MPWT19-14442

Corrosion Management in Hydrocracking and Hydroprocessing Units

Hendrik J. Debruyn
Saudi Aramco
Dhahran, 31311
Saudi Arabia

ABSTRACT

Hydrocracking and other refinery hydroprocessing units have a common goal to convert organic sulfur
compounds to hydrogen sulfide (H2S) that can be removed, thereby producing low-sulfur refinery
products. Corrosion and equipment degradation risks range from high-temperature hydrogen attacks
(HTHA) to ammonium bisulfide and ammonium chloride corrosion in the downstream heat recovery and
fluid separation equipment.

This paper provides an overview of corrosion management principles that can be applied to reduce
operating risks in new and existing units, focusing equipment susceptible to ammonium bisulfide (NH4HS)
and ammonium chloride (NH4Cl) corrosion. Best practices for materials selection, as well as designing
for corrosion management through adequate provision of corrosion management related instrumentation
and sampling points are covered.

Key words: Hydrocracking, hydroprocessing, ammonium bisulfide (NH4HS), ammonium chloride (NH4Cl),
and corrosion management.

INTRODUCTION

Hydroprocessing and hydrocracking units use hydrogen at elevated temperatures and pressures to
improve the quality of the different feedstock. Hydrogen sulfide (H2S) and ammonia (NH3) are produced
from the reaction of hydrogen with sulfur and nitrogen present in the hydrocarbon feed. Several other
reactions can also occur, including the conversion of any chlorides in the feed to hydrochloric acid (HCl).
Figure 1 shows a typical process flow diagram for a hydrocracking unit.1

Corrosion in refinery hydroprocessing and hydrocracking units has been a known problem since the
1960’s.2 In 1976, Piehl published the NACE T-8-1 survey of corrosion in hydrocracker effluent air coolers
(REACs).3 This report identified the following parameters governing corrosion in the coolers:

• Fluid velocity in the reactor effluent air cooler (REAC) tubes and associated piping
 • Partial pressures of hydrogen sulfide (H2S) and ammonia (NH3)
• Ammonium bisulfide (NH4HS) concentration in the downstream separator sour water
• Piping header configurations
• Use of single vs multiple water injection points
• % Vaporization of water at the REAC inlet

During the following years, numerous surveys have been conducted by process licensors such as UOP
4,5
and the American Petroleum Institute (API).6 These surveys concurred on the above controlling
parameters and identified the importance of the wash water quality.

Figure 1: Typical hydroprocessing process flow diagram 1

The American Petroleum Institute (API) published guidelines for corrosion control through the design,
materials selection, fabrication, operation, and inspection of hydroprocessing reactor effluent air cooler
(REAC) systems in 2004. These guidelines were updated in 2012 and amended in 2014 following the
availability of a joint industry research program’s results on the same subject.1

Corrosion Mechanism

The deposition of ammonium salts (NH4HS & NH4Cl) is possible in effluent from hydrocracker and
hydroprocessing units. The formation of the salts occurs through the following reactions:

𝐻𝐻2 𝑆𝑆 + 𝑁𝑁𝑁𝑁3 ↔ 𝑁𝑁𝑁𝑁4 𝐻𝐻𝐻𝐻

𝐻𝐻𝐻𝐻𝐻𝐻 + 𝑁𝑁𝑁𝑁3 ↔ 𝑁𝑁𝑁𝑁4 𝐶𝐶𝐶𝐶

Ammonium chloride (NH4Cl) salt can form below its salt deposition temperature (see Figure 2) and could
deposit inside the REAC feed piping and/or tubes. Upon further cooling, ammonium bisulfide (NH4HS)
salt may form below its salt deposition temperature (see Figure 3). In many cases, the NH4HS deposition
temperature is below the water dew point so that solid NH4HS deposition is not observed.

