Conversion of SulfinolSM to BASF’s aMDEA®

Incitec Pivot has converted the carbon dioxide (CO2) removal system in its Gibson Island
ammonia plant from SulfinolSM to aMDEA® in early 2007. SulfinolSM solution is a mixture of
DIPA (di-isopropanolamine), sulfolane (tetrahydrothiophene dioxide) and water. The SulfinolSM
system had been used for more than 35 years and a solvent change was needed to reduce ongoing
chemical costs of the ammonia plant.

The sequence of project implementation, challenges encountered in design, commissioning and

operation of BASF’s aMDEA® system (activated methyl di-ethanol amine) is explained in detail in
this paper.

Venkat Pattabathula, Incitec Pivot Ltd

Gibson Island, Brisbane, Australia

Dr. Torsten Katz

BASF East Asia Regional Headquarters Ltd., Hong Kong

replaced with a Hydro Agri (now Yara)

Introduction fluidised bed granulation unit in 1999.

The plant is located at Gibson Island (GI) in the

I ncitec Pivot operates an ammonia plant

originally of 600 mtpd, designed by J.F.
Pritchard, which has been upgraded to 800
mtpd over the years since its commissioning in
the late sixties. The unique features of this
suburbs of Brisbane City on the East Coast of
Australia.

ammonia plant are a low pressure (450 psig, 32 Background

bar) front-end, a high-pressure back-end (2600
psig, 182 bar), a medium pressure steam system In ammonia plants, the carbon dioxide (CO2)
(400 psig, 28 bar, 750 °F, 400 °C), a closed loop removal section is a key part of the ammonia
refrigeration system and a jet engine that drives plant front-end where CO2 from process gas is
a reaction turbine, which in turn drives the separated to provide more pure hydrogen (H2)
synthesis gas (syngas) compressor. The site also and nitrogen (N2) for the ammonia synthesis
has a urea plant of Vulcan Cincinnati design, reaction. The recovery of CO2 is also required
which has also been upgraded over the years to as a supply for the production of granular urea
about 850 mtpd. The urea prilling section was and liquid CO2. The economics of the ammonia
plant heavily depends on the efficiency of

2007 25 AMMONIA TECHNICAL MANUAL

solvent systems used for the removal of CO2 maintain its levels in the system. The SulfinolSM
from process gas. Over the last five decades, system had been very reliable with corrosion-
there have been many industry innovations from free operation ever since arsenic was added to
ordinary water wash to potassium solutions to the system. Antifoam was also injected on a
primary, secondary and tertiary amines. needs basis to deal with foaming issues in the
CO2 stripper and absorber. The SulfinolSM
The SulfinolSM CO2 removal solution consists of chemical makeup rates were quite high due to
sulfolane (tetrahydrothiophene dioxide) and degradation of the solution to oxazolidone and
DIPA (di-isopropanol amine) up to a total the costs were on an increasing trend due to
concentration of 65% in the system. SulfinolSM higher chemical prices.
was the preferred solvent when the Gibson
Island (GI) ammonia plant was built in the late Many SulfinolSM systems in natural gas plants
sixties. have changed over to aMDEA® solvent for
capacity increases and reduced chemical costs.
The CO2 removal system at GI is a single stage The GI plant could be one of the few NH3
lean/rich solvent system (Figure 1) that consists plants in the world operating with SulfinolSM.
of major unit operations such as an absorber, Typical composition of SulfinolSM solution:
stripper and several heat exchangers. The lean - DIPA: 50-55%; Sulfolane: 10-15%;
SulfinolSM solvent is fed to the CO2 absorber Oxazolidone: 10-15%; water: 20-25%.
where CO2 in process gas is absorbed in
SulfinolSM solution to produce CO2 rich
solution. The rich solution is sent to the CO2 aMDEA® Process Simulation and
stripper after exchanging heat with the lean
solution from the stripper in the lean/rich
Design
solution exchangers.
BASF carried out an initial simulation of the
A HP flash drum was installed as part of earlier CO2 removal section. The recommended
plant upgrade to remove inert gases from the strength of aMDEA® was 40 wt%. BASF
solution. The lean solution is further cooled identified the need to replace the random
against cooling water (CW) where remaining packing with structured packing in the CO2
heat is removed. This additional heat load on the stripper (D601), as it was very short (5 m or 17
cooling tower consumes a significant amount of ft) compared to their earlier plant retrofits.
city water, which has special importance due to Sulzer performed design checks on the stripper
water supply restrictions from Brisbane City internals and supplied the new internals.
Council. The SulfinolSM solvent is circulated
between absorber and stripper by two parallel Orica Engineering Services were involved in the
pumps and a third pump is standing by. initial design checks and prepared engineering
specifications for the side stream filtration unit.
The ammonia plant has a SulfinolSM reclaimer
where degraded chemical product known as Lean solution pump (P604s) curves were
oxazolidone is removed through vacuum checked and found suitable for the aMDEA®
distillation and the sludge is used to coat a conversion. The Stripper overhead reflux pump,
product to suppress dust in the granulation plant. (P603s) curves were also checked & found to be
About 6 tonnes per day of steam are used in the adequate, but new valve trim was required for
reclaimer reboiler. the stripper reflux drum (T604) level control
valve, LCV602A.
An arsenic based solution that acts as a
corrosion inhibitor is added on weekly basis to

