Failure of Reactor Effluent Air Cooler (REAC)

in Hydrocracker Units.
A Literature Search

Muhammad Ramli Ahmad Bahri/ Syed Sham Ariff

Muhammad Amani/ Noraini Dahlan/ Mohd Faiz Md Izani
19th March 2018 Pengerang

http://www.totalenergy.com/SNGPlant/Section100Exchangers.htm#PhotoE102

Fion Zhang/ Charlie Chong

Reactor Effluent Air Cooler (REAC)

REAC
Reactor Effluent Air Cooler (REAC)

NH3 + H2S →NH4HS

https://www.honeywellprocess.com/library/marketing/whitepapers/CorrosionNACE06_Paper_06577.pdf
Reactor Effluent Air Cooler (REAC)
Reactor Effluent Air Cooler (REAC)

https://www.osha.gov/dts/hib/hib_data/hib19940729.html
Reactor Effluent Air Cooler (REAC)

https://www.nickelinstitute.org/~/media/Files/KnowledgeBase/Presentations/20151126Duplex%20Stainless%20Steel%20Congress%20ChinaGary%20CoatesEnglish.ashx
Reactor Effluent Air Cooler (REAC)

https://www.nickelinstitute.org/~/media/Files/KnowledgeBase/Presentations/20151126Duplex%20Stainless%20Steel%20Congress%20ChinaGary%20CoatesEnglish.ashx
Reactor Effluent Air Cooler (REAC)- Macrostructural Examination of the
Failed Weld Joints of REAC fire at Indian Refinery of DSS Construction.

https://store.nace.org/492e2a5c-a5ba-e311-a396-0050569a007e
Reactor Effluent Air Cooler (REAC)- EDS at Ductile Fracture Location of
REAC fire at Indian Refinery
Energy Dispersive X-Ray Spectroscopy (EDS)
EDS was carried out at the ductile fracture location, at the ductile-brittle (mixed mode) fracture location, and at the brittle fracture location during SEM
examination. The presence of Chlorides (0.26% to 2.68%) along with Sodium (0.32% to 1.61%), Magnesium (0.11% to 0.48%), Aluminum (0.13% to 0.65%),
Silicon (0.22% to 1.40%), Sulfur (0.58% to 2.17%), Calcium (0.23% to 0.37%) are reported. EDS reports are shown in Figures 14 (a), (b), (c).

https://store.nace.org/492e2a5c-a5ba-e311-a396-0050569a007e
Reactor Effluent Air Cooler (REAC) - Fire at ConocoPhillips Refinery

https://www.nickelinstitute.org/~/media/Files/KnowledgeBase/Presentations/20151126Duplex%20Stainless%20Steel%20Congress%20ChinaGary%20CoatesEnglish.ash
01 O bjective
Initiated by the bulletin1 from one REAC licensor on the possible failure of
REAC with DSS construction, literature search was conducted to investigate
the possible root cause of REAC tube explosion. From the literature search
there have been several fire incidences of REAC failure2,3,4 with 8 publically
reported serious incidents worldwide with significant impact3.

Root cause analysis was conducted based on this literature search; summary
and recommendations were suggested. Detailed manufacture data book MDR
reviews were performed. Conclusion on the quality of equipment fabrication
and reliability of equipment was make.

1 CLG’s bulletin to Petronas on DSS REAC failures.

2 Failure Analysis of Reactor Effluent Air Cooler (REAC) in a Hydrocracker Unit
https://www.nace.org/cstm/PaperTrail/Authors/Submission.aspx?id=a32f252b-9da1-e211-ac5b-0050569a007e
3 SURVEY OF CORROSION IN HYDROCRACKER EFFLUENT AIR COOLERS.
https://www.researchgate.net/publication/282387247_SURVEY_OF_CORROSION_IN_HYDROCRACKER_EFFLUENT_AIR_COOLERS
4 Corrosion of Reactor Effluent Air Coolers
https://www.onepetro.org/conference-paper/NACE-97490
5 Nickel Institute article Special Considerations for Welding of Thick Duplex Stainless Steel by Gary Coates
https://www.nickelinstitute.org/~/media/Files/KnowledgeBase/Presentations/20151126Duplex%20Stainless%20Steel%20Congress%20ChinaGary%20CoatesEnglish.ashx
02 D amage Mechanism for REAC
For REAC failure, depending on the material of construction, there were two
kinds of failure at the tube to tube-sheet welding (1) Ammonia bisulfide
corrosion for carbon steel 6 and (2) Stress corrosion cracking 5,7 (Sulfide stress
corrosion) for corrosion resistance alloys including duplex stainless steel DSS.
REAC Failure

Ammonia Bisulfide Sour

Water Corrosion: Carbon Steel
Thinning/ Erosion For DSS REAC-
Sulphide Stress Cracking
is the principle failure
mechanism. 2,3

Stress Corrosion Corrosion Resistance Alloy-

Cracking SCC/ Sulphide Duplex Stainless Steel &
Stress Cracking Stainless Steel

3 Nickel Institute article Special Considerations for Welding of Thick Duplex Stainless Steel by Gary Coates
https://www.nickelinstitute.org/~/media/Files/KnowledgeBase/Presentations/20151126Duplex%20Stainless%20Steel%20Congress%20ChinaGary%20CoatesEnglish.ashx
6 API571 Chapter 5.1.1.2 Ammonium Bisulfide Corrosion (Alkaline Sour Water)
7 CLG Bulletin https://www.cbi.com/getattachment/b93f3734-f9f4-4263-97db-de12fa77cd8f/Reactor-Effluent-Air-Cooler-Safety-through-design.aspx
03 C ASE STUDY
Case Study 1: Failure Analysis of Reactor Effluent Air Cooler (REAC) in
a Hydrocracker Unit
https://www.nace.org/cstm/PaperTrail/Authors/Submission.aspx?id=a32f252b-9da1-e211-ac5b-0050569a007e