Solid NH4Cl forms in this area

Dissociated NH4Cl in vapor

phase this area

Figure 2: Estimating NH4CI Deposition Temperature from Process Stream Composition

Ammonium salts depositing in cooler tubes will affect heat transfer efficiency. If not removed during an
outage, such deposits can restrict flow or completely plug cooler tubes. The associated increase in
pressure drop will promote flow maldistribution, which in turn could significantly increase the velocities in
some tubes and even cause maldistribution of the wash water. The latter will have a direct impact on
corrosion rates.

Aqueous NH4HS forms an alkaline, sour water solution. Corrosion rates increase with increasing NH4HS
concentrations, H2S partial pressure, and velocity. The predominant mechanism is erosion-corrosion.
However, under stagnant conditions, the concentrated salt solutions will also be corrosive.

Solid NH4Cl salt can form directly from NH3 and HCl when present in the vapor phase. Dry NH4Cl salt is
not corrosive, but could foul equipment and plug heat exchanger tubes. The salt is hygroscopic and can
get wetted due to trace amounts of free water in the reactor effluent stream. This will result in low pH
conditions under the salt deposits, producing localized corrosion. If sufficient wash water is not present
downstream of the injection point to dissolve and dilute the salt deposits, then the salt wet deposits will
be highly corrosive.

Note that wet H2S solutions can promote cracking, such as sulfide stress cracking (SSC), hydrogen
induced cracking (HIC), stress-oriented hydrogen induced cracking (SOHIC), and hydrogen blistering, in
susceptible materials.
 Solid NH4HS forms in this area

Dissociated NH4HS in vapor

phase this area

Figure 3: Estimating NH4HS Deposition Temperature from Process Stream Composition

Controlling Parameters
Process Parameters

Ammonium Bisulfide Concentration

The primary process parameter that determines corrosivity is the ammonium bisulfide (NH4HS)
concentration. Both the referenced surveys have indicated that an ammonium bisulfide (NH4HS)
concentration of 2% is an acceptable upper limit to ensure low corrosion rates of carbon steel.3,4,5 An
older industry limit of 8% NH4HS with velocities less than 6.1 m/s (20 ft/s), has in many cases resulted in
severe corrosion damage.

In hydroprocessing and hydrocracker units, there are typically more H2S than NH3. The NH4HS
concentration is therefore determined by the unit feed nitrogen content and unit severity.

Controlling the NH4HS concentration by reducing either the nitrogen content of the feed or level of
denitrification is neither practical nor economical. It is therefore more appropriate to manage the NH4HS
concentration through sufficient wash water addition rates.

NH4HS concentrations in the sour water should be determined by appropriate process modeling with
ionic equilibria considerations or obtained through sampling and laboratory testing.

Industry experience suggests that in the reactor effluent systems, the first condensed water droplets do
not contain large concentrations of NH4HS.8 The concentration increases as the effluent stream is
cooled. In a system with wash water injection, the dew point is forced with the injection water. If the
process stream contains HCl, then the first water droplets could be slightly acidic. The pH of these first
droplets it will not be very low pH because of buffering.

Fluid Velocities

The second important corrosion controlling parameter is the bulk fluid velocity. For any given NH4HS
concentration, increasing the velocity will increase corrosion rates.

To prevent corrosion damage, refineries have historically limited velocity to a maximum of 6.1 m/s (20
ft/s) for carbon steel systems and 9.1 m/s (30 ft/s) for alloy systems, regardless of the NH4HS
concentration. Later experiences showed that carbon steel tubes and piping have corroded significantly
at 6.1 m/s (20 ft/s), especially at higher NH4HS concentrations, and that it is not appropriate to establish
simple velocity rules.

A joint industry project established in 2004, shows isocorrosion diagrams for several alloys 8. These
diagrams show the relationship between NH4HS concentration and velocity. One such diagram for carbon
steel is shown in Figure 4.

