BASF Operating Handbook Rev June 2008

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Handbook of the

®
aMDEA
Process
Operation of aMDEA Plants
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

Handbook of the
®
aMDEA

Process

Revision 3.1, June 2008

Operation of aMDEA Plants

CONFIDENTIAL page 1 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

1 Cleaning procedure

1.1 General Aspects


The cleaning procedure prior to the start-up of an aMDEA unit consists of the following
steps:
• Pre-cleaning
• Preparation for flushing by circulation
• Potash solution flush
• First condensate/demineralized water flush
• Second condensate/demineralized water flush
For new plants, all five cleaning steps above are usually required. For revamps and solution
swaps, the scope of cleaning work has to be decided individually, based on the actual
condition of the system. According to BASF's experience, the following rules of thumb can
be given:
• Anytime a new piece of equipment is installed into an operating aMDEA acid gas
removal unit, it needs to be degreased by a potash solution flush. Even when The
flushing can be limited to the affected parts. Note that new packing is usually oily
due to the manufacturing process. Even so called "degreased" packing, which can
be ordered from the manufacturers, typically contains more oil than can be
tolerated in the aMDEA process. Hence, a caustic cleaning step is also required in
this case. A cleaning of the packing outside the columns might be feasible.

1.2 Pre-cleaning
The pre-cleaning of the unit is done by air or steam blasting and by water flushing using fire
hoses. Thereby, coarse grime which may have been introduced during construction is
removed. The vortex breaking packing should not yet have been installed at this stage of the
cleaning procedure.
• open manholes and bottom drains of the columns and tanks
• remove orifice meters in the liquid lines and, in advance, close the taps in the
impulse pressure line connections
• plate and frame heat exchangers should be disconnected or bypassed during the
initial cleaning steps until the plant is sufficiently clean. Otherwise, they could get
plugged rapidly.
• flush the equipment with water using fire hoses
• clean lines in sections in the same manner
It is recommended to remove the grease and oil from the vortex breaking packing outside the
columns. The reason for this recommendation is that during the caustic flushing step, sludge
and debris usually gathers in the bottoms of the columns, which can only be removed when
the vortex breaking packing is not yet installed. On the other hand the oil from this packing
needs to be removed, which can be done effectively by using a caustic or potash solution. In
general the same chemicals, temperatures, procedures, etc. as for the cleaning of the plant can
be applied. The cleaning can eventually be carried out in a pit or in a container, which can be

CONFIDENTIAL page 2 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

heated up using live steam. The cleaning can then be done by submerging big bags with the
packing in the solution and leaving them there for some time. Afterwards, the caustic solution
shall be flushed away. Appropriate safety measures are required.
The vortex breaking packing should not be installed before the first condensate/demin water
flush to allow for easy removal of solids and sludge.

1.3 Preparation for flushing by water circulation


The following steps should be taken to prepare the system for flushing by circulating a liquid:
• Install strainers on the suction side of the pumps
• Check that the pumps are not mechanically blocked by coarse grime
• Check operation of all remote-controlled actuators and control valves
• Check operation of all equipment activated by the safety shutdown system
(simulate shutdown conditions)
• Leak test by pressurizing the system with nitrogen, e.g. to 1 bar (gauge). Check the
flanges and cover seals on the columns and tanks, which were opened for the
water flush for gas leakage using a suitable indicator (e.g. soap solution).

1.4 Flushing with 3 % (wt.) potash solution


Before any alkaline flush will be carried out some operators prefer to have an acid flush first
to remove some scale and rust. If an acid flush step (using citric acid or similar) is carried out,
a water flush has to follow, before flushing with 3% (wt.) potash solution starts.
The following steps should be taken to prepare the system for flushing with a 3 % (wt.)
potash solution:
• Prepare the solution from condensate or demineralized water and potash (K2CO3).
The pH value of this solution is about 12. A technical quality of potash can be
used. It is recommended to keep the chloride content of the potash solution below
100 to 500 ppm (wt.). This corresponds to a chloride content of the water-free
potash of 0.34 to 1.65 %(wt.), calculated as Cl-. A higher chloride content should
be avoided due to corrosion concerns.
• Instead of potassium carbonate, tri-sodium-phosphate (Na3PO4), sodium
carbonate, sodium hydroxide or potassium hydroxide can be applied. The pH
value is higher in these cases (pH 13 and 14, respectively). Therefore, it is not
recommended to exceed the maximum temperature of 70°C (158°F) to prevent
corrosion damage of the equipment.
• A higher concentration than 3 %(wt.) is possible and might be recommended for
plants with very dirty equipment. In practice NaOH solution with a concentration
of up to 5 %(wt.) has been applied successfully.
• Introduce the solution into the plant at a suitable location, e.g. at the bottom of LP
flash vessel.
• Pressurize the absorber to approx. 3 to 5 bar (gauge) with nitrogen. In the
regenerator a pressure of 0.1 to 0.5 bar (gauge) might be maintained by means of
the pressure controller in the CO2 off-gas line.