A major fire incident took place in Reactor Effluent Air Cooler (REAC, 04-EA-001 D) of the Hydrocracker Unit
(HCU) on April 07, 2012 evening at 18.35 hrs. in one of the Indian refineries. The cooler had failed after a period
of 2 years in operation. Among four air coolers (04-EA-001 A, B, C & D), 04-EA-001 C & D were severely
damaged. The damage in air cooler (04-EA-001C) was less in comparison with air cooler (04-EA-001D). Cracks
were observed on the welding joints between top plate & tube sheet, bottom plate & tube sheet of the floating
header of air cooler (04-EA-001D). The reactor effluent air coolers (04-EA-001A/B/C/D) were designed by the
hydrocracker process licensor for the process fluid (HHPS vapour - H2+H2S+NH3+HC+ Water).

The material of construction was Duplex Stainless Steel (DSS) conforming to UNS S32205. The documents
related to fabrication of the air cooler (04-EA-001D) were reviewed. Visual inspection, liquid penetrant testing
and ultrasonic thickness measurement were carried out on the failed portion of the air cooler (04-EA-001D). A
systematic metallurgical investigation such as Scanning Electron Microscopy (SEM), Energy Dispersive x-ray
Spectroscopy (EDS), mechanical testing was conducted on the failed samples as a part of a failure analysis.
High hardness and low charpy impact energy indicted a very less ductile weld metal. Porosities and slag
inclusions at weld root were acceptable in radiography examination, but their presence was in favour of localized
corrosion (crevice and pitting) for the intended service. The higher percentage of chlorides was reported in EDS
results. DSS material had suffered crevice and pitting corrosion as the metal temperature was about 100°C.
Localized corrosion at weld root was corroborated the ductile fracture (dimples) by SEM. Once crack was
initiated at weld root by localized corrosion mechanism, there was continuous charging of the weld by high
pressure process fluids during operation. A complete failure was attributed to the reactor effluent air cooler (04-
EA- 001D) by a combination of low ductile and hard weld metal at very high pressure of process fluid. The
sudden failure of the weldment was characterized by brittle mode of fracture (cleavage).
 Case Study 2: CUSTOMER BULLETIN: Failures in Duplex Stainless
Steel Reactor Effluent Air Coolers in High Pressure Hydrogen Service
November 2017 Chevron Lummus Global bulletin to Owner.
Summary
This Bulletin is to notify CLG licensees of reports of failures of duplex
stainless steel (DSS) 2205 reactor effluent air coolers (REACs) in high
pressure hydro processing service in the refining industry, and to advise
them of recommendations where these DSS REACs are in service. For
those licensees with existing DSS REACs in operation, CLG recommends
that a risk assessment and mitigation plan be promptly implemented to
validate that any DSS REACs were fabricated rigorously to CLG's DSS
standards by qualified vendors and to perform additional inspections on
existing DSS REACs. Going forward, CLG will specify either Carbon Steel or
Alloy 825 (see below) as options for hydroprocessing REAC service in our
future designs. Based on service conditions, licensees should also consider
replacing their existing DSS REACs in high pressure service (1000 psi
hydrogen partial pressure and higher) with Carbon Steel or Alloy 825.
History
Duplex 2205 has been widely recommended throughout the industry for use in
REACs over the last twenty years. However, licensees and others have reported
failures of DSS REACs in high pressure, hydro processing services. For example, a
published report concerning this topic can be found in the paper PVP2016-63927,
Proceedings of the ASME Pressure Vessels and Piping Conference, July 17- 21,
2016, Vancouver, British Columbia, Canada . In addition, API RP 932-B, Design,
Materials, Fabrication, Operation, and Inspection Guidelines for Corrosion Control in
Hydroprocessing Reactor Effluent Air Cooler (REAC) Systems, 2"d Edition 2012,
Section 7.2.2 (API RP 932-B), discussed duplex stainless steel failures and attributed
those failures to improper fabrication and hydrogen embrittlement cracking. At the
2013 AFPM annual meeting, and at its 2014 Licensee symposium, CLG presented
an industry paper titled "Reactor Effluent Air Cooler (REAC}: Safety Through Design"
which highlighted CLG's stricter fabrication and welding practices which are above
and beyond those specified in API TR 938C and explained select design
considerations that are incorporated in a basic engineering package for licensees.
Initial problems associated with Duplex 2205 appeared to be controlled through
CLG's stricter fabrication protocols. However, preliminary review of recent failures
has shown that variations in fabrication practices can cause DSS REACs to be
vulnerable to failure.
 Case Study 3: Quality-controlled replacement of carbon steel with
Duplex 2205 for revamps can increase the service life and reliability of
the REAC in the high-pressure loop Chevron Lummus Global
https://www.cbi.com/getattachment/b93f3734-f9f4-4263-97db-de12fa77cd8f/Reactor-Effluent-Air-Cooler-Safety-through-design.aspx

…………….. Duplex 2205 REAC failure can be attributed to not respecting the
guidelines specific to duplex material.
………………………. …. Hardness values in the heat-affected zones (HAZ) and at the
weld of failed specimens were higher than those recommended (in the range of 313-
359 HV10 vs 310 HV10 maximum). As a result, CLG concluded that REAC failure in
this case was due to sulphide stress cracking (SSC).
 Case Study 4: Special Considerations for Welding of Thick Duplex
Stainless Steel The 5th China International Duplex Stainless Steel Congress Gary Coates Beijing, China , 26 Nov. 2015
https://www.nickelinstitute.org/~/media/Files/KnowledgeBase/Presentations/20151126Duplex%20Stainless%20Steel%20Congress%20ChinaGary%20CoatesEnglish.a
shx