AMMONIA TECHNICAL MANUAL 26 2007

BASF advised on the solvent piping stress- feature that is required for this type of
relieving requirements for aMDEA® system. solvent system. Since the new system
Fortunately, no stress relieving measures were requires lower circulation rates with
required for using aMDEA®. aMDEA® as compared with SulfinolSM,
most of the existing equipment was
adequate.
Modifications to Existing 9. Corrosion coupons in rich & lean
SulfinolSM System solution lines.

The following changes were made to the CO2 No changes were made to the absorber
stripper: column and its internals already had SS
1. Replacement of current random packing random packing.
with high efficiency structured packing
(Figure 2) of Sulzer Mellapak® to
increase mass transfer efficiency and Risk Assessments and HAZOP Study
capacity.
a. Bottom 11 layers, Mellapak This project was justified based on the reduced
170X for higher capacity (of that chemical costs, and savings from cooling water
3 layers thicker sheet material for and steam.
added strength).
b. Top 13 layers, Mellapak M2X All phases of this project posed risk - design,
for higher efficiency. engineering and implementation. Poor
2. Replacement of liquid downcomers with implementation could have resulted in delays to
envelope type downcomers for top wash the plant start up due to the extension of the
trays. post-2007 shutdown period. These risks were
3. Replacement of the flash gallery (Figure minimised by the following:
3) to conform to BASF design
requirements. - Choosing BASF’s aMDEA® process with
4. Replacement of the liquid distributor more than 200 plants in operation.
(Figure 4) to improve liquid distribution
in the column. - The supplier of chemical plant internals for
5. New support grid (Figure 5) that is absorption and desorption columns, Sulzer,
suitable for structured packing. carried out design checks and also suggested
6. Opening up of all bubble caps (Figure 6) modifications suitable for the GI application.
on the wash trays: some caps previously Sulzer has been a main vendor for many of
had been blanked off. BASF’s designed plants & retrofit applications.
7. Installation of stiffening plates (Figure
7) on two wash trays in order to prevent - Orica Engineering Shared Services (OESS)
any damage to the wash trays during reviewed the BASF and Sulzer designs, and all
operation. This had become necessary, other existing equipment. OESS’s expertise in
as the distance between the flash gallery the design review of the packed columns further
and trays was only 300 mm versus an mitigated risks to the project.
optimum design of 500 mm.
8. A new side stream filtration unit and an - Design reviews, risk assessments and HAZOP
improved antifoam dosing system were studies were carried out.
also installed as part of the project. The
side stream filtration is a common