CONFIDENTIAL page 3 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

• Circulate the solution through the system for about 8 hours at a temperature of 50
to 70°C (122 to 158°F) at full flow rate. For this purpose the solvent circulation
pumps have to be taken in operation according to the vendor's instructions. As
soon as steady conditions are achieved, check the circulation rate by means of the
FIC valve positions. Simultaneously, the level indicators should be checked.
• Full flow rate means 100 % of design flow rate. Pumps and spare pumps should be
taken into service and cleaned one after the other. Do not operate all pumps
simultaneously in order to avoid an extremely high flow rate, which could exceed
the hydraulic limits of the plant.
• Empty the entire system. Take liquid samples.
• If the potash solution after flushing is extremely dirty, the caustic flushing step
will have to be repeated, eventually several times. This applies especially to plants
which are very dirty or rusty, e.g. new plants in hot and humid climate zones,
plants operated formerly with amine solution containing arsenic for corrosion
protection, hot pot units with severe arsenic or vanadium deposits inside the
vessels and lines, etc. In other cases two caustic flushing steps should be enough.
• According to BASF's experience, it is extremely difficult to remove arsenic or
vanadium residues totally from the vessel walls and column internals in plants
operated formerly with amine solution containing arsenic or in revamped Hot
Potassium Carbonate systems. Even after several flushing steps the flushing water
might still contain arsenic or vanadium in the range of 100 ppm (wt.). It is
recommended to remove these contaminants with reasonable effort as far as
possible in order to keep the aMDEA solution clean. However, there are no
detrimental effects on the performance of the system known, which are caused by
traces of arsenic or vanadium.
• Remove and clean strainers in the pump suction lines.
• Re-install the suction side strainers of the pumps.
In case the waste water has to be neutralized prior to disposal, the neutralization must be
carried out outside the CO2 removal unit.

1.5 First condensate/demineralized water flush


The following steps should be taken for the first flushing with condensate/demineralized
water:
• Install the carefully cleaned additional packing for the bottom section (vortex
breaking packing) into the bottom of the absorber (and hp flash).
• Reinstall orifice meters.
• Plate and frame heat exchangers can be taken on line. They should be protected by
strainers in order to prevent plugging.
• The first water flush is carried out as described in section 1.4. The water is initially
heated to about 70 °C (158 °F) and the system is flushed for about 5 hours at full
flow rate. The flow rate can be indicated by means of the reinstalled orifice meter.

CONFIDENTIAL page 4 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

• Full flow rate means 100 % of design flow rate. Pumps and spare pumps should be
taken into service and cleaned one after the other. Do not operate all pumps
simultaneously in order to avoid an extremely high flow rate, which could exceed
the hydraulic limits of the plant.
• Take a liquid sample from the water used for flushing and add about the same
volume of MDEA or aMDEA to the sample so that the specified amine
concentration is approximately met. Check this diluted amine solution for foaming
activity (see separate manual: "Analysis Manual for the BASF aMDEA Process").
The foaming tendency is considered low when the foam volume is not higher than
300 ml and the collapse time 20 s or less. However, a somewhat higher foaming
tendency during operation can be compensated by an increased antifoam dosage
rate.
• Compare the result of the foam test with a foam test carried out with a mixture of
aMDEA and demineralized water. This blind test gives you the baseline for the
foam tests carried out with samples from the system.
• Check the pH value of the solution. The pH value should be ≤ 9. A higher pH
value indicates too high a potassium carbonate content.
• Drain the water and check the suction strainers for dirt.
• If the flushing water is clean, the foaming tendency is low (foam volume ≤ 300 ml
and collapse time ≤ 20 s) and the pH value is not too high, the second
condensate/demineralized water flush can be omitted.

1.6 Second condensate/demineralized water flush


The following steps should be taken for the second flushing with condensate/demineralized
water:
• The flush is carried out as described for the potash solution in section1.4.
• Circulate the water through the system for about 6 hours at full flow rate and
simultaneously raise the temperature to the operating temperature.
• Take a liquid sample from the water used for flushing and add about the same
volume of MDEA or aMDEA to the sample so that the specified amine
concentration is approximately met. Check this diluted amine solution for foaming
activity (see "Analysis Manual for the BASF aMDEA Process"). If foaming
activity exceeds the guidelines, a repeat of the caustic flushing with 3 % (w/w)
potash solution according to section 1.4 , followed by condensate/demineralized
water flushes according to section 1.5 and 1.6 as described above should be
considered.
• Check pH of the solution. The pH value should be ≤ 9. A higher pH value
indicates too high a potassium carbonate content.