REAC vessels – scope of the problem

 There have been 8 publically reported serious incidents worldwide
 This resulted in a joint MTI (Materials Technology Institute) and API (American Petroleum Institute) activity
to identify the root cause and prevent other failures.
 Many 2205 REACs were operating without any problems
 A REAC is used in hydroprocessing which involves hydrogen at high temperature and pressure.
 Sulphur and nitrogen compounds are converted by a catalyst in the first stage reactor to hydrogen sulphide
and ammonia. As the effluent stream from the reactor cools down, the ammonia and hydrogen sulfide
combine to form solid ammonia bisulfide.
 In the absence of liquid water, the ammonia bisulphide condenses directly from the vapor phase to form a
crystalline solid which can result in rapid plugging.
 To prevent this plugging, water is injected ahead of the REAC. This prevents fouling, however, a highly
corrosive ammonium bisulphide solution is created. High rates of carbon steel failures led the industry to
select duplex 2205 (S31803 or S32205) for REAC and associated piping as the most economical alloy
choice meeting the corrosion requirements.

REAC vessels – history and investigation

 Higher ferrite and high hardness in the 2205 welds were noted in many of the failures reported. Sometimes
only one weld pass had the high ferrite, but it was the weld exposed to the corrosive conditions.
 Sulphide Stress Cracking is the principle failure mechanism.
 Some REACs are made of Ni-Cr-Mo Alloy 825 (N08825), and have not reported any issues. 825 is not
susceptible to the same issues as the 2205 duplex alloy. However 825 is more expensive and not as strong
as 2205.
Case Study 5: Failure Analyses: In Retrospect
Nurul Asni Mohamed
PETRONAS Group Technical Solutions
[email protected]
Co-authors: Norhariti Hassan and Naimah Azizan
Malaysian Refining Company Sdn Bhd (MRCSB)

Failure Analyses: In Retrospect Corrocon Paper No.11851

http://www.nace-malaysia.org/docs/corcon2017/corcon2017-nurul-asni-full-paper.pdf

During the commissioning of the DSS 2205 in 2002, leak of one air-fin cooler bundle
was detected along with the smell of H2S. Snoop or bubble leak test was performed
and leaks were observed to have occurred at various tube to tube sheet welds of all
four REAC tube bundles. A detailed root cause failure analysis was conducted with
tube samples sent to a third party failure analysis laboratory in the UK. The results
revealed that the tube to tubesheet weldments failed due to sulphide stress cracking
(SSC) which occurred during the introduction of H2S containing hydrocarbon gas along
with the presence of water. ….. At the point of the investigation conclusion, the principal
causes of the observed failures were the initiation of Sulphide Stress Cracking at the
weld surface, due to the limited tolerance of the localised ferrite content of the tube to
tubesheet weldments of DSS 2205 to the process environment.
 Case Study 6: Prediction And Assessment Of Ammonium Bisulfide
Corrosion Under Refinery Sour Water Service Conditions
https://www.honeywellprocess.com/library/marketing/whitepapers/CorrosionNACE06_Paper_06576.pdf

Abstract
This paper summarizes results of a joint industry program (JIP) to address ammonium bisulfide
(NH4HS) corrosion in H2S-dominated alkaline sour waters typically found in refinery services
such as the reactor effluent air cooler (REAC) systems of hydroprocessing units. The impacts of
several process variables on corrosion were quantified. Key learnings support a paradigm shift
from the rules of thumb previously applied to these systems. Data collected were used to develop
a software tool to predict the corrosion rate of 14 materials evaluated in the program.

FIGURE 4 – Material Resistance to NH4HS Corrosion

 Case Study 7: Reading on NACE “Corrosion Control in The Refining
Industry”

Corrosion Control in
The Refining Industry
January 2010
7.4.5 Effluent Air Coolers
Effluent air coolers are probably the piece of equipment most vulnerable to
ammonium bisulfide (NH4HS) corrosion. Most plants initially install carbon
steel tubes for effluent air coolers, but some units with high Kp values have
installed duplex stainless steel, alloy 800, or alloy 825.

Duplex stainless steels, such as type 2205, are increasingly used for tubes
and header boxes, but special requirements should be imposed on the
materials as well as the fabrication and welding practices. Welds or HAZs that
do not have the proper ratio of austenite/ferrite in their microstructure can be
susceptible to hydrogen embrittlement and SSC.
 Case Study 8: Reading on NACE MR0103/ISO 17495-1:2016

ANSI/NACE MR0103/ISO
17495-1:2016
Petroleum, petrochemical and natural
gas industries — Metallic materials
resistant to sulfide stress cracking in
corrosive petroleum refining
environments
A.7 Duplex stainless steels (identified as material types)
A.7.1 Materials chemical compositions
Table D.7 lists the chemical compositions of some duplex stainless steel alloys that can, but do not necessarily,
meet the restrictions of this materials group. In some cases, more restrictive chemistries than those shown
in the Table D.7 are needed.
13.8 Duplex stainless steels
13.8.1 General requirements for duplex stainless steels
13.8.1.1 Wrought and cast duplex stainless steel products shall be in the solution-annealed and liquid-quenched
condition. Tubing shall be rapidly cooled by liquid quenching, or by air or inert gas cooling to below 315 °C (600
°F). The ferrite content shall be 35 vol% to 65 vol%.

