of primary importance to fouling and corrosion in the reactor
effluent system. Hydrocracking and hydrotreating are commonly used hydroprocessing methods.

Figure 2: Process overview of the REAC

In the hydrocracking process a combined hydrogen-feed mixture is heated to the desired temperature in
a furnace and then passed over a suitable catalyst at high pressure in the reactor vessels, where the
reaction takes place in the presence of hydrogen. The effluent of the first stage reactor is cooled and sent
to a Hot High-Pressure Separator (HHPS). The vapor is further cooled in the HHPS vapor/recycle gas
exchanger or in some designs goes directly to the REACs for maximum hydrocarbon recovery, along
with wash water. The REAC is very important in hydrocracking as it is the last cooling solution before
separating the vapor from the oil effluent and sour water. Water is continuously injected into the inlet

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piping of the REAC to prevent the deposition of ammonium salts. Figure 2 shows a simplified flow diagram
of a hydrocracking unit. 4 This (water injection) may not be needed if the feed quality is good and therefore
no salts are deposited.2-3

The material selection and design of equipment and piping affect their performance in REAC systems.
An understanding of how differences in these equipment and piping details change the dependence upon
the scope and frequency of inspection and the range of the operating envelope is beneficial to promoting
reliability.

PROCESS CONTROLS

Ammonium Bisulfide & Ammonium Chloride

Typical operational parameters in a DSS hydrocracker REAC, based on a survey carried out as part of
an ongoing joint industry project, are shown in Table 2.

Table 2: Operating Parameters

Parameter Value
Pressure 2600 psig
Temperature 130°F
H2S partial pressure 80 psia
NH4HS concentration 12 wt%

The combined operational conditions of high pressure and low temperature bring significant problems to
REAC systems, such as ammonium bisulfide (NH4HS) and ammonium chloride (NH4Cl) precipitation.
These in-turn cause an increase in pressure drop, corrosion and/or erosion-corrosion, ultimately reducing
the effectiveness of the REACs over time. The deposition of NH4HS and NH4Cl salts in REACs has been
recognized as the main concern in hydroprocessing units. Therefore, correct material selection for the
REACs and associated piping, along with other design and operational conditions, are of critical
importance.

Carbon steel is effective with NH4HS concentrations up to 3 wt%. However, having more sour feed means
more precipitation/concentration of NH4HS salts, which in turn dictates the selection of more corrosion-
resistant materials such as duplex stainless steel, nickel-based alloys (for example alloys 625, 800 &
825). Duplex stainless steels are suitable for NH4HS concentrations of 3-8 wt%, whereas nickel alloys
are suitable for up to 15 wt% NH4HS. It is generally recommended that DSS use should be limited to
cases where the NH4HS concentration does not exceed 8%. For this to be valid, the feed should also
contain low chloride levels, implying very low rates of NH4Cl deposition. It should be noted that
intermittent higher chloride content feeds could lead to NH4Cl salt precipitation.

The operating temperature is another factor that influences the precipitation/concentration of these salts,
as the precipitation occurs in certain temperature ranges only for given concentrations in the stream. For
example, the precipitation of NH4HS and NH4Cl salts typically occur when the operating temperatures
are between 80-150°F (25-65°C) and 350-450°F (175-230°C) respectively. API RP 932-B provides
guidance on the calculation of the NH4HS precipitation temperature (see Eq. 1 & Figure 3). 4

𝐾" = {𝑁𝐻'"" } × {𝐻* 𝑆"" } (1)

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 Figure 3: Deposition temperature of NH4HS

Wash Water

In order to prevent any ammonium salts deposition, wash water injection should be maintained at 3 - 5%
of the fresh feed upstream the REAC. This can be confirmed by taking a sample from the separator boot
to determine the amount of liquid water which should be approximately 25%. Regardless of the wash
water source, wash water must be high quality water to prevent any chloride pitting and increase in
corrosion. 5-7 Typical wash water quality requirements are shown in Table 3.

Table 3: Wash Water Quality

Clean Stripped Sour Combined

Parameter
Condensate Water Injection Water
Total Dissolved Solids ppm <25 <3 <10
Total Suspended Solids ppm 0.2 0.2 Nil
Dissolved Oxygen ppm <50 <50 <15
H2S ppm Nil <20 <10
NH3 ppm Nil <20 <10
Cl- ppm <5 <1 <5
pH 7 to 9 7 to 9 7 to 9
Cyanide ppm Nil Nil Nil
Dissolved Iron ppm <1 <1 0.1

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Iron should be maintained as low as 1 ppm in the water as it could form insoluble iron sulfide which
deposit in the tubes and equipment. Suspended solids should be kept to a minimum as well to avoid
plugging spray nozzle or quill depending upon the design. 4-5

FLOW AND PIPING DESIGN

The objective of the wash water injection system ahead of an air cooler is to obtain an even distribution
of both the process fluid and the wash water through each tube of the air cooler. To achieve natural
development of the flow in vapor and liquid phases in each REAC bundle, the piping configuration must
have a sufficient straight run to obtain a uniform regime and profile. In addition to that, the velocity profile
and flow regime passing every tee should be symmetrical with the tee centerline. On the other hand,
single phase turbulent flow can have a nearly uniform velocity profile within 10 pipe diameters. This can
be achieved by having a maximum mixture superficial velocity in piping and exchangers after the addition
of wash water is 30 ft/s (9 m/s). Furthermore, the interfacial area is influenced by the piping orientation.

