Challenges in Commissioning and

Operation of OASE® Solvent Systems

MDEA based solvents for CO 2 removal in ammonia plants came into existence in the early 1980s, and
energy consumption of these systems were the lowest. Since then, more than 200 ammonia plants are
operating with BASF's OASE® solvent system which was earlier known as aMDEA®. There have
been many new ammonia projects that have come on stream in all parts of the globe, and hence it is
important to recap the lessons learned from these recent projects. In this paper, the challenges in
pre-commissioning, commissioning and operation of OASE® solvent systems are described.

Dr Torsten Katz and John Nichols

BASF

Venkat Pattabathula
Incitec Pivot

George Colman
Kellogg Brown & Root (KBR)

flipside, those designs lead to higher capital ex-

Introduction penditure. Figure 1 shows the most common
configuration in the industry. The synthesis gas,

T
which shall be purified from CO 2 , enters the ab-
he growth of ammonia industry has been sorber column at the bottom.
languishing in the USA for about 30 Treated Flash Acid

years. However, a step change has oc- Gas Gas Off-Gas

curred since the shale gas industry was Make-up

Water

developed and the gas prices became affordable. Condenser

Hence, more ammonia capacity is being added to

C2

supplement existing operating capacities to meet Lean

the USA’s ammonia demand. cooler C4

C7

C1
C9

BASF’s OASE white Process

®
Feed
Gas

The Acid Gas Removal Units (AGRU) in Am- Solvent/solvent

Reboiler

monia plants are usually designed in line with the 2-stage Absorber HP flash
exchanger
LP flash Stripper

Basis of Design Information, provided by the Figure 1. Typical OASE® white configuration
main engineering company. For most plants, an
operating expenditure optimized design using a The majority of CO 2 is removed from the gas in
two-stage absorber is the preferred setup. On the the lower bulk absorber section (C1). Co-ab-
sorbed H 2 and other inert gases are released in

2018 213 AMMONIA TECHNICAL MANUAL

 the HP flash (C4), and the rich amine solution is c) All pipe work is in place and hydro tested
partly regenerated to the semi-lean quality in the d) All instrumentation is in place and commis-
LP flash drum (C7). A minor part of the semi- sioned.
lean amine solution is fully regenerated in the
stripper (C9) to a lean solution quality. The lean e) A suitable supply of clean, filtered, low chlo-
amine solution enables a deep CO 2 removal in ride (< 50ppmw/ w ) water is available.
the lean absorber (C2), down to less than 500 f) A suitable supply of demineralized water is
ppmv in the Treated Gas. available.
As a heat integration measure, a solvent/solvent g) A suitable supply of nitrogen is available for
exchanger and the recycle of the stripper vapor pressurization of the CO 2 absorber and HP
into the LP flash sump is implemented. With the flash.
two solvent loops of lean amine and semi-lean h) A suitable system is in place for the disposal
amine, the process offers high operational flexi- of waste water and alkaline solutions gener-
bility and is very forgiving in case of upsets. The ated by the cleaning activities.
hot synthesis gas serves as the heating medium in
the reboiler before it is further cooled down in i) A suitable supply of electricity and/or steam
several heat exchangers and before it enters the (if steam turbine driven pumps form part of
absorber as Feed Gas. Consequently, the Steam the system) is available.
to Carbon ratio in the steam reformer defines the j) Pump related interlocks have been function-
available energy input which will end up in the ally checked and are in service.
AGRU. Usually, the split between lean and
k) The plant’s Distributed Control System
semi-lean flow rate is well balanced for the avail-
(DCS) is available for use.
able amount of energy in the hot synthesis gas.
l) Sufficient pipe fitting resources are available
to support the cleaning of pump suction
Pre-commissioning and strainers
commissioning guidelines
Pre-commissioning of an OASE® white system
Some Items to Be Considered When Planning generates a significant quantity of:
for the Pre-Commissioning of an OASE® a) Rust contaminated water during the pre-
white system cleaning and cold / hot water recirculation
Allow a minimum of 6 weeks in the overall plant steps.
pre-commissioning schedule for cleaning of the b) Weak alkaline solution and high pH water
OASE® white system (note: this duration ex- during the alkaline degreasing and water rins-
cludes pre-cleaning). ing steps.