Figure 4: Isocorrosion diagram for Carbon Steel 8

In the past, some refineries have applied a minimum velocity of 3 m/s (10 ft/s) to air cooler tubes to ensure
sufficient flow to prevent salt deposition and to remove salt deposits. Prevention of salt deposits by proper
contacting of the injection water with the vapor phase to remove ammonium salts from the vapor phase
and to dissolve it in the water is now considered much more critical than maintaining a minimum velocity.1

Hydrogen Sulfide (H2S) Partial Pressure

The H2S partial pressure is also a variable that determines corrosivity of the reactor effluent streams.8
Laboratory studies showed that corrosion rates increased with an increase in H2S partial pressure at
given NH4HS levels. At high NH4HS concentrations, this effect becomes more pronounced.

This effect is also prevalent on stainless steels such as alloy 20 (UNS N08020), and nickel-base alloys
such as alloy 825 (UNS N08825), alloy 600 (UNS N06600), and alloy 625 (UNS N06625).

Flow Regime
NH4HS corrosion is fundamentally an erosion-corrosion damage mechanism. The flow regime is
therefore also a controlling parameter, albeit difficult to define and control.

Flow regimes that strip away and remove the protective iron-sulfide scale are considered detrimental.
Low velocity stratified and annular flows are considered less detrimental.

Chlorides

Chlorides entering a unit in the hydrocarbon feed stream or the hydrogen stream are converted to
hydrochloric acid (HCl). HCl can promote corrosion through aqueous HCl corrosion, NH4Cl fouling, and
corrosion by wet NH4Cl deposits.

Aqueous HCl corrosion can be very aggressive when present in the reactor effluent streams. Damage
frequently occurs at the first water condensation point. This is often at the wash water injection point.

Solid NH4Cl salt can form directly from the NH3 and HCl present in the reactor effluent stream. This salt
often deposits at temperatures above the water condensation point (up to 200°C/400°F or higher).

Deposition is possible in the following areas:

• Reactor effluent heat exchangers (upstream of the water injection)

• At the inlet end of the reactor effluent coolers
• In the top section and overhead system of the fractionator

Dry NH4Cl salts are not corrosive but can create significant fouling problems. However, the salts are
hygroscopic, and tend to absorb moisture from the process stream, becoming very corrosive.

Controlling fouling and corrosion associated with NH4Cl usually focuses on eliminating or at least
minimizing the deposition of the salt by:

• Determining the source of chlorides and attempting to lower their concentration or eliminate them
from unit feed streams
• Maintaining the temperature above the salt deposition temperature
• Adding wash water

Knowing the salt deposition temperature and monitoring of chlorides to detect changes is essential. Direct
analyses and monitoring of chlorides in the feed streams (both hydrocarbon and hydrogen) are preferred.

Temperature Control

Process licensors frequently specify minimum cooler outlet temperatures that are above the NH4HS
sublimation temperature for a specific design. The purpose of such temperature limits is to ensure that
NH4HS salt precipitation and subsequent fouling does not occur in the coolers.

Other Process Variables

A number of other process variables that could influence the corrosivity of the process fluid include
temperature, cyanide concentration, and the oil/water ratio. These however, have only minor influences
on corrosion rates.8
Wash Water

Purpose and Quantity

Wash water should be injected with sufficient quantities to lower the dissolved NH4HS and NH4Cl
concentrations to levels where corrosion rates are minimized. The wash water should also scrub HCl
from the vapor phase into the water phase.

The wash water injection rate should be based on the following objectives:

• Ensuring an acceptable NH4HS concentration in the separator water to minimize corrosion

• Allow sufficient condensed (free) water between the injection point and the reactor effluent cooler
inlet

Common recommendations are to maintain a minimum wash water addition rate of 3% of the total unit
feed for reactor effluent coolers. However, to ensure that there is sufficient free water, the rule-of-thumb
is to have at least 25 % remaining as a liquid after the injection point.1

Wash Water Quality

The quality of water is important so as not to contribute to the corrosion potential. Table 1 lists the typical
quality parameters for wash water.1

