Metallurgical and Catalyst Effects

from Airflow Condition into HTS

The initial startup and reduction of the High Temperature Shift (HTS) catalyst is a procedure which
is performed relatively infrequently in ammonia plants. This procedure allows for a safe, controlled
reduction of the HTS catalyst primarily by operating at a high S/G ratio at the Primary Reformer. A
proper initial startup is important to ensure that the catalyst is able to achieve maximum CO conver-
sion combined with a long on-stream life. While many ammonia plants (including the CF Industries
Verdigris site) have performed HTS startups with no problems, events can occur that can lead to poor
catalyst performance, reduced HTS reactor efficiency, and more serious issues including loss of ves-
sel integrity.

In 2010 - the CF Industries No. 1 Ammonia Plant in Verdigris, OK installed a reload of ShiftMax®
120 HTS catalyst. The reduction was deemed a success and the plant came up to normal operating
rates. Upon the first detailed analysis of catalyst performance after startup, the HTS catalyst CO con-
version was less than expected. This trend continued for 1 year until the plant decided that they could
not continue to operate at this HTS performance level. Upon shutdown in 2011 and subsequent anal-
ysis of initial startup process conditions after the HTS catalyst reduction, it was found that air had
been inadvertently introduced into the HTS reactor with reduced catalyst. This caused a previously
undetected exotherm through the catalyst bed which damaged catalyst and raised several vessel integ-
rity questions.

This paper explains the effects of the air introduction into the HTS reactor, including metallurgical
concerns and steps taken to ensure proper vessel integrity and safety, the effect this event had on the
HTS catalyst, and overall lessons learned.

Sean Ukele and Shawn Carnine

CF Industries

Zachary Singer
Clariant Corporation

Introduction 2011, Clariant as catalyst provider worked with

the CF site to provide guidance and troubleshoot-

T
he CF Industries No. 1 Ammonia Plant in
Verdigris, OK experienced poor HTS cat-
alyst performance upon startup following
installation of a new catalyst charge in
October of 2010. From startup until December
ing efforts. The work included recommending
steps to take to try and improve performance,
testing catalyst retain samples, and reviewing the
loading process and initial catalyst reduction to
see if anything looked out of line. After this re-