13.8.1.2 The hardness of grades with PREN ≤ 40,0 % according to Formula (1) shall not exceed 28 HRC.
13.8.1.3 The hardness of grades with PREN > 40,0 % according to Formula (1) shall not exceed 32 HRC.
13.8.1.4 Brinell hardness measurements obtained on duplex stainless steels cannot be converted to Rockwell C
hardness values using existing tables in ASTM E140 or ISO 18265. Use of empirically derived tables for this
hardness conversion is subject to the approval of the end user.

13.8.2 Welding requirements for duplex stainless steels

Fabrication and repair welds in all wrought and cast duplex stainless steels shall be produced using a welding
procedure qualified by performing the following tests on specimens taken from the WPQT coupon(s).

a) A hardness survey shall be performed in accordance with Annex C. The average hardness shall not exceed
310 HV, and no individual reading shall exceed 320 HV.
b) Metallographic ferrite measurements shall be performed in accordance with ASTM E562. The average
ferrite content in the weld deposit and HAZ shall be within the range of 35 % to 65 %, with a relative
accuracy of 10 % or lower.

Note: 13.7.2 … PREN = %Cr + 3,3 (%Mo + 0,5 × %W) + 16 × %N

(https://www.bssa.org.uk/topics.php?article=111)
 Case Study 9: Reading on “A Study of Corrosion in Hydroprocess
Reactor Effluent Air Cooler Systems” API PUBLICATION 932-A
SEPTEMBER 2002

API PUBLICATION 932-A

SEPTEMBER 2002
5.3 REACTOR EFFLUENT AIR COOLERS
Where corrosion has been serious and persistent, unit operators have sometimes invested in
Alloy 800 or Alloy 825 as a permanent solution. Alloy 800 has been used for at least 17 years with
no major failures (Plant B); however, pitting corrosion has been reported (Plants Q and E) so that
the long-term reliability has been put in question.

5.9 ALLOY SUBSTITUTION (CS) TO PREVENT CORROSION

The alloy solution is costly. A recent study 10 concluded that to upgrade REAC exchanger and
piping materials from carbon steel to Alloy 825 would cost $1 million for a hydrocracker
unit with 6,160 ft2 of air cooler surface. Alternative solutions, however, carry more risk. This is
because the parameters affecting corrosion are not quantitatively well defined and there often is
great difficulty predicting the sites where the process parameters may fall outside of the
guidelines. Some of the alternative materials selections to replace or upgrade from carbon steel
have been discussed by Singh et al.11, and Shargay and Lewis12……..

Another approach to avoiding these problems was to employ duplex alloys which have inherent
resistance to both phenomena. 3RE60 has been used successfully (Plant CC) downstream of the
water injection point for more than 18 years with no plans to replace it. Alloy 2205 has been used
for both air cooler tubes and piping with varying success. Problems can arise if the material is not
properly specified and fabricated13. High residual hardness after welding can lead to sulfide stress
cracking and must be avoided. In addition one respondent reported selective leaching of the
ferrite phase by ammonium chloride.
 Case Study 10: Reading on: “Design, Materials, Fabrication,
Operation, and Inspection Guidelines for Corrosion Control in
Hydroprocessing Reactor Effluent Air Cooler (REAC) Systems”

API RECOMMENDED PRACTICE 932-B

SECOND EDITION, MARCH 2012
7.2.2 Duplex Stainless Steels
Duplex stainless steels are often successfully used in these systems because they offer
advantages of both the ferritic and austenitic stainless steel families. They are often cost effective
due to their higher strength and reduced alloy element content compared to other higher alloys.
However, since this material consists of dual phase microstructure, heat-treating, fabrication and
welding techniques need to be carefully reviewed and monitored to assure that the balanced
microstructure is not compromised.13 In the past, Alloy 3RE60 was successfully used, but it
had inferior corrosion resistance and toughness at the welds and is no longer available. The most
commonly used grade today is Alloy 2205.

Duplex stainless steels have failed by hydrogen embrittlement cracking in these services, but
these problems were attributed to improper fabrication. Specific considerations to minimize the
possibility of deterioration are to specify a minimum of 0.14 % N content and a water quench. This
helps avoid intermetallic precipitates. Weld procedures should be developed to assure ferrite
content in the 35 % to 65 % range (measured by ferrite scope). Higher ferrite content can lead to
hydrogen-related cracking and reduced corrosion resistance. There have been a few failures in
duplex stainless steel header box welds and duplex stainless tube-to-tubesheet welds the
designer or user need to be aware of. Additional guidance on materials and fabrication practices
to achieve good corrosion resistance in duplex stainless steels are given in API 938-C.

Super duplex stainless steels such as Alloy 2507 are predicted to perform better than Alloy 2205,
and hence are promising for resisting severe environments.
 Case Study 11: Reading on: “Use of Duplex Stainless Steels in the Oil
Refining Industry”

API TECHNICAL REPORT 938-C

SECOND EDITION, APRIL 2011
5.3 Hydrogen Stress Cracking/SSC
……..A newer NACE standard (MR0103-2007) [10] is similar to older versions of NACE MR0175
but is targeted for the refining industry. It limits DSS base materials in severe wet sour services
are 28 HRC maximum hardness. It also limits ferrite content to 35 to 65 volume percentage for
weld procedure qualification, but that was based on earlier versions of this document (API 938-C).
Some welding restrictions are also given including thickness and heat input limits.