Table 1: Wash Water Requirements

Units Source
Clean Stripped Sour Combined
Parameter
Condensate Water Injection Water
Minimum Requirements Recommended
Total Dissolved Salts wt-ppm < 25 <3 < 10
Total Suspended
wt-ppm 0.2 0.2 0
Solids
Dissolved oxygen wt-ppb < 50 < 50 < 15
H2S wt-ppm 0 < 20 < 10
NH3 wt-ppm 0 < 20 < 10
Cl- wt-ppm <5 <1 <5
pH 7.0 – 9.0 7.0 – 9.0 7.0 – 9.0
Cyanide wt-ppm 0 0 0
Dissolved iron (Fe) wt-ppm <1 <1 0.1

Suspended solids are normally minimized as particulates can plug spray nozzles or quills used for wash
water injection.

Oxygen content is a critical variable as this will increase potential corrosion due to chloride pitting at and
just downstream of the water injection point. Oxygen also increases corrosion due to sulfides, especially
at lower concentrations NH4HS, and will react with the bisulfide ion to form elemental sulfur.

Iron levels should be low as higher levels will form insoluble iron sulfide and could deposit in the cooler
tubes and equipment. 11.3 m3/hr (50 gpm) of wash water containing only 1 ppm of iron will form more
than 136 kg (300 lbs) of iron sulfide in a year.
Plant Design

Piping

The design of the piping system in and out of the coolers should ensure that velocity limits are maintained
and turbulence is minimized.

Balanced flow through the coolers and inlet/outlet piping is important to reduce the potential for localized
corrosion and fouling. It should be noted that while corrosion is material of construction dependent, fouling
is independent of material of construction. Unbalanced flow conditions can create high flow rates in some
coolers and low flow rates in others. These conditions can also result in variations in wash water
distribution.

Piping configurations that increase the pressure drop through a particular air cooler bank can cause
maldistribution of the process flow. The use of a balanced inlet and outlet piping configuration is the most
common approach to ensure proper distribution.

Balanced flow may be the intent of the design, but when the system is in service, the flow can be
influenced by operational factors. Particular air cooler banks can be operated differently, which promotes
greater fouling or increased cooling in one than another. This is especially true when the fans are
operated unevenly. These actions can increase the pressure drop, and therefore, unbalance the flow.

A recent paper illustrated how wash water maldistribution could occur, even with a balanced inlet and
outlet piping design.9

Wash Water Injection Systems

Wash water injection systems are configured with either a single or multiple injection points, depending
upon the configuration of the inlet piping.

For balanced, symmetrical systems, single injection points are used, assuming that the water will be
distributed equally through the system. For an unbalanced system, it can be difficult to assess the process
flow through each inlet leg and therefore, harder to determine the amount of water needed at each
injection point.

The material used for the construction of piping and air coolers also influences the selection since alloy
materials are generally more forgiving of poor water distribution when considering NH4HS corrosion.

It is preferred to always use an injection quill for wash water injection. Further best practices for the
injection system are as follows:

• Symmetrical about the centerline of the pipe

• Full-cone spray
• In the direction of flow
 Materials Selection

In refinery hydroprocessing and hydrocracking units, the materials of construction and mechanical design
of equipment/piping have a significant impact on corrosion damage. According to the 1998 API survey, 6
and later published guidelines,1 alloy materials are selected for high severity units in order to allow greater
flexibility in the mechanical design and operation. For existing installations where carbon steel failed or
was predicted to have deterioration problems, many refineries have selected to upgrade to more resistant
alloys.

Carbon Steel

Carbon steel is used for piping and pressure vessels in colder sections of the reactor effluent system,
and for air coolers operating under low severity NH4HS conditions, i.e. < 2wt% in cold separator sour
water. It has the least resistance to NH4HS corrosion 8 and is susceptible to wet hydrogen damage if not
specifically mitigated.10 Carbon steel suffers, similarly to many other alloys, extremely high corrosion
rates under wet NH4Cl deposits.

