SAUDI ARAMCO MOBIL REFINERY CO.

, LTD
TECHNICAL INSPECTION
CORROSION MANUAL
Title: NAPHTHA HYDROTREATING Orig. Issued September 2001
Page 1 of 6
UNIT Revised December 2002

I. PROCESS OVERVIEW

The primary function of the Naphtha Hydrotreating (NHT) Unit is to desulfurize the
naphtha feed to the CCR Unit. Other feed impurities such as nitrogen are also treated in
the NHT Unit.

The naphtha charge to the Unit, mainly from the Crude Unit, is received in the Feed
Surge Drum (21-D-01), where the fuel gas is knocked out. The feed is then mixed with
hydrogen, which is needed for the treatment reaction, hence, the process is called
“Hydro”-treating. The hydrogen gas is supplied from the CCR Net Gas Compressor.
Subsequently, the combined feed (hot naphtha and hydrogen) is heated first in the
Combined Feed/Effluent Exchangers (21-E-01’s) and then in the Charge Heater (21-B-
01). The combined feed is then sent to the Hydrotreating Reactor (21-D-02), where the
reaction takes place. Hydrotreating is accomplished by converting organic sulfur and
nitrogen into Hydrogen Sulfide (H2S) and Ammonia (NH3) respectively, under high
temperature and pressure conditions and in presence of catalyst.

The reaction products are cooled via the Combined Feed/Effluent Exchangers, Reactor
Product Condenser (21-E-02) and Reactor Product Trim Cooler (21-E-07), and finally
sent to the Product Separator (21-D-05). The Product Separator disengages hydrogen
from hydrocarbons and routes it as a make up gas to the CHD Make-up Gas Compressor
(32-K-01). Sour water that is collected at the Product Separator boot is sent to the Sour
Water Stripper (SWS) Unit. The treated naphtha continues to the Depentanizer Tower
(21-C-01) after pre-heating against the Tower bottom in the Depentanizer Feed/Bottom
Exchangers (21-E-03’s). The Depentanizer overhead off-gas and liquid streams are sent
to the Saturate Gas Plant (SGP) and the bottom effluent goes to the Dehexanizer (21-C-
02).

The Dehexanizer splits light hydrocarbons (overhead stream) from the treated naphtha
(bottoms); the bottom naphtha is the CCR feed. Both the Depentanizer and Dehexanizer
fractionating heat requirements are provided by fired heaters: Depentanizer Reboiler (21-
B-02) and Dehexanizer Reboiler (21-B-03) respectively. A simplified process flow
scheme for the NHT Unit is attached.

II. CORROSION OVERVIEW

Mixture of hydrogen and Hydrogen Sulfide (H2S) is very corrosive to most metals used in
the refinery plants. High temperature Sulfidation corrosion is a main corrosion problem
in the reaction section of hydrotreating units. Therefore, special alloys are used for the
 SAUDI ARAMCO MOBIL REFINERY CO., LTD
TECHNICAL INSPECTION
CORROSION MANUAL
Title: NAPHTHA HYDROTREATING Orig. Issued September 2001
Page 2 of 6
UNIT Revised December 2002

Heater’s tubing, transfer piping and the Reactor in SAMREF’s NHT Unit. Heater’s tubes
and associated piping are constructed from Stabilized Austenitic Stainless Steel grade
321SS, while the Reactor overlaid with 347 SS to mitigate Sulfidation corrosion.

Another vulnerability introduced by hot, high pressure hydrogen environment in the

reaction section is High Temperature Hydrogen Attack (HTHA). HTHA is particularly
pronounced in the Reactor and the Feed/Effluent Exchangers Section. HTHA starts when
hydrogen atoms diffuse into the steel and react with carbides and dissolved carbon in the
steel lattice to form Methane (CH4) gas. The gas so formed will accumulate preferably at
the grain boundaries. Continued exposure can produce extensive intergranular
microfissuring that may drastically reduce the metal ductility. The metal lattice becomes
locally distorted which restricts the dislocation mobility, thus the deformation ability of
the lattice will be limited. Loss of strength from De-carburization (carbon depletion) and
cracking and/or blistering are additional possible results of HTHA. Cracking is normally
accelerated by residual stresses, particularly at welds and HAZ’s.

If ammonia is present along with water and H2S, a layer of ammonium hydrosulfide
(NH4HS) can be formed on the steel substrate. NH 4HS could result in heavy erosion-
corrosion to steels. The severity of ammonium hydrosulfide erosion-corrosion is affected
greatly by its concentration and the stream velocity. This phenomenon is described
further under the CHD Unit Section of this Corrosion Manual.