Cleaning of the OASE® white system can only Before starting to pre-commission, the OASE®
proceed after the following items are in place: white system, plans shall be in place to capture
the waste streams and dispose of them in accord-
a) All packing and internals have been installed
ance with company and local authority regula-
in the towers and drums.
tions.
b) All machinery is in place and all pre-commis-
sioning steps such as motor solo runs, align-
ment, lube oil system flushing, etc. have been
completed.

AMMONIA TECHNICAL MANUAL 214 2018

 Main OASE® white Solution System Pre- Further removal of particulate matter from the
Commissioning Activities OASE® white system is performed by using the
installed pumps to recirculate demineralized or
Cleanliness of the OASE® white system is the reverse osmosis water around the system and
key in ensuring a trouble-free start-up. Contam- capture any remaining particulate matter on a
inants such as oils, greases, particulate matter, fine mesh fitted to each pump suction strainer.
and construction dirt/debris result in serious Prior to the start of water recirculation, plan to
foaming issues during the initial start-up and op- bypass any plate and frame exchangers in the sys-
eration of the system. tem and remove all erosion susceptible instru-
mentation. To be able to establish water recircu-
OASE® white system cleaning is split into 10 lation it is necessary to pressurize both the CO 2
steps: Absorber and HP Flash vessel with nitrogen. To
i. Pre-cleaning of towers and drums achieve effective particle removal, one should
ii. Pre-cleaning of large bore pipe work aim to attain a water recirculation flow rate of
iii. Loading tower and drum packing greater than 90% of the OASE® white solution
iv. Cold and hot water recirculation process flowsheet. Before starting this activity,
v. Alkaline degreasing it is essential that all interlocks provided to pro-
tect the recirculating pumps have been function-
vi. Water rinsing
ally tested and placed in service. Additionally,
vii. Internal inspection of towers and drums throughout water recirculation, all precautions
viii. Cleaning and loading of vortex packing must be taken to ensure that the recirculation
ix. Final water rinsing pumps are not cavitated or that any pump suction
x. OASE® white solution preparation and strainer is not collapsed due to excessive pressure
filling drop. To aid in cleaning of the system, every 36
hours, the entire contents of the system should be
Pre-cleaning of towers and drums comprises of drained and replenished with clean water. Typi-
power brushing the walls of all towers and drums cal acceptance criteria for this step is, with a wa-
to remove particulate matter, i.e. mill scale and ter recirculation flow of greater than 90% of the
surface rust, from the vessel walls. This activity OASE® white process flowsheet flow, a recircu-
is best completed when each item of equipment lating water temperature of 50 - 70oC (120 -
is in the horizontal position while vessel “dress 160oF), and 80 mesh screens or larger fitted to all
out” activities are ongoing. pump suction strainers, to maintain these condi-
tions for 48 hours without it becoming necessary
Pre-cleaning of large bore OASE® white pipe to clean any pump suction strainers.
work is best affected by either air blowing or
once through water flushing. The most effective All the wetted surfaces of the OASE® white sys-
form of cleaning large bore pipe work is to use tem are to be degreased by using the installed re-
the tower or drum as a volume tank and perform circulation pumps to circulate a weak alkaline so-
a rapid decompression air blow of the pipe work. lution at greater than 90% of the process
Loading of tower and drum packing may proceed flowsheet of OASE® white solution. The system
after pre-cleaning activities have been com- temperature is maintained at between 50-70oC
pleted. However, the vortex breaker packing lo- (120-160oF) for 12–24 hours. The most effective
cated in the bottom of both the CO 2 Absorber and alkaline degreasing solutions are 3-5%w/ w
HP Flash should not be loaded until after the final K 2 CO 3 solution, 3%w/ w KOH or 3-5%w/ w NaOH
water rinse is completed. solution. To eliminate corrosion concerns, the
concentrated KOH or NaOH used for the prepa-
ration of the dilute alkaline degreasing solution