Duplex Stainless Steel

Duplex stainless steels are often successfully used in reactor effluent cooler service as these materials
offer considered more cost-effective than nickel-base alloys.

22% Cr duplex stainless steel (UNS S31803 / UNS S32205) has failed by hydrogen embrittlement
cracking in REAC service, but problems were initially attributed to improper fabrication. More recently,
serious failures have raised serious questions regarding the suitability of these alloys in alkaline sour
environments.11

Ferritic Stainless Steels

The type 400 ferritic stainless steels have limited use in REAC service, and their use is no longer
recommended. Pitting has been experienced in a few applications as a result of chlorides, especially at
low velocities.

Austenitic Stainless Steels

The type 300 austenitic stainless steels alloys have improved resistance to NH4HS corrosion compared
to carbon steel, but should be avoided in REAC service due to chloride stress corrosion cracking (Cl-
SCC) concerns above 60°C (140°F).

Alloy 800

Alloy 800 (UNS N08800) was a standard material in the past due to its resistance to NH4HS and chloride
stress corrosion cracking (Cl-SCC). However, several failures attributed to polythionic acid stress
corrosion cracking (PTA-SCC) decreased its use in favor of Alloy 825 (UNS N08825).

Alloy 400

Alloy 400 (nickel-copper alloy, UNS N04400) has successful service in a few isolated cases. There are
concerns about the use of this alloy in elevated pH, high ammonia (NH3) content REAC systems.
Alloy 825

Alloy 825 (UNS N08825) is widely used for its resistance to NH4HS corrosion, polythionic acid stress
corrosion cracking (PTA- SCC), and chloride stress corrosion cracking (Cl-SCC). The pitting resistance
of this alloy in high chloride environments and where deposits are likely to form, makes it less suitable in
refineries where REAC fouling is a problem. It will also perform unpredictably where serious NH4Cl
corrosion is problematic.

Alloy C-276 and Alloy 625

Nickel-base alloys Alloy C-276 (UNS N10276) and Alloy 625 (UNS N06625) have performed very well
under severe conditions, mainly owing to the high molybdenum content in these alloys. Alloy 625 (UNS
N06625) has been used successfully for cladding and weld overlay in cold separators and REAC piping.

Relative Ranking

A relative ranking of engineering alloys for REAC service has been published in API RP-932B.6 This
ranking diagram is presented in Figure 5. Note that this diagram is only valid for NH4HS corrosion, and
that the performance of these alloys may be different if in NH4Cl salts are present.

Figure 5: Relative Corrosion Resistance to Alkaline, H2S dominated, NH4HS Corrosion 6

DISCUSSION

In a reactor effluent air cooler (REAC) system, intrusive corrosion monitoring techniques cannot be used.
Also, the high pressures encountered in hydrocrackers often exclude the use of such monitoring
approaches.

Instead, strict process control and monitoring of relevant process parameters are essential to ensure that
corrosion damage due to ammonium bisulfide (NH4HS) and ammonium chloride (NH4Cl) is minimized.
Table 2 shows a list of process parameters required to define integrity operating windows (IOWs) for
hydrocracker and hydroprocessing REAC corrosion.

Understanding the nitrogen content in the feed to these units, and the conversion of this to ammonia,
helps to understand the likely concentration of ammonium bisulfide (NH4HS) in the reactor effluent
stream. Similarly, knowing the level of chlorides entering the unit, either in the unit feed of possibly
through contamination of the hydrogen stream, helps to understand the potential to form ammonium
chloride (NH4Cl).