Make-up hydrogen to the NHT Unit comes from the CCR Unit, which contains some
amounts of chloride. The presence of chloride and ammonia in the system results in
composing ammonium chloride (NH4Cl) salt, which is severely corrosive. Further,
ammonium chloride at low temperature, generally under 180°C, precipitates to cause on-
stream plugging of equipment. Salts formation is more likely to take place at the Reactor
effluent stream. It increases with increased concentrations of ammonia and chlorides.
Chlorides in the system can also cause pitting corrosion and Chloride Stress Corrosion
Cracking (ClSCC) of Austenitic Stainless steels. After commissioning of the CCR Net
Gas Scrubber in 1988, milder corrosive chloride environment had been incorporated in
SAMREF’S NHT Unit.

The NHT reaction produces H2S, which in turn reacts with steel in an aqueous phase and
generates atomic hydrogen at the internal surface of equipment. This atomic hydrogen
then migrates into the steel causing many potential damages such as Hydrogen Blistering
and Embrittlement, Hydrogen Induced Cracking (HIC), Stress Oriented Hydrogen
Induced Cracking (SOHIC) and Sulfide Stress Cracking (SSC). The details of each
damage mechanism, factors and mitigation means are covered in the FCC Unit of this
Corrosion Manual.
 SAUDI ARAMCO MOBIL REFINERY CO., LTD
TECHNICAL INSPECTION
CORROSION MANUAL
Title: NAPHTHA HYDROTREATING Orig. Issued September 2001
Page 3 of 6
UNIT Revised December 2002

Austenitic Stainless steels could be sensitive to preferential attack by polythionic acids

due to the depletion of chromium from the metal microstructure. That is commonly
referred to as Polythionic Acid Stress Corrosion Cracking (PSCC). The sulfide layer on
the metal ID surface oxidizes to polythionic acid when exposed to air and moisture during
equipment shutdowns. Stabilized Stainless steels such as 18Cr-10Ni-Ti (321SS) and
18Cr-10Ni-Cb (347SS) exhibit substantial resistance to PSCC. Low carbon Stainless steel
grades too are recommended for PSCC resistance.

III. CORROSION CONTROL

Material Selection

As stated previously, high temperature Sulfidation corrosion in the NHT Unit is slightly
unique and more dynamic due to the presence of hydrogen. Standard Low alloy steels like
5% Cr and 9% Cr alloys that are used in Sulfidation environment do not perform
satisfactorily enough in the NHT Unit case. Higher alloys such as 18Cr-8Ni Stainless
steels are used in the reaction circuit of the NHT Unit in order to resist Sulfidation
corrosion. The Heater’s tubes are constructed from 321 SS metallurgy for the added
value of Stabilization. The advantages and limitations of materials/alloys commonly used
in the NHT Unit are provided in Table 1.

Alloy additions of Cr and Mo are used to improve the resistance of steel to HTHA.
Different metallurgies showed specific temperatures and H 2 partial pressures thresholds
against HTHA. Operating temperature and pressure data for Carbon and Low alloy steels
in hot H2 environment was first collected by George A. Nelson in 1949. The data gathered
was organized in series of curves to allow for steel selection against Hydrogen Attack.
These became known as Nelson Curves. The American Petroleum Institute (API)
combined Nelson’s early work with API sponsored research and produced API
Puplication-941 in 1970. Since that date, many revisions have been published.

There has been a great concern with C-½ Mo steel use in HTHA environment. API-941,
with its second revision in 1977, lowered the limits for C-½ Mo steel. Yet, the failures of
C-½ Mo grades continued. Therefore, with the 1995 revision of API-941, C-½ Mo steels
were discontinued from the use in hot hydrogen service. In other words, on material
selection for equipment with respect to HTHA resistance, current practices give no credit
for C-½ Mo over normal Carbon steels. This brief background is a good reasoning for the
unpredictability associated with the C-½ Mo equipment that failed due to HTHA
 SAUDI ARAMCO MOBIL REFINERY CO., LTD
TECHNICAL INSPECTION
CORROSION MANUAL
Title: NAPHTHA HYDROTREATING Orig. Issued September 2001
Page 4 of 6
UNIT Revised December 2002

throughout the last decades. SAMREF’s specifications have therefore discontinued the
practice of using C-½ Mo material in any high pressure, hot hydrogen service.

Similarly, there is a wide industrial thought that Austenitic Stainless steel (SS) internal
protection cladding or overlay normally mitigates the potential of HTHA because the
permeability of H+ is lower in SS than base metal. Taking credit of the internal
Austenitic SS lining protection is not normally done for new construction, but is a widely
accepted practice for “Fitness For Service” considerations for existing equipment
assessment. In most cases, it sums up to the judicious deliberation of many factors
(fabrication data, lining inspection history & effectiveness, operating conditions) in a
“case-by-case” evaluation basis.1

Design & Fabrication Quality Control

In many cases, Wet H2S damages can be virtually minimized by proper measures and
requirements at the design and fabrication stages such as hardness and strength control by
Post Weld Heat Treatment (PWHT) and chemical composition. These requirements are
provided in the FCC Unit Section-Corrosion Manual.