2018 215 AMMONIA TECHNICAL MANUAL

 must be low in chlorides, less than 100 ppm, by diluting OASE® white concentrate with de-
membrane grade material. The alkaline degreas- gassed demineralized water is charged to the sys-
ing solution is prepared by diluting the concen- tem.
trated alkali with demineralized water in a tem-
porary vessel outside of the AGRU. If after the Main OASE® white Solution System
prescribed cleaning period the alkaline degreas- Commissioning Activities
ing cleaning solution is very dirty, replace the
dirty solution with clean solution and repeat the Immediately following the charging of the
operation. When the appearance of the used al- OASE® white solution to the system, recircula-
kaline degreasing solution is determined to be ac- tion of the solution should be started, and the side
ceptable, fully drain the solution from the system. stream filtration unit commissioned with 100-mi-
cron elements and placed in service.
Trisodium phosphate (TSP) can also be used for
degreasing the system. If the supplied chemical To prevent contamination of the OASE® white
was in TSP form, the required chemical strength solution from upstream equipment it is essential
in the solution should be 3-5%, whereas, if it was that:
supplied in the form of dodeca-hydrate a) Upon completion of the Low Temperature
(Na3PO4.12H2O), its strength should be a mini- Shift (LTS) catalyst reduction that the LTS
mum of 7%. catalyst bed is effectively de-dusted to the
front-end flare.
Following alkaline degreasing, it is necessary to
rinse the entire system with demineralized water b) That equipment and pipe work upstream of
until the pH of the rinse water is < 9.0 and the the CO 2 Absorber is blown clean by venting
foaming tendency of a 40%w/ w OASE® white so- process gas immediately up stream of the
lution prepared using a sample of the rinse water CO 2 Absorber at a flowrate equivalent to
and a sample of the OASE white Premix, has a 40~50% of the flowsheet value.
foam height less than 350 mls and a collapse time Before the introduction of process gas to the CO 2
of less than 35 seconds. Experience shows for a Absorber, the anti-foam injection system shall be
large OASE® white system, 4 – 5 water rinses are made ready for service.
necessary to achieve the acceptance criteria.
Prior to the introduction of process gas to the
After water rinsing has been completed, an inter- CO 2 Absorber it is necessary to passivate all the
nal inspection of all towers and drums is to be wetted surfaces within the OASE® white system.
performed and any damaged components must Before the start of the system passivation, suffi-
be repaired. In advance of reaching this step in cient anti-foam is charged to establish an anti-
the sequence, the tower vortex breaker packing foam concentration of approximately 50ppmw/ w
must be degreased, and water rinsed external to in the recirculating OASE® white solution The
the system in readiness for installing it in the CO 2 unit should be operated with the cooling medium
Absorber and HP Flash after the inspection. for the lean cooler blocked in and the amine cir-
culated at design conditions and at a temperature
After closure of the system, 2 or 3 water rinses close to but less than 70oC (160oF) or as close to
should be performed to remove any dirt that may design conditions as can be achieved throughout
have entered the system during the inspection the OASE® white system for 72 hours.
and vortex breaker packing loading activities.
Passivation is completed after the amine solution
Once the final rinse has been completed, 45%w/ w has been circulated for 72 hours at the conditions
OASE® white solution which has been prepared specified above.

AMMONIA TECHNICAL MANUAL 216 2018

 Challenges Experienced in Case Study 3
Commissioning In several new plants, large spills of OASE®
In several new ammonia plants, ineffective white solution have occurred when temporary
cleaning of the OASE® white system has resulted gaskets, which remained undetected from plant
in foaming events either in the CO 2 Stripper/LP pre-commissioning, failed during plant opera-
Flash which have led to OASE solution loss of tion.
containment from the CO 2 vent into environment
surrounding the plant, or in the Absorber which Case Studies of Failures in
results in not meeting the CO2 treated gas speci-
fication. Some of these cases are discussed be-
Operating Plants
low. Operational issues have occurred over the years
due to design recommendations not being
Case Study 1 followed. Some of those instances are discussed
in the case studies presented below.
In one plant due to an ineffective alkaline de-
greasing after charging the OASE white solution
Case Study No.1
to the system, instead of it being colorless it had
a yellow discoloration. The discoloration can be Observations:
an indication that some of the contaminates that • Leakage in semi-lean line pump discharge
should have been removed in the commissioning (Original material of construction was carbon
steps were not removed and remained in the sys- steel)
tem. This yellow discoloration was removed by • Line thickness found to be paper thin
passing the solution through a carbon bed for ap- • 8-10 mm pitting in flow control valve in the
proximately 1 week. same line
• Flow control valve became non-operational
Case Study 2
Root cause
In one plant, it was not possible to operate at
• Material of construction was not in line with
plant loads above 60% due to the CO 2 vent valve
BASF’s recommendations
being fully opened and the CO 2 Stripper/LP
• Line velocities should not exceed 2 m/sec
Flash pressure increasing above the design value.
(6.5 ft/sec) (max for carbon steel) because at
An investigation determined that the CO 2 vent si-
these velocities erosion corrosion have been
lencer was partially plugged with construction
reported in API 945
debris. (See Figure 2) The root cause was inef-
fective cleaning of the CO 2 product pipe work
Corrective action
during pre-commissioning.
• Upgrade to stainless steel material for replac-
ing the affected portion of the piping in line
with BASF ‘s recommendation