2014 169 AMMONIA TECHNICAL MANUAL

 view, one key in-process variable was identified
as being suspect and this pointed to some possi-
ble scenarios which could cause this performance
issue. After these reviews, however, nothing was
conclusive. It was decided in December 2011 to
bring the plant down to repair other process
equipment. During this short outage, it was de-
cided to also take the opportunity to replace cata-
lyst in the HTS reactor. Upon observations from
unloading of the catalyst and additional review of
process data, it was determined that shortly after
the initial catalyst reduction in October 2010, air
was inadvertently introduced into the Secondary
Reformer which reached the reduced catalyst in
the HTS reactor, causing a major high tempera-
ture event in the bottom of the vessel.
This paper will attempt to outline troubleshoot-
ing efforts undertaken – both during the catalyst
operation and also during the unloading of the
catalyst reactor. Also shared will be the effects
that this event had on the catalyst and, more im-
portantly, the reactor. Many steps were taken to
ensure sufficient vessel integrity upon this reac-
tor being placed into service after the event.
Initial Catalyst Performance
The plant is a MW Kellogg designed for 1,150
STPD with current revamp operating capacity
near 1,650 STPD. Upon startup of the ShiftMax®
120 HTS catalyst in October 2010, CO conver-
sion was less than anticipated. The reactor was
leaking over 3 mol % CO compared to an ex-
pected 2-2.5% (based on the #1 plant process
conditions and historical performance and expe-
rience with the catalyst). We then reviewed the
initial catalyst reduction data. The reduction was
performed by CF Operations and both parties
agreed that it was a “textbook” reduction with no
issues. However, based on the temperature pro-
file from the reduction and current operation, we
found that TI-9, which previously showed ex-
otherm during the reduction, was not showing
exotherm during operation. This pointed to a
possible screen failure, or some kind of settling
event which would cause the bed to shrink. TI-9
AMMONIA TECHNICAL MANUAL
was located at a depth of 15 ft. However, there
was no identified pressure drop increase across
the reactor. At the time, this one piece of infor-
mation was not conclusive and did not point to a
known incident which could have affected per-
formance. From the time the catalyst was start-
ed up until December 2011, Clariant recom-
mended temperature increases to try and improve
CO conversion. These steps were undertaken by
CF but did not improve the catalyst performance.
Unloading of Catalyst and Trouble-
shooting
In December 2011, CF decided to take the plant
down to undergo some repairs on other process
equipment. During this time, it was also decided
to change the HTS catalyst due to the high CO
leakage of the HTS reactor. Clariant personnel
were on-site to supervise the unloading process
to help troubleshoot the cause of the poor per-
formance.
Initial Findings
When the catalyst handler entered the vessel (un-
der N2 atmosphere) and removed the floating
screen, the first thing observed was a 3 ft (.91 m)
drop in the outage to the ShiftMax® G catalyst
guard layer compared to the as-loaded outages.
When the removal of the ShiftMax® G guard
layer was completed down to the 6x6 mesh
screen that was sitting on top of the catalyst, the
outage to the catalyst was found to be at 14 ft 2-
inches (4.43 m), 3 ft 5-inches (1.04 m) greater
than the As-Loaded outage of 10 ft 9-inches
(3.28 m). Figures 1 and 2 show how a compari-
son of the “As-Loaded” and “After-Operation”
outages and catalyst quality The top layer of
ShiftMax® G guard material and also the first 4 ft
(1.22 m) of ShiftMax® 120 catalyst were in rela-
tively good condition with very minor break-
age/dust. At an outage depth of 18 ft 2-inches
(5.54 m), some of the catalyst was compacted
and no longer free flowing. Figures 3 and 4 pro-
vide a comparison between good catalyst in the
first 4 ft (1.22 m)
170 2014
 9'8"
10' 9"
ShiftMax® G + Top Grid
ShiftMax
® 120 6x6
mm Tab
d = 12.75 ft
127.7 ft3/ft
Figure 1. - Relevant As-Loaded Outages
and the clumping that was observed slightly
deeper than the 18 ft 2 in (5.54 m) outage.
Further evidence of fused catalyst was observed
below the 18 ft 2-inches outage. Surprisingly,
catalyst was found that had shrunk to approxi-
mately 50% of its original size. Most of the
fused catalyst was found in the center of the bed,
while around the sides of the reactor the catalyst
was still mostly free flowing. The floating
screen at the bottom of the bed above the support
media was located where the As-Loaded diagram
predicted it would be at 20 ft 4-inches (6.20 m).
Investigating the screen further, we found evi-
dence of what appeared to be a high temperature
excursion which had melted large portions of the
screen and catalyst. Sections of catalyst were
found fused to the bottom floating screen, which
in turn, was fused to the bottom 1 in support ma-
terial. Figures 5 and 6 below show images of
the findings near the bottom of the reactor. The
support screen was located at the expected out-
age depth of 20 ft 4-inches (6.20 m) and the as-
observed catalyst outage depth was 20 ft 3-
inches. Therefore, the as-observed total depth of
2014
12'11"
14' 2"
ShiftMax®G + Top Grid
18' 2"
Free flowing
20' 4" catalyst and
6x6 mm
20' 3"
#REF!
Clumped and fused
catalyst. 3x3 mm
particles throughout
#REF!
127.7 ft3/ft
Figure 2. - Relevant After Operation Outages
catalyst was 6 ft 1-inch (1.74 m) (i.e., 20 ft 3-
inches minus 14 ft 2-inches). The original cata-
lyst depth was 9 ft 5-inches (2.87 m) indicating
that the catalyst had shrunk by approximately
36%. However, more surprisingly, based on the
free flowing nature of the first 4 ft (1.22 m) is
that in reality the last 5.5 ft (1.65 m) had shrunk
to less than 2 ft 1-inch (0.63 m) or an incredible
near 62% reduction. Figure 5 shows the extreme
shrinkage that the catalyst suffered due to the
high temperatures experienced in the bottom of
the vessel. Clariant’s standard catalyst size for
HTS applications is 6x6 mm. Catalyst where the
high temperature event occurred was found to be
3x3 mm in size. Figure 6 shows another effect of
the high temperature excursion. This picture
shows the 1-inch (2.54 cm) support ball which
was fused to the screen at the bottom of the reac-
tor. This screen is also fused to catalyst particles.
After reviewing all observations, it was evident
that the bottom of this reactor had been exposed
to extremely high temperatures. Focus was then
shifted to finding the cause of the temperature
excursion.
171 AMMONIA TECHNICAL MANUAL
 Figure 4. - Fused catalyst at 18 ft. 2 in. (5.54 m)