2007 27 AMMONIA TECHNICAL MANUAL

- Visits were made to existing ammonia plants All new internals for the CO2 stripper were
in the US and Western Australia that have chemically cleaned prior to shutdown by
successfully changed over their SulfinolSM submerging them into a 3 wt% caustic solution
systems to aMDEA®. The long operating in a warmed-up bath outside the plant. The
experience gained at these plants was applied to purpose of the chemical cleaning is to remove
GI design and implementation. manufacturing oils, which are responsible for
foaming of the amine solution. After the
- BASF provided classroom training to all shift chemical cleaning, the internals were rinsed
operating teams prior to shutdown where unit with demin water and it was confirmed there
operations of CO2 removal system were was no potential for foaming in the rinse water.
discussed in detail.
The old internals such as flash gallery, liquid
- Based on BASF information, a comprehensive distributor and SS random packing (raschig
training package for the new aMDEA® system rings) were removed and the vessel was
was developed for the ammonia plant operators. inspected. We observed heavy scale build up on
the CO2 stripper vessel walls and as much of it
- Incitec Pivot laboratory was supplied with new as possible was removed within the maintenance
analytical procedures by BASF and discussions window by chipping it from the vessel. Then the
were held with BASF regarding tests for vessel was cleaned.
aMDEA® strength and foam.
Extensive scale build up was also noticed on the
The Project schedule was as follows: bubble caps of stripper top wash trays and they
Capital approval: May 2006 were sandblasted prior to reinstallation (Figures
Detail design: June 2006 8 and 9).
Order material: June 2006
Delivery of material: December 2006 The tube bundles of process gas reboilers,
Installation & Commissioning: E602A/B were removed and hydro blasted and
February/March 2007. the shells, which had SulfinolSM sludge deposits,
were flushed with demin water.

Pre-Commissioning/ Also inspected were the CO2 absorber (D602),

Commissioning vapour lines from E602s/E678, tube sheets of
solvent/solvent exchangers (E604s) and D601
During shutting down of the plant, all the solution outlet lines.
SulfinolSM solution was transferred to its storage
tank, T605. Then, the system was flushed with Old packing support clips were removed and
condensate (demin water) by circulating with new shims were provided prior to the
the lean solution pumps. First wash water was installation of new internals.
recovered to use it in another plant and 2nd wash
water that had very low levels of SulfinolSM was New internals were installed in the CO2 stripper
drained to plant effluent system. To insure that under the supervision of a Sulzer field engineer.
hydrogen was removed from the SulfinolSM This took about a week.
solution, the solution was regenerated by using
the auxiliary steam reboiler prior to draining to Once the unit was handed back from
storage tank. maintenance, the system was flushed with
demin water twice to ensure that suspended

AMMONIA TECHNICAL MANUAL 28 2007

solids & iron levels were within BASF antifoam than was originally anticipated.
recommendations. Overall, there are more benefits than originally
envisaged from this change to aMDEA®, such
For commissioning, the system demin water as reduced solvent circulation rates, lower
was first added to the system and circulation regeneration heat load and reduced heat
was established after pressuring the CO2 rejection to cooling tower.
absorber with nitrogen. Then aMDEA® was
added to the water and solvent circulation was
established in early March 2007, well ahead of N2 blanketing system
gas introduction to the CO2 absorber while the
reformer and shift converters were being heated A new nitrogen blanketing system (Figure 10)
up. Finally, process gas was introduced to the was installed on aMDEA® solution storage tank,
absorber and the entire aMDEA® system was as it was not there on the original SulfinolSM
run for a week at reduced gas rates during solution tank. As part of this, a pressure
synthesis converter catalyst reduction. regulator in the N2 supply line, a pressure relief
coupled with vacuum breaker and a rupture disc
The side stream filter was first commissioned in the old tank vent line were installed (Figure
with 20-micron polypropylene cartridge filters 10). The anchor plates of the tank foundation
and then switched to 5-micron filters. About 10 were reinforced with additional supports and
litres of antifoam were injected to the system as this has helped to improve tank safety and
an initial charge prior to gas feed. integrity.

Operating procedures were also modified to

Operating Experience ensure that, during plant outages, only lean
aMDEA® is transferred to the storage tank after
The ammonia plant was initially operated at 600 regeneration of solution.
mtpd until all the catalysts were reduced. No
issues were observed with the aMDEA® system.
Plant rates were then raised to 740 mtpd for few Summary
days where the system was steady and finally,
the plant rates were raised to a maximum of • SulfinolSM conversion to aMDEA® was a
860-865 mtpd. successful project that helped to reduce
operating costs of the Gibson Island
At about 860 mtpd carryover of aMDEA®
ammonia plant.
solution was experienced from the CO2 stripper
• Significant energy savings were achieved by
into the top reflux drum and then into the urea
not using the 2 bar (30psig) steam auxiliary
plant. It was brought under control by dosing
reboiler (E678), and by complete isolation
antifoam. Initially, it was necessary to dose
of the old SulfinolSM reclaimer system that
antifoam almost every 2 hours. The system
consisted of a steam reboiler, condenser and
strength was about 38% and it was brought up
sludge handling system.
to 40% by adding more aMDEA®. We then
started isolating the side stream filter during the • Handling of heavy metals such as arsenic
dosing of antifoam. Both these conditions based corrosion inhibitors have been
helped us to reduce foaming. discontinued with aMDEA®, as the system
no longer requires a corrosion inhibitor.
Overall, the aMDEA® system has been fairly • The water make up to the CO2 removal
steady except for the need to dose slightly more section was reduced from 2 Tonnes/hr to
0.75 Tonnes/hr.