SSC susceptibility is dependent on many variables: partial pressure of H2S, pH, chloride content,
temperature, microstructure, hardness, cold work, surface finish, etc. In the NACE TM0177 [11]
test for SSC, most DSS do not show any cracking until the applied stress is well above the proof
strength. Cold work decreases the threshold failure stress. Figure 10 shows suggested chloride
and H2S partial pressure limits for S31803 and S32760 based on testing by TWI. [2]

There have been SSC failures in refinery applications; however, they have been attributed to
improper fabrication. The hardness limit of 310 HV average (320 HV max) for weld procedure
qualification given in Annex B, along with the tight control of welding variables to help ensure that
the production welding matches the qualified procedures, are the primary means of minimizing the
risk of HSC/SSC. The 25 % Cr DSS require a higher limit due to their higher yield strength, and
testing indicates they are acceptable to higher values.
04 D iscussion
Hydrocracking, or hydroprocessing, is a two stage process combining catalytic
cracking and hydrogenation. Sulfur and nitrogen compounds are converted by
a catalyst in the first stage reactor to hydrogen sulfide H2S and ammonia. As
the effluent stream from the reactor cools down, the ammonia and hydrogen
sulfide combine to form solid ammonium bisulfide NH3 + H2S →NH4HS.
Ammonium bisulfide, also called ammonium hydrogen sulfide (NH4HS).

At REAC the process stream also contained variable amount of uncombined

hydrogen sulfide (H2S), ammonia (NH3) and hydrogen chloride (HCl)
NH4HS precipitates out of the gas phase in the reactor effluent stream (REAC)
at temperatures below about 150°F (66°C), depending on the concentration of
NH3 and H2S, and may cause fouling and plugging unless flushed away with
wash water.
NH4HS salt deposits lead to under deposit corrosion and fouling. The salts are
not corrosive unless they become hydrated at which point they are very
corrosive.
Oxygen and iron in the wash water injected into hydroprocessing reactor
effluent can lead to increased corrosion and fouling. Presence of cyanides
increases severity of corrosion in FCC gas plants, coker gas plants and sour
water stripper overheads by destroying the normally protective sulfide film.
NH4HS concentration, H2S partial pressure, velocity and/or localized
turbulence, chloride ions, pH, temperature, alloy composition and flow
distribution are all critical factors to consider. Corrosion increases with
increasing NH4HS concentration and increasing velocity. Below 2 wt %,
solutions are not generally corrosive. Above 2 wt % NH4HS, solutions are
increasingly corrosive.
Depending on material of construction, REAC may fail by;
Carbon Steel- Ammonia bisulfide corrosion8
DSS Duplex Stainless Steel- Stress Corrosion Cracking (Sulfide stress corrosion)

Sulfide stress corrosion is initiated by the H2S in the process stream at REAC, it is a
form of HAC Hydrogen Assisted Cracking.9,5,7,10
H2S corrosion in the presence of tensile stress may result in catastrophic failure as a
result of hydrogen embrittlement by mechanisms such as Sulfide Stress Cracking
(SSC) and Stress Corrosion Cracking (SCC).These failures are often delayed, but
happen abruptly with no visible warning and may happen at stresses well below the
yield strength. Factors contributing may include partial pressures of H2S and chloride
ions concentration (HCL), temperature, pH, and stress.
NACE MR0103 serves as the industry guideline for selection of materials and welding
for equipment used in sour service. This has also been specified by CLG bulletin for
section dealing with dissimilar metal welding9.

5 Nickel Institute article Special Considerations for Welding of Thick Duplex Stainless Steel by Gary Coates
https://www.nickelinstitute.org/~/media/Files/KnowledgeBase/Presentations/20151126Duplex%20Stainless%20Steel%20Congress%20ChinaGary%20CoatesEnglish.ashx
7 CLG Bulletin
https://www.cbi.com/getattachment/b93f3734-f9f4-4263-97db-de12fa77cd8f/Reactor-Effluent-Air-Cooler-Safety-through-design.aspx
8 OSHA Hazard Information Bulletins: Corrosion of Piping in Hydroprocessing Units
https://www.osha.gov/dts/hib/hib_data/hib19940729.html
9 Evaluation of the Susceptibility of Duplex Stainless Steel 2205 to Hydrogen Assisted Cracking in REAC Systems
http://proceedings.asmedigitalcollection.asme.org/proceeding.aspx?articleid=2590542
Download paper: https://etd.ohiolink.edu/pg_10?0::NO:10:P10_ACCESSION_NUM:osu1471554106
10 Evaluation of the Susceptibility of Duplex Stainless Steel 2205 to Hydrogen Assisted Cracking in REAC System
https://etd.ohiolink.edu/pg_10?0::NO:10:P10_ETD_SUBID:117471
05 L iterature search- Summary & Recommended Actions:
The RC Root Cause & conclusion of DS2205 REAC failures;
-The failure of REAC with DSS 2205 construction is at the welding area
-Appearance or Morphology of Damage - Crack
-The Nickel Institute & Licensor CLG point the root cause to sulfide stress cracking SSC
-The Licensor attributing the SCC susceptibility to poor welding practices (high hardness &
austenite/ferrite ratio)
-NACE Publ. “NACE Corrosion Control in The Refining Industry” indicated that improper ratio of
austenite/ferrite may lead to SCC
-NACE MR0103/ISO 17495-1:2016, specified the requirement of maximum harness and
austenite/ferrite ration

Compliances for Reliable and Safe Operation;