Figure 3. - Whole catalyst particles at free flow-

ing catalyst bed depth of 16 ft 2-inches (4.93 m)

Examination of Historian Data

Even though the reduction data had already been
reviewed previously, Clariant recommended an- Figure 5. - Compacted 3x3 mm tablet compared
other review of minute by minute bed TI averag- to fresh 6x6 mm tablet at 20 ft. 3 in. (6.17 m)
es from the HTS startup in October 2010. Again
it was found that the reduction was a success
with no high temperatures that could cause the
observed catalyst and reactor damage. Attention
was then focused on bed TI averages during sub-
sequent operation in order to determine the
source and timeline of the supposed high temper-
ature excursion. It was during this review when
CF found evidence of a high temperature event
shortly after startup which led to extreme tem-
peratures in the bottom of the HTS reactor. Up-
on reviewing this data, CF opted to perform a
full inspection of the bottom head of the vessel to
determine vessel integrity.
Figure 6. - Support ball fused to screen, which in
turn is fused to catalyst particles
Vessel Inspection and Corrective
Action
ed a metallurgical consultant to inspect and per-
To evaluate the vessel integrity following the
form integrity testing. The consultant performed
high temperature event, plant personnel contract-
the following inspections:

AMMONIA TECHNICAL MANUAL 172 2014


 Internal/external visual examinations,
 Wet fluorescent magnetic particle (WFMP)
weld inspections,
 Optical microscope examination of several
areas of the vessel surface, and
 Field hardness testing on various vessel com-
ponents
High temperature hydrogen attack (HTHA) was
deemed to be the most likely result of the high
temperature event. The consultant reported that
the visual examination of the vessel did not indi-
cate any signs of HTHA. Two weld cracks were
identified via WFMP that also did not appear to
have been HTHA-related. Minimal grinding was
performed to remove the cracks and subsequent
remaining vessel thickness was determined to be
adequate. The optical microscope examination
also yielded positive results indicating no signs
of overheating including excessive grain growth,
decarburization, phase changes, or fissuring.
Field hardness testing did indicate signs of over-
heating particularly in the bottom portion of the
vessel. Elevated hardness was observed on the
vessel’s internal surface while the external sur-
face hardness was determined to be lower than
the minimum required by API Standard 579.
The metallurgical consultant concluded that these
hardness testing results were attributable to the
high temperature event and recommended cor-
rective measures be taken prior to placing the
vessel back in service.
Two options were proposed to improve the ves-
sel’s integrity to an acceptable level including a
full anneal at 1,650°F (899 °C) for the standard
ASME dwell time or, as a temporary alternative,
post-weld heat treatment (PWHT). The PWHT
option was chosen as a path forward and post-
PWHT hardness testing showed marked im-
provement. The vessel was cleared for service
on December 24, 2011. In response to this inci-
dent, plant personnel made a plan to replace the
vessel in the subsequent turnaround by instituting
2014
a metallurgy specification change to mitigate the
risk of HTHA.
Incident Root Cause Analysis
The root cause of the high temperature event was
determined to be introduction of oxygen to the
HTS resulting in rapid oxidation of the catalyst
and a significant elevation in vessel temperature.
The oxygen was introduced when compressed
process air pressure exceeded process gas pres-
sure impeding process gas flow to the HTS. His-
torically, this balance between process gas and
air pressures was maintained using a manually-
operated vent that allows the elimination of ex-
cess air pressure during plant start-up. However,
due to process-control modifications made dur-
ing turnaround, the lack of process gas flow was
not recognized.
Several process-control modifications were made
during turnaround including implementation of a
new safety-instrumented system and the elimina-
tion of a two-step low-flow trip that was histori-
cally used during start-up. The functionality of
the two-step low-flow trip was removed, but the
switch remained in place on the board causing
additional confusion during start-up. This was
identified as a contributing factor in the root
cause analysis.
The HTS bed temperature profile during the ini-
tial catalyst reduction, high temperature event,
and secondary catalyst reduction are shown on
Figure 7 below. As shown, the rapid increase in
HTS temperature decreased back to 600°F (316
°C) within 25 minutes and went un-noticed. Fol-
lowing the secondary catalyst reduction, plant
start-up was completed without further issue.
The catalyst performance issue was identified
later during post-start-up analysis of HTS CO
conversion. There were no pressure drop prob-
lems even after the high-temperature sintering of
the catalyst and shrinkage of a portion of the bed
to 3x3mm tabs.
173 AMMONIA TECHNICAL MANUAL
 FIGURE 7. HTS BED TEMPERATURES 
1,800