Table 2: Process Parameters to Monitor the Potential for NH4HS/NH4Cl Corrosion

Measurement Suggested
Process Parameter
Units Frequency
Unit Feed
Sulfur in unit feed ppm weekly
N2 in unit feed ppm weekly
Chloride in unit feed ppm weekly
Chloride in hydrogen ppm weekly
Reactor Effluent
H2S partial pressure in reactor effluent kPag (psig) weekly
NH3 partial pressure in reactor effluent kPag (psig) weekly
Wash Water
Total Dissolved Salts ppm monthly
Total Suspended Solids ppm monthly
Dissolved oxygen (O2) ppb monthly
H2S ppm monthly
NH3 ppm monthly
Cl- ppm monthly
pH ppm monthly
Cyanide ppm monthly
Dissolved iron (Fe) ppm monthly
Wash water rate % of feed rate online
Reactor Effluent Air Cooler (REAC)
REAC inlet temperature °C/°F online
REAC outlet temperature °C/°F online
REAC inlet pressure kPag/psig online
REAC outlet pressure kPag/psig online
Cold High Pressure Separator Sour Water
H2S content in sour water ppm weekly
NH3 content in sour water ppm weekly
NH4HS content in sour water
ppm weekly
(calculated)
Chloride (Cl-) content in sour water ppm weekly

Analyzing the wash water quality will ensure that the influence of contaminants on the corrosion
performance of the REACs are minimized. It is particularly important to ensure that oxygen levels are
controlled, and that the level of chlorides is understood. The latter might not directly influence the
formation of ammonium chloride (NH4Cl), but chlorides in the wash water will contribute to pitting and
potential chloride stress corrosion cracking (Cl-SCC) of REAC tube alloy materials.

Monitoring the parameters in the cold high-pressure separator sour water will provide an overview of the
effectiveness of the wash water addition and general NH4HS and NH4Cl levels.
 CONCLUSIONS

This paper has provided an overview of hydrocracker and hydroprocessing unit corrosion that can occur
in the reactor effluent air coolers (REACs), through the formation of ammonium bisulfide (NH4HS) and
ammonium chloride (NH4Cl). Optimum design, materials selection and process control have been
discussed.

For any design, it is important to monitor process parameters that will ensure efficient corrosion
management.

ACKNOWLEDGEMENTS

The author would like to thank Saudi Aramco management for allowing us to submit and present this
work.

REFERENCES

1. API Recommended Practice 932-B, “Design, Materials, Fabrication, Operation, and Inspection
Guidelines for Corrosion Control in Hydroprocessing Reactor Effluent Air Cooler (REAC) Systems”,
American Petroleum Institute (API), 2014.

2. R.L. Piehl, “Corrosion by Sulphide-Containing condensate in Hydrocracker Effluent Coolers,”

Proceedings of American Petroleum Institute Division of Refining, 33rd Midyear Meeting, paper no. 12-
68, (Philidelphia, PA, May 15th, 1968).

3. R.L. Piehl, “Survey of Corrosion in Hydrocracker Effluent Air Coolers,” Materials Performance, pp.
15-20, January 1976.

4. C. Harvey, R.L. Piehl, A. Singh, “Corrosion of Reactor Effluent Coolers,” UOP – 1995.
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paper no. 490. NACE International, 1997.

6. API Publication 932A, “A Study of Corrosion in Hydroprocess Reactor Effluent Air Cooler systems,”
American Petroleum Institute, 2002.

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

8. R.J. Horvath, M.S. Cayard, R.D. Kane, “Prediction and Assessment of Ammonium Bisulfide Corrosion
under Refinery Sour Water Service Conditions,” NACE CORROSION 2006, paper no. 06576. NACE
International, 2006.

9. G.E. Jacobs, C.A. Shargay, J. Cabrera, K. Moore, “Single vs Multiple Injection Points for REAC Wash
Water Systems – Interesting Process Simulation Results,” NACE CORROSION 2016, paper no. 7202.
NACE International, 2016.

10. NACE MR0103/ISO 17945, “Petroleum, Petrochemical and Natural Gas Industries — Metallic
Materials Resistant to Sulfide Stress Cracking in Corrosive Petroleum Refining Environments,” 23
November 2015.

11. S. Ghosal, “Failure Analysis of Reactor Effluent Air Cooler (REAC) in Hydrocracker Unit”, NACE
CORROSION 2014, paper no. 3730. NACE International, 2014.