In addition to Licensor recommendation1,7, REAC equipment shall be checked on compliances
with NACE MR0103/ISO 17495-1:2016 to ensure reliable and safe operation.
(Licensor recommendations were checked and were found to be in lined with NACE MR0103 requirements)
1 CLG Bulletin CPM-SU-5011-E: Materials & Fabrication Requirements For Duplex Stainless Steel
7 CLG Bulletin https://www.cbi.com/getattachment/b93f3734-f9f4-4263-97db-de12fa77cd8f/Reactor-Effluent-Air-Cooler-Safety-through-design.aspx
 Quality follow-up: (Equipment being delivered)
Clarification with Licensor (if necessary):
- Check with Licensor the relevancy of NACE MR0103 as a mean of material
requirements and welding requirements. With further clarifications on:
1. NACE MR0103 was quoted for dissimilar welding only
2. Why REAC was not specified by Licensor to be meeting metallurgical requirements
of MR0103/ISO 17495-1:2016?
- Checks/ reaffirms with Licensor on the suitability of equipment material of construction
on the operation conditions and expected variations.
- Check on Licensor recommendations on parent material and welding, whether inline
with PTS, NACE MR0103/ISO 17495-1:2016 requirements
(The Licensor recommendations on A/F ratio and hardness were found to be inline with NACE MR0103)

MDR Reviews:
- Review REAC MDR (manufacturer data record)
▪ MTR
▪ Welding
▪ Tube bending infor.
▪ Fabrication records
Site Verification: (if necessary)
-Performed hardness & ferrite testing on the adjacent parent metal & finished
weld accessible to testing near tube sheet.
-Performed internal assessment with respect to PTS, NACE MR0103/ISO
17495-1:2016 & Licensor parent metal & weld recommendation;
(Licensor: Hv310 max/ 40-60% in the base metal and 35-60% in the weld metal. These were inline with NACE
MR0103/ISO 17495-1:2016)
-Feed back to the Licensor the hardness survey data for advice on
the reliability of equipment.
-Only weld cap hardness could be performed
06 C ompliance Check
Based on the literature search summary recommendations; compliance check on
equipment actually fabricated, was performed by MDB (Manufacturer Data Book) reviews
for compliances with;
- NACE MR0103/ISO 17495-1:2016
- Licensor welding recommendation CLG; CPM-SU-5011-E
Compliance Check
Base Metal Weldment & HAZ
Code/
Specification Heat A/F Ratio Hardness PREN Heat A/F Ratio Hardness Consuma-
Treatment Treatment ble

Solution- The ferrite PREN ≤ 40,0 PREN ≤ 40,0 As weld The The average Not
MR0103/ISO annealed and content shall % HRC≤ 28 % HRC≤ 28 average ferrite hardness shall Specified
liquid- be 35 vol% to (286 Hv) (286 Hv) content in the not exceed 310
17495-1:2016 quenched 65 vol%. PREN > 40,0 PREN > 40,0 weld deposit HV, and no
condition % HRC ≤ 32 % HRC ≤ 32 and HAZ shall individual reading
(318 Hv) (318 Hv) be within the shall exceed 320
range of 35 % Hv.
to 65 %.

Materials Ferrite Post weld heat Ferrite content Hardness shall Sandvik
CLG shall be content at treatment at these not be above 22.8.3L or
furnished in these (PWHT) is locations shall Hv310. Sandvik
CPM-SU- the annealed locations shall prohibited
1 be 35-60% in 25.1 0.4.L or
5011-E and water be 40-60% in unless the 25.1 0.4.LR
quenched the base specified by weld metal. 22.9.3.LR
condition metal the Company Avesta
2507/P100
Avesta 2205

Actual As weld Note 3 Note 4

Avesta 2205
A1: 245/256/268/246/235
11,12 A1: Within Range
(Weld) A5:262/266/275/243/252 Sandvik
A5: Within Range D1:247/277/260/254/251
D1: Within Range B1:243/255/270/265/263 25.1 0.4.L
B1: Within Range BM / HAZ / W / HAZ / BM

Cold finished, Within Range 248/248 35.376

solution 246/248 35.497
Actual annealed &
(Material) pickled
2016083116289002
1 CLG CPM-SU-5011-E: 2.0 MATERIALS
b. Each heat of material shall be tested in accordance with ASTM A923 Test Methods A and C.
c. The corrosion rate determined in Test Method C shall not exceed 10 mdd and the results specified in the Certified Materials Test Report (CMTR).
(ASTM A923 - 14 Standard Test Methods for Detecting Detrimental Intermetallic Phase in Duplex Austenitic/Ferritic Stainless Steels)
11 Project REPORT NO: FCR-2016-519-2 Sample: TF10
12 Project REPORT NO: 21C15519-16-09-13 Sample: TF10
07 M anufacturing Data Book Reviews
Finding Summary of Review on Part II Vendor’s MDB (Manufacturing Data Book) for REAC’s
Duplex Stainless Steel from Package 2
No Item Comment
1 Qualification Certification No Comment
2 Inspection Release Certificate No Comment
3 Certificate of Conformity No Comment
4 Manufacturer Data Report No Comment
5 Certificate of Inspection Authority No Comment
6 Nameplate Copy No Comment
7 Material No Comment
8 Welding
i. Weld Map No Comment
ii. Joint Configuration No Comment
iii. WPS & PQR Mechanical Test Reports were not attached however all the information had been included in PQR
with stamped and reviewed by 3rd Party Inspector (HSB GS).
9 NDT No Comment
10 Test Report of Production Test Plate No Comment
11 Hardness Testing No Comment
12 PMI Testing PREN Calculation (Production weld sampling), complied.
13 Ferrite Check Report No description provided on reference point.
14 Surface Protection No Comment
15 Dimensional Inspection Report No Comment
16 Hydrostatic Test a. There is no Water Analysis Report attached.
b. There is no copy of Pressure Gauge Calibration Report attached.
17 Air Leak Test Report There is no copy of Pressure Gage Calibration Report attached.
18 Approved Drawings No Comment
19 Steel Sructure No Comment
20 Motor No Comment
21 Fan No Comment
22 Vibration Transmitter No Comment
23 Shop Running Test No Comment
24 Inspection Test Plan No Comment
25 Vendor Concession Request No Comment
08 Operation Consideration:
From the literature search there were insufficient corrosion data to fully understand and predict the corrosiveness of
REAC over a wide range of concentration and velocity encounter during operations to avoid REAC failure13,14. The
effect of other parameters such as pH, temperature, partial pressures of H2S and NH3, and solution contaminants
such as oxygen, chlorides, and cyanides need to be quantified for safe operations. It is recommended the operation
condition15,16, corrosion monitoring and inhibition shall be within the IOW integrity operating window as specified by
the equipment licensor 7.