Horizontal Orientation

The interfacial area decreases radically when moving further downstream the injection point. Stratified-
wavy or semi-annular flow regime is created since a significant portion of the droplets coalesce on the
pipe wall, then drain by gravity to the bottom of the pipe which would reduce heat transfer with the effluent
vapor, but will promote some heat transfer with effluent liquid, if present.

Vertical Orientation

The gravity factor for droplet settling is eliminated in the vertical orientation resulting in an annular regime
which would increase the interfacial area and have better heat transfer. 5-7

Injection quills or spray nozzles design should assure that a good contact with the process vapor stream
is achieved and direct impingement upon the pipe wall is avoided. 5

WELDING AND CONSTRUCTION

Duplex stainless steels are an excellent choice when high corrosion resistance and superior mechanical
properties are required. The production and processing (including fabrication) of duplex stainless steels,
however, are sometimes technically difficult due to their metallurgical characteristics and sensitivity to
changes during processing. Mechanical properties of duplex stainless steel welds are dependent on the
microstructural characteristics such as the phase balance, precipitation of secondary phases and level
of microslag inclusions. There is good understanding on the factors to control for good quality welds.
These include consumable compositions, gas composition and cleanliness, heat input during welding
and control of cooling rates through management of appropriate interpass temperatures. Most of these
controls are more stringent than those for welding ferritic or austenitic steels. API TR 938C gives some
good guidelines and controls for fabrication and welding of duplex stainless steels. 7 However, even these
controls seem inadequate to prevent cracking of DSS welds in REACs. Most of the DSS REAC failures
were attributed to hydrogen embrittlement cracking in the welds between the top/bottom plates of header
box and tube sheet or tube to tube connections. The actual mechanism of cracking and the causes are
still under debate in the industry. It is generally known that the austenite phase provides good formability,
toughness, weldability and good resistance to hydrogen embrittlement whilst the ferrite phase contributes
to the high tensile and fatigue strengths of DSS.

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Based on the failures and the challenges involved in controls during fabrication, process licensors are
moving away from DSS REACs and recommending alloy 825 if the corrosion rates mandate the need for
a higher corrosion resistant alloy. However, there are still a number of DSS REACs still in service, and
in high pressure hydrogen operation. These need implementation of a risk assessment and mitigation
plan that includes due diligence in reviewing the fabrication and operational history of these units. This
due diligence process should include assessment of the experience and expertise level of the fabricator
in the fabrication of DSS REACs, and whether the operational history of the unit is consistent with original
design specifications. Note that units with higher ferrite contents at weldments may be at greater risk of
cracking. Hence, if welding procedure qualifications and the manufacturing data records do not give
confidence on the ferrite levels in critical header box connection welds, these should be determined at
the first possible opportunity during future turnarounds. Mockups should be developed and simulated to
as close of actual configuration as possible. These should be used for developing techniques and
procedures for ferrite estimation in the welds, especially given the challenges in access for the same.

In conjunction with the above an inspection plan specifically developed for each DSS unit, should be
established and implemented. Monitoring using techniques such as acoustic emission with good
inspection effectiveness may be necessary to determine the onset of cracking in such systems. If any
cracking onset is suspected, detailed inspection plans, and techniques should be in place to confirm and
quantify the cracks. All this should be built into the risk assessment and mitigation plan. 6,7,8

CONCLUSIONS

The control parameters mentioned in this paper provide guidelines to minimize risks in operating the DSS
REACs which are monitoring the ammonium bisulfide and ammonium chloride concentration in the feed,
maintaining efficient quantity and quality of wash water, balance piping and flow configuration and good
weld fabrication by maintaining the ferrite and austenite balance. That being said, there is still a debate
in the industry of the root cause and the damage mechanism of the cracking in DSS despite most
accidents attributed the failure to weld fabrication.

REFERENCES

1. J. Turner, “Design of Hydroprocessing Effluent Water Wash Systems”, NACE CORROSION 98, paper
no. 593. NACE International, 1998.

2. E. Lin, R.E. Risse, “Reactor effluent air cooler safety through design”, Chevron Lummus Global, 2013.

3. S. Ghosal, “Failure Analysis of Reactor Effluent Air Cooler (REAC) in Hydrocracker Unit”, NACE
CORROSION 2013, paper no 3730. NACE International, 2013.

4. API RP 932-B, “Design, Material, fabrication, operation and Inspection Guidelines for Corrosion Control
in Hydroprocessing Reactor Effluent Air Cooler (REAC) Systems,” American Petroleum Institute, 2012.

5. G.E. Jacobs, C.A. Shargay, J. Cabrera, K. Moore, “Multiple Injection Points for REAC Wash Water
Systems – Interesting Process Simulation Results,” NACE CORROSION 2016, paper no. 7207. NACE
International, 2016.

6. A. Bhattacharya, “Stress Corrosion Cracking of Duplex Stainless Steels in Caustic Solutions”, Georgia
Institute of Technology, 2008.

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7. API Technical Report 938-C, First Edition, (2005), “Use of Duplex Stainless Steels in the Oil Refining
Industry,” American Petroleum Institute, year 2005.

8. S. Naskar, “Performance in Super-Duplex Welds”, Sandvik Materials Technology, 2017.