Case Study #2
Thinning of a pipeline due to erosion corrosion
was also reported in another plant in the semi-
lean piping downstream of a flow orifice (see
Figure 3). Also, the body of a block valve in the
Figure 2. Partial plugging of CO 2 vent silencer. same pipe showed major corrosion attack, (see
Figure 4).

2018 217 AMMONIA TECHNICAL MANUAL

 • To ensure continuous operation and flexibil-
ity, an additional lean/semi-lean exchanger
installed in parallel to existing one.

Figure 3. Corrosion of carbon steel semi-lean

pipe downstream of flow orifice

Figure 5: Corroded valve parts and inlet piping

Figure 4. Corrosion of CS steel block valve

body downstream of control valve in semi-lean Figure 6: Corroded packing
pipe

Case Study #3
Corrosion occurred in another plant which re-
sulted in BASF modifying its design recommen-
dations for the metallurgy.

Observations:
• Corrosion of the carbon steel parts of the
body of the semi-lean and rich control valves
(See Figure 5)
• Corrosion of packing internals (See Figure 6)
• Solids blocking exchanger inlet (See Figure
7)
• Solids blocking plate and frame plate (See Figure 7: Solids blocking exchanger inlet.
Figure 8)

Corrective action:
• Upgrade to stainless steel material - BASF’s
recommendation

AMMONIA TECHNICAL MANUAL 218 2018

 Case Study #5
Flooding in LP Flash Vessel

A two-stage amine system in an ammonia plant

was experiencing flooding of the LP flash. The
indications of the problem were:
• Abnormal behaviour of tower’s high and
low-level switches
• Wrong actuation due to foaming and accu-
mulation of antifoam in dead legs of level
switches
Figure 8: Solids blocking exchanger plate • Too much antifoam dosing – its deterioration
products resulted in more foaming, and the
spent antifoam accumulated in the system
Case Study #4 • Strong amine smell in CO 2 stream due to tri-
methyl amine formation
In this case study, an ammonia plant was having • Amine spilled from CO 2 Vent
the following issues:
• High CO 2 slip The following corrective actions were imple-
• Low purity CO 2 mented:
• Fouling of exchangers • Adjustments in column levels were done very
• Leaking lean solvent FCV slowly and step wise
• Minimum concentration was to be main-
After reviewing the operational data of the plant, tained in the range of 38 to 42%
a plan of attack was developed. The plant imme- • Antifoam injection directly into LP flash ves-
diately sel
• Increased the anti-foam dosage • Dosing rates were optimized from 4 to 1 li-
• Increased the solvent strength to 45% wt. tre/day (0.3 gal/day)
• Steam / carbon ratio to be maintained as per
At the next shutdown, the following actions were design conditions
taken:
Case Study #6
• Upgraded the stripper packing to stainless
steel material - BASF’s recommendation OASE entrained vapor escaped through the CO2
• Cleaned the lean / semi-lean exchanger to vent silencer on two occasions.
bring the lean amine temperature closer to
design value The first occurrence was due to increased foam-
• Installed a strainer upstream of lean / semi- ing when OASE solvent was pumped from the
lean exchanger sump into the system. The level transmitters
• Changed the lean inlet flow control valve were invariably inaccurate and the level control
material of construction to stainless steel - valve from the HP flash to LP flash column
BASF’s recommendation opened wide. The result was about 10 m3 (2600
gal) of diluted OASE solvent flowed through the
The plant has operated without any issues after CO2 vent silencer and across the site.
these changes were made.

2018 219 AMMONIA TECHNICAL MANUAL

 The antifoam dosing procedures and makeup
from the sump to the system were revised. Side
stream filter change out frequency was increased.

The second event occurred soon after startup.