Minimizing turbulence and direct injection points by proper design is helpful to control
NH4HS erosion-corrosion problem. In piping design, large diameter lines or long radius
bends are preferred. The general rule of thumb is to maintain the flow velocity below 6
m/s for Carbon steel and 9 m/s for alloy steel piping.

Corrosion Monitoring

Corrosion monitoring program in the NHT Unit is a comprehensive program including

applicable Non Destructive Tests (NDT) while equipment is in-service and out-of service.
On-stream programs include piping and vessel Ultrasonic thickness measurements and
visual routine checks. Opportunities during unit turnarounds are utilized to perform
additional assessment using UT-Shearwave (UTS) and Wet Fluorescent Magnetic Testing
(WFMT) techniques. WFMT has proved remarkable sensitivity in detecting Wet H 2S
damages.

Detection of HTHA problems is quite a challenge due to the micro-structural nature of the
HTHA mechanism; there will be no apparent manifestation until failure. Conventional
techniques have not effectively demonstrated their capabilities in detecting HTHA signs
in early stages. Therefore, HTHA is an especially dangerous type of damage because of
1
Presuming absolute protection from the Austenitic SS does not seem to be a conservative approach, while assuming
nil protection sounds very conservative, on the other hand.
 SAUDI ARAMCO MOBIL REFINERY CO., LTD
TECHNICAL INSPECTION
CORROSION MANUAL
Title: NAPHTHA HYDROTREATING Orig. Issued September 2001
Page 5 of 6
UNIT Revised December 2002

this difficulty in early detection. New models of Automated UT techniques have been
developed extensively throughout the past decade to provide higher confidant detection
approach for HTHA. ID metallography replication is another useful method in searching
for HTHA evidence. The obstacle for this technique is that most equipment that is prone
to HTHA is internally lined with higher corrosion resistant material.

Process Control

Heat exchangers heat transfer duties and pressure drop across them are proved evidence
for fouling and probable subsequent corrosion problems. Frequent monitoring of
chlorides in the hydrogen gas generated from the CCR Unit is essential in preventing
chloride-induced corrosion problems.

Control of the system temperature and pressure is another measure of corrosion and
deterioration control. Those factors are actually held almost constant as an essential
requirement for process reasons such as reaction yield and catalyst life and activity.

Practices

Water wash practice is one of the most effective control means against salt deposition
such as ammonium chloride. SAMREF has water wash facilities for the Reactor effluent
stream equipment and intermittent wash operations are executed as needed.

Equipment alkaline washing (2% soda ash solution) during unit outages and prior to
exposing the Stainless steel components to air and moisture has been the general best
practice to minimize the probability of PSCC. The intent of the alkaline wash is to
remove the iron sulfide layer by converting it to oxides. Iron sulfide is an essential factor
in formation of polythionic acid. Alkaline washing also neutralizes chlorides, thus
lessening the possibility of ClSCC.

IV. UNIT CORROSION SUMMARY

Corrosion in the NHT Unit has been minimal, mainly because of the proper metallurgy
application and relatively low nitrogen content in the feed. The Combined Feed/Effluent
Exchangers (21-E-01’s) have suffered from continuous pitting corrosion. Corrosion was
attributed to chloride content of the feed from the CCR net gas. The corrosive
environment had been less aggressive since the commissioning of the Net Gas Scrubbers.
Higher Stainless Steel grade (SS 317L) was installed in 2002 T/A for the first four
 SAUDI ARAMCO MOBIL REFINERY CO., LTD
TECHNICAL INSPECTION
CORROSION MANUAL
Title: NAPHTHA HYDROTREATING Orig. Issued September 2001
Page 6 of 6
UNIT Revised December 2002

exchangers’ tube bundles for better pitting corrosion resistance due to higher
Molybdenum content (3.0% - 4.0%).

The Depentanizer Feed/Bottom Exchangers (21-E-03’s) experienced corrosion attack on

the tube bundles in varying degrees. The tube bundles of exchangers B, C and D were
replaced in 1990. Exchanger A tube bundle was replaced in 1988. Both bundles of
exchangers C and D were replaced again in 2000. Also, bundles A& B were replaced
with retubed bundles in 2002 T/A.

During the 2002 T/A, about 40% of the Naphtha Splitter Reboiler (21-B-03) tube middle
supports were fell down due to fasteners (bolts & nuts) oxidation. These bolts & nuts
were surprisingly of C/S material. As a result, the bolts & nuts were all replaced with SS
(ASTM A4530-660) metallurgy.

SPECIAL REFERENCES

1. API Publication 941 “Steels for Hydrogen Service at Elevated Temperatures and Pressures
in Petroleum Refineries and Petrochemical Plants”, 5th Edition, January 1997.
2. Mobil Technology Company (MRCTEC), “ Materials Corrosion Inspection,” May 1997.