Temperature spike following
introduction of oxygen
HTS BED 1ST TEMP
1,600
HTS BED 2ND TEMP
HTS BED 3RD TEMP

Plant Start‐Up Continued
HTS BED 4TH TEMP TA97
1,400
Temperature  (°Fahrenheit)

1,200

1,000
Initial HTS
Catalyst Reduction Second HTS
Reduction
800

600

400

Data collected by Mr. Rick Allred, CF Industriess ‐ Verdigris Complex

Figure 7. - Excerpt from process data showing catalyst reduction, temperature exotherm from ox-
ygen spike, and the subsequent 2nd HTS catalyst reduction

Additionally, two operational changes were

Lessons Learned
To address the potential for high temperature hy-
drogen attack (HTHA) of the HTS vessel, plant
personnel elected to upgrade the vessel’s metal-
lurgy to a 1.25 percent chrome 0.5 percent mo-
lybdenum steel alloy material. This material was
selected based on data presented to API by Mr.
G.A. Nelson in 1949 (aka, “Nelson Curve”). The
Nelson Curve depicts the temperatures and pres-
sures at which certain steel materials will begin
to show signs of internal and surface decarburi-
zation and is updated as new data become avail-
able. The trend for the material selected indi-
cates a higher resistance to HTHA than the
original carbon steel material.
made to reduce the likelihood of introduction of
oxygen to the HTS during start up.
The first included a modification of the plant
start-up procedure to minimize the possibility of
introducing oxygen to the HTS. The plant is
equipped with a low-process-gas-flow trip that
recirculates the air compressor (i.e., stops the
process air flow into the plant) upon loss of pro-
cess gas flow. However, the previous plant start-
up procedure required temporary modification of
this trip until adequate flows of both process gas
and process air could be established. The revised
start-up procedure requires that the process gas
flow rate be increased to a level at which intro-
duction of oxygen to the HTS is highly unlikely
prior to starting the process air compressor.

AMMONIA TECHNICAL MANUAL 174 2014

 This change increased the quantity of process gas
(i.e., natural gas) utilized for start-up but pro-
vides adequate protection of the HTS. As a sec-
ond level of protection, a process air to process
gas ratio (flow based) trip was installed that will
also recirculate the process air compressor if the
ratio exceeds the trip set point.

The combination of the metallurgy upgrade,

start-up procedure revision, and installation of
the air:gas ratio trip provides for the safe start-up
and operation of the HTS.

Conclusion

Process air was inadvertently introduced to the

reduced ShiftMax® 120 HTS catalyst during the
CF Industries No. 1 ammonia plant startup after
turnaround in October of 2010. This event was
unknown to the plant at the time. The catalyst
was operated for over a year before the plant de-
cided to come down and change the catalyst.
Upon working with Clariant catalyst personnel
on-site, a review of process data shortly after the
initial HTS reduction showed that an extreme
exotherm passed through the HTS catalyst short-
ly after reduction. This along with findings dur-
ing the unloading of the catalyst bed pointed to
the conclusion of a high process air flow event.
Subsequent activities by CF personnel to under-
stand the root cause and ensure vessel integrity
were put into place.

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AMMONIA TECHNICAL MANUAL 176 2014