Operators observed erratic level in the LP flash
column and downstream knock out drum. The
levels through the system was behaving erratic as
well. Antifoam was added but this did not help.
Eventually the level in the knock out drum went
>110%, and OASE® white went out through the Figure 9. Maximum feed gas capacity versus re-
silencer. boiler duty

Further investigation revealed that the cause was Since the nature of the curve in Figure 9 shows
most likely the gas blow through. The HP flash only a flat optimum, certain deviations of the de-
vessel wet leg drained out when the plant tripped sign Steam to Carbon Ratio can be managed by
and caused the level to remain at 55%. The fix the AGRU process, but the differential pressure
was to ensure that these transmitters were all across the stripper should be monitored to avoid
checked whenever the system tripped before re- malfunction.
start.
Operation at capacity limit
Troubleshooting in normal Whenever the ammonia price is high, operations
operation tend to push the production capacity to the limits.
For those plants, where the AGRU is the bottle-
Higher than design steam to carbon ratio neck in the overall process, a mid- and long-term
damage of the plant can be the consequence. Of-
Many NH 3 plants are being operated with higher ten, operations try to upgrade pumps to increase
than design Steam to Carbon Ratio in the steam the lean or semi-lean amine solution flow rates.
methane reformer because operations often want A velocity of 2 m/s (6.5 ft/s) in carbon steel liquid
to minimize the risk of coking on the primary re- piping however shall not be exceeded, otherwise
forming catalyst. As a result, this can cause an erosion corrosion is likely to occur. For plants
energy oversupply to the AGRU: due to the with stainless steel piping, this criterion is not rel-
higher water content, the hot synthesis gas con- evant, except if the flanges at the vessels are
tains more energy. Figure 9 shows that a slightly made of carbon steel and the velocity limit is ex-
higher than design reboiler duty has only a mar- ceeded there. Figure 10 shows corrosion in a
ginal impact on the maximum achievable feed temporary bypass line between the absorber and
gas capacity of the AGRU. However, due to the the HP flash due to too high velocity (5.5 m/s,
increased hydraulic load in the stripper, flooding 18ft/s).
is more likely to happen. In the example of Fig-
ure 9, flooding in the stripper starts at reboiler du-
ties larger than 110% of the design value.

AMMONIA TECHNICAL MANUAL 220 2018

 operating under such critical conditions, which
affect the long-term integrity of the equipment, a
temperature indicator (TI) with an appropriate
warning to avoid operation under pinched condi-
tions is a simple countermeasure.

Figure 10. Corrosion in carbon steel amine solu-

tion piping due to too high velocity (5.5m/s,
18ft/s)

Another corrosion pattern, which has been ob-

served in plants that are pushing the capacity to
CO 2 breakthrough limits, goes back to operation
at pinched conditions. In such a scenario, the up-
ward flowing gas stream is in equilibrium condi-
tion with the down coming amine solution.
Nearly constant temperature and CO 2 gas phase
profiles, as shown for the red curves in Figure 11
in the lower part of the lean absorber, are the con- Figure 12. Corrosion in CS amine solution pip-
sequence. ing due to too high velocity

Conclusion
After over 40 years of experience in designing
and operating OASE Acid Gas removal units,
BASF continues to make changes to its proce-
dures and design practices to improve the com-
missioning and operation of Ammonia plants.
Because of the various lessons learned over the
years, BASF has recommended and implemented
Figure 11. Corrosion in CS amine solution pip- various changes to their design best practices.
ing due to too high velocity Some of these include:

The increase in temperature goes hand in hand i. Install stainless steel packing in all the
with breakthrough of the CO 2 profile (see left columns.
graph in Figure 11). Under the red curve condi- ii. Follow BASF guidelines in materials of
tions, the plant was still able to manage NH 3 pro- construction for piping, elbows, bends
duction. However due to minor local maldistri- etc.
bution effects, or splashing of the loaded amine iii. Follow BASF recommendations for
solution on the liquid re-distributors, local CO 2 amine velocity in CS piping
degassing took place. This led to severe corro- iv. Conduct routine analysis of amine
sion damage as shown in Figure 12. To avoid strength and foam tests.

2018 221 AMMONIA TECHNICAL MANUAL

 v. Send lean amine solvent samples and
plant operating data to BASF every quar-
ter for complete analysis.
vi. Ensure CO2 absorber operates far away
from high temperature zone that could
contribute to potential corrosion.
vii. Perform reclaiming operation if there
were any buildup of degraded products.

AMMONIA TECHNICAL MANUAL 222 2018