From the literature search, it sheds lights on corrosion tendency in REAC. It is therefore important that the
Operation to develop a comprehensive inspection program and perform regular inspection monitoring of REAC plus
the inlet and outlet piping during operation 17,18,19, detecting general corrosion, erosion, thinning and stress cracking
in the early stages to avoid early equipment failure.

Inspection and continuous monitoring data (corrosion rates and damage mechanism )may be used to justify
resistant materials upgrades such as Alloy 825 1, 7, 20 .
7 CLG bulletin
https://www.cbi.com/getattachment/b93f3734-f9f4-4263-97db-de12fa77cd8f/Reactor-Effluent-Air-Cooler-Safety-through-design.aspx
13 API Publication 932-A, “A Study of Corrosion in Hydroprocess Reactor Effluent Air Cooler Systems”, (Washington, DC: American Petroleum Institute,
14 Prediction And Assessment Of Ammonium Bisulfide Corrosion Under Refinery Sour Water Service Conditions September 2002).

https://www.honeywellprocess.com/library/marketing/whitepapers/CorrosionNACE06_Paper_06576.pdf
15 Aramco SAES-L-133: Corrosion Protection Requirements for Pipelines, Piping and Process Equipment, Clause 7.3.5
16 NACE Publication 01543 Design Considerations To Minimize Ammonium Chloride Corrosion In Hydrotreater Reac's

https://store.nace.org/01543-design-considerations-to-minimize
17 Failure Analyses: In Retrospect Corrocon Paper No.11851

http://www.nace-malaysia.org/docs/corcon2017/corcon2017-nurul-asni-full-paper.pdf
18 API 574 Inspection Practices for Piping System Components
19 NACE Corrosion 97: Paper 490 Corrosion Of Reactor Effluent Air Coolers

https://store.nace.org/2964ca67-dfca-4574-b034-df2c720e63e3
20 Prediction And Assessment Of Ammonium Bisulfide Corrosion Under Refinery Sour Water Service Conditions

https://www.honeywellprocess.com/library/marketing/whitepapers/CorrosionNACE06_Paper_06576.pdf
09 CONCLUSION:
On random checks on the MDB of 1211-E-107 & 1211-E-207, 1212-E-107 &
1212-E-207; checks were conducted on the material of construction and welding
against CLG CPM-SU-5011-E and NACE MR0103/ISO 17495-1:2016
requirements. The equipment were found generally to be satisfactory with
respect to Licensor welding recommendations and generally satisfy the NACE
MR0103/ISO 17495-1:2016 requirements with comments a, b.

a For equipment to comply with MR0103/ISO17495-1:2016; WPS/PQR to be developed in accordance with Clause 13.8.2 with hardness survey
shall be performed in accordance with Annex C.

bFor equipment to comply with MR0103/ISO17495-1:2016; On the fabricator’s WPS 11.04, PQR and other WPS, the welding procedure
qualification hardness survey layout in accordance with MR0103/ISO 17495-1:2016, Annex C need to be submitted for review.
References:
Ref Titles Links
No
1 CLG’s bulletin to Petronas on DSS REAC failures. Internal document.

2 Failure Analysis of Reactor Effluent Air Cooler https://www.nace.org/cstm/PaperTrail/Authors/Submission.aspx?id=a32f252b-9da1-e211-ac5b-

(REAC) in a Hydrocracker Unit. 0050569a007e
3 Survey Of Corrosion In Hydrocracker Effluent Air https://www.researchgate.net/publication/282387247_SURVEY_OF_CORROSION_IN_HYDRO
Coolers. CRACKER_EFFLUENT_AIR_COOLERS
4 Corrosion of Reactor Effluent Air Coolers. https://www.onepetro.org/conference-paper/NACE-97490

5 Nickel Institute article Special Considerations for https://www.nickelinstitute.org/~/media/Files/KnowledgeBase/Presentations/20151126Duplex%2

Welding of Thick Duplex Stainless Steel by Gary 0Stainless%20Steel%20Congress%20ChinaGary%20CoatesEnglish.ashx
Coates.
6 API571 Chapter 5.1.1.2 Ammonium Bisulfide https://www.techstreet.com/standards/api-rp-571?gclid=CjwKCAjws6jVBRBZEiwAkIfZ2sOgc-
Corrosion (Alkaline Sour Water) vbnXzQqLcrigt6ZfFg5ZcLpmWqhONucPXS9xA28xF5ut48ERoCzg0QAvD_BwE&sid=goog&pro
duct_id=1785786
7 CLG Bulletin https://www.cbi.com/getattachment/b93f3734-f9f4-4263-97db-de12fa77cd8f/Reactor-Effluent-
Air-Cooler-Safety-through-design.aspx
8 OSHA Hazard Information Bulletins: Corrosion of https://www.osha.gov/dts/hib/hib_data/hib19940729.html
Piping in Hydroprocessing Units
9 Evaluation of the Susceptibility of Duplex Stainless http://proceedings.asmedigitalcollection.asme.org/proceeding.aspx?articleid=2590542
Steel 2205 to Hydrogen Assisted Cracking in https://etd.ohiolink.edu/pg_10?0::NO:10:P10_ACCESSION_NUM:osu1471554106
REAC Systems