2007 29 AMMONIA TECHNICAL MANUAL

 • The previous very frequent manual handling new system has paid off well. There were no
of chemical drums is no longer required. major hiccups after change over of the
The aMDEA® makeup requirements are solvent.
quite negligible in comparison to the
SulfinolSM system. Authors’Acknowledgment
• The aMDEA® solvent circulation rates were
reduced by about 25% v/s SulfinolSM and The authors acknowledge the support provided
hence, there are energy savings from by Agrium Kenai Nitrogen Operations (Bill
reduced heat load on the cooling tower and Switzer etal), Alaska for having shared their
also from the lean solvent pumps. experience in converting SulfinolSM to
• The CO2 removal system with aMDEA® aMDEA®.
will allow us to operate the plant as high as
900 mtpd provided we don’t have any other Also thanks is given to Yaso Vesely and Terry
constraints in the plant. This will be a Moses of Sulzer, Govind Mudaliar of Orica, GI
significant benefit for the long-term ammonia plant operations, the maintenance,
operation of the plant. project engineering and laboratory teams, and
• A systematic approach to process design, GI 2007 Shutdown team, who were involved in
risk assessments, design reviews, hazop the successful completion of this project from
study, shutdown plans for the installation of conceptual stage to commissioning.
new internals in the CO2 stripper, reference
plant visits, operator training, pre-
commissioning and commissioning of the

Table 1. Physical properties SulfinolSM v/s aMDEA®

SulfinolSM aMDEA®
pH: 10.7 10.1
Density, gm/ml 1.064 1.055
Viscosity, cP 92 6.4
Boiling point
of water free amine
mixture, °C ( o F) 285 (545) 247 (477)
Combustible No No
Flammable No No

AMMONIA TECHNICAL MANUAL 30 2007

 Table 2. Operating conditions SulfinolSM v/s aMDEA®
SulfinolSM aMDEA®
Production mtpd 820 860
Lean solvent
Circulation flow, 705 535
Tonnes/hr
Lbs per hour x 1000 1,554.5 1,179.6

CO2 stripper, D601

Overhead temp, °C (°F) 87 (188) 77 (170)

CO2 slip ppm, D602 200 130

CO2 stripper, D601 5.5 2

Reflux flow, Tonnes/hr

Water make up to 2 0.75

aMDEA® system,
Tonnes/hr

Regeneration heat load 121 (114) 92 (87)

GJ/hr (BTU/hr)

2007 31 AMMONIA TECHNICAL MANUAL

 Treated Gas Flash Gas Acid Off-Gas
Condenser
E-606

Make-Up
Water

Lean Solution
Cooler
E-605 A/B Absorber hp flash Stripper
C1 C4 C9

Reboiler
Feedgas E-602 A/B E-678

Solvent/Solvent
Heat Exchanger
E-604 C/D/E/F Lean Solution E-604 A/B
Pump
Figure 1: Flow sheet of CO2 removal system

Figure 2. New structured packing and locating grid

AMMONIA TECHNICAL MANUAL 32 2007

 Figure 3. New flash gallery

Figure 4. New liquid distributor in CO2 stripper

2007 33 AMMONIA TECHNICAL MANUAL

 Figure 5. New support grid for packing in stripper

Figure 6. Wash tray on top of CO2 stripper

AMMONIA TECHNICAL MANUAL 34 2007

 Figure 7. New stiffening plates on the bottom of wash trays

Figure 8. Scale build up on old bubble caps from old trays

2007 35 AMMONIA TECHNICAL MANUAL

 Figure 9. Bubble caps after sand blasting

Figure 10. Nitrogen blanketing system for aMDEA® storage tank

AMMONIA TECHNICAL MANUAL 36 2007