10 Evaluation of the Susceptibility of Duplex Stainless https://etd.ohiolink.edu/pg_10?0::NO:10:P10_ETD_SUBID:117471

Steel 2205 to Hydrogen Assisted Cracking in
REAC System
11,12 Project MDR Project Report Project MDR Project Report
References:
Ref Titles Links
No
13 API Publication 932-A- A Study of Corrosion in https://www.techstreet.com/standards/api-tr-932-a?product_id=1035468
Hydroprocess Reactor Effluent Air Cooler Systems
14 Prediction And Assessment Of Ammonium Bisulfide https://www.honeywellprocess.com/library/marketing/whitepapers/CorrosionNACE06_Pap
Corrosion Under Refinery Sour Water Service Conditions er_06576.pdf
September 2002).
15 Aramco SAES-L-133: Corrosion Protection -
Requirements for Pipelines, Piping and Process
Equipment, Clause 7.3.5
16 NACE Publication 01543 Design Considerations To https://store.nace.org/01543-design-considerations-to-minimize
Minimize Ammonium Chloride Corrosion In Hydrotreater
Reac's
17 Failure Analyses: In Retrospect Corrocon Paper http://www.nace-malaysia.org/docs/corcon2017/corcon2017-nurul-asni-full-paper.pdf
No.11851
18 API 574 Inspection Practices for Piping System https://www.techstreet.com/standards/api-rp-574?product_id=1936468
Components
19 NACE Corrosion 97: Paper 490 Corrosion Of Reactor https://store.nace.org/2964ca67-dfca-4574-b034-df2c720e63e3
Effluent Air Coolers

20 Prediction And Assessment Of Ammonium Bisulfide https://www.honeywellprocess.com/library/marketing/whitepapers/CorrosionNACE06_Pap

Corrosion Under Refinery Sour Water Service Conditions er_06576.pdf
Charlie Chong/ Fion Zhang
UNS Number N08825
Other common names: Alloy 825, Inconel® 825

Incoloy 825 is a nickel-iron-chromium alloy with additions of molybdenum, copper and titanium. This
nickel steel alloy’s chemical composition is designed to provide exceptional resistance to many
corrosive environments. It is similar to alloy 800 but has improved resistance to aqueous corrosion.
It has excellent resistance to both reducing and oxidizing acids, to stress-corrosion cracking, and to
localized attack such as pitting and crevice corrosion. Alloy 825 is especially resistant to sulfuric and
phosphoric acids. This nickel steel alloy is used for chemical processing, pollution-control equipment,
oil and gas well piping, nuclear fuel reprocessing, acid production, and pickling equipment.
Alloy 825 (UNS N08825) Chemical Composition, %

Ni Fe Cr Mo Cu Ti C Mn S Si Al
38.0- 22.0 19.5- 2.5- 1.5- 0.6- 0.05 1.0 0.03 0.5 0.2
46.0 min 23.5 3.5 3.0 1.2 max max max max max
PREN = %Cr + 3,3 (%Mo + 0,5 × %W) + 16 × %N
PREN min = 27.75

https://www.sandmeyersteel.com/images/SSC825-Spec-Sheet.pdf
https://www.sandmeyersteel.com/A825.html
Duplex 2205
Duplex 2205 stainless steel (both ferritic and austenitic) is used extensively in applications that
require good corrosion resistance and strength. The S31803 grade stainless steel has undergone a
number of modifications resulting in UNS S32205, and was endorsed in the year 1996. This grade
offers higher resistance to corrosion.

At temperatures above 300°C, the brittle micro-constituents of this grade undergo precipitation, and
at temperatures below -50°C the micro-constituents undergo ductile-to-brittle transition; hence this
grade of stainless steel is not suitable for use at these temperatures. The properties that are
mentioned in the below tables pertain to flat rolled products such as plates, sheets and coils of the
ASTM A240 or A240M. These may not be uniform across other products such as bars and pipes

Alloy 825 (UNS N08825) Chemical Composition, %

Grade C Mn Si P S Cr Mo Ni N
2205 Min - - - - - 21.0 2.5 4.5 0.08
(S31803) Max 0.030 2.00 1.00 0.030 0.020 23.0 3.5 6.5 0.20

2205 Min - - - - - 22.0 3.0 4.5 0.14

(S32205) Max 0.030 2.00 1.00 0.030 0.020 23.0 3.5 6.5 0.20

PREN = %Cr + 3,3 (%Mo + 0,5 × %W) + 16 × %N

PREN min = 34.14

https://www.sandmeyersteel.com/A825.html
http://www.duplex2205.net/difference-between-duplex-and-super-duplex-steel/
 UNS Number N08825/ Duplex 2205
Comparison of DSS 2205 & Alloy 825 (UNS N08825)
Grade C Mn Si P S Cr Mo Ni N
2205 Min - - - - - 22.0 3.0 4.5 0.14
(S32205) Max 0.030 2.00 1.00 0.030 0.020 23.0 3.5 6.5 0.20

Alloy Min - - - - - 19.5 2.5 38.0 -

8251 Max 0.05 1.0 0.5 0.03 23.5 3.5 46.0

1 Alloy 825 (UNS N08825) Other Chemical Composition not specified in DSS 2205, %

Grade Cu Ti Al
Alloy Min 1.5 0.6 -
8251 Max 3.0 1.2 0.2