CONFIDENTIAL page 5 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

• If the flush water is clean, the foaming tendency is low (foam volume ≤ 300 ml
and collapse time ≤ 20 s) and the pH value is not too high, the aMDEA can be
charged. Otherwise, flushing with 3 %(w/w) potash solution and/or the
demineralized water flush has to be repeated. A foam volume not higher than 300
ml and a collapse time of 20 s or less are required for a low foaming tendency.
However, these figures still have to be compared with the results of a blind test
(foam test with a mixture of pure aMDEA and demineralized water), which
defines the baseline for the foaming tendency. Better values than in the blind test
can usually not be achieved. An exception might be revamped systems, where
traces of the antifoam agent formerly used might be present in the wash water. A
somewhat higher foaming tendency than recommended during operation can be
compensated by an increased antifoam dosage rate.
After the final water flush, the content of particles in the wash water should be small. As a
rule of thumb, the solid content can be judged as follows:
<10 ppm (wt.) solids: excellent
<50 ppm (wt.) solids: good
<100 ppm (wt.) solids: acceptable
A higher content of solids usually leads to an excessive foaming tendency. In this case, a
further flushing step is required.

CONFIDENTIAL page 6 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

2 aMDEA solution – preparation and activator system

2.1 Absorption mechanism


The aMDEA solvent reacts with CO2 as shown in Figure 1. MDEA, as a tertiary amine, can
only react as a base with the sour CO2. This reaction is fairly slow. For this reason activators
are added, which reacts rapidly with CO2 by forming a carbamate. MDEA can then react with
the carbamate, whereby the CO2 is transferred. All these reactions are equilibrium reactions.
In the regenerator the same reactions as in the absorber take place in the opposite direction.

GAS PHASE LIQUID PHASE

activator MDEAH+ + HCO3-


system
CO2 FAST

activator MDEA + H2O


+CO2
system

MDEAH+ + HCO3-

CO2 SLOW

MDEA + H2O

CO2 + H2O + MDEA MDEAH+ + HCO3-

Figure 1: CO2 absorption mechanism

According to the formulas shown, water is not just a diluent but also a reactant. Hence, a too
dilute solution as well as a too concentrated solution leads to a deterioration of absorption
performance.
H2S reacts with both, MDEA and activators in a fast reaction of an acid with a base as
follows:
H2S + MDEA ↔ MDEAH+ + HS-

CONFIDENTIAL page 7 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

2.2 Solution strength


The aMDEA solvent systems are delivered as premix solutions, which consist of MDEA, the
activators and a low water content. For application in the gas treatment unit the solvent has to
be diluted with demineralized water. The type of solution and the recommended solution
strength are defined individually for each project. Usual amine concentrations are 40, 45 and
50 % (wt.). During operation, the recommended range of the amine content is as follows:
target figure tolerance range
40 % (wt.) 37 to 45 % (wt.)
45 % (wt.) 42 to 50 % (wt.)
50 % (wt.) 46 to 55 % (wt.)
During a test run the solution strength shall not be lower than the design figure.
The amine concentration can be varied by adjusting the flow rate of make-up water to the
system.

2.3 Activator content


The activator system used in the aMDEA solution primarily influences the CO2 absorption
rate rather than the CO2 absorption capacity. The target figure for the activator content is
different for each type of aMDEA. For each project a special aMDEA type is specified with a
specific activator content. Thereby, it is ensured that the desired CO2 slip is met. Optimization
during operation is possible, i.e. at a lower activator content the CO2 slip might still be met,
depending on actual operating conditions, plant load, packing type used in the absorber,
quality of liquid distribution etc. Too low an activator content can be balanced by a higher
solution flow rate.

2.4 Water quality


It is recommended to use degassed, demineralized water or condensate for diluting the
aMDEA premix, as well as for water make-up. The presence of oxygen during plant operation
might increase the corrosiveness, although the aMDEA solvent is hardly affected by oxygen.
Hence, the use of oxygen-free (below 10 wppm) make-up water is recommended. In case the
oxygen content will be significantly higher, the use of oxygen scavengers may be considered.
Companies like Nalco or Alken-Murray are offering oxygen scavengers, however, BASF has
no experience in aMDEA-service so far.
For ions and particles the following maximum levels should not be exceeded:
• max. 1 to 2 ppm (wt.) of Cl-
• max. 3 ppm (wt.) of Na+
• max. 3 ppm (wt.) of K+
• max. 5 ppm (wt.) of Si
• max. 10 ppm (wt.) of dissolved Fe
• max. 50 ppm (wt.) for total hardness, expressed in terms of Ca2+
• max. 100 ppm (wt.) of suspended solids, max. particle size 10 µm, max. 35 % (wt.) of
these, i.e. 35 ppm (wt.) in range of 5 to 10 µm, remainder below 5 µm.

CONFIDENTIAL page 8 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

The electrical conductivity at 25°C (77°F) should be less than 10 µS/cm (25.4 ⋅ 10-6Ω-1inch-1).
For chloride see also section 2.5. The amount of suspended solids should be limited due to the
increased foaming propensity encountered with high particle levels. The other specifications
are given as a precaution in order to keep the solution clean and free of contaminants. Hence,
deviations from the recommendations above are still possible, depending on the water quality
available on site. Please contact BASF's aMDEA group in case of doubt. There is no
detrimental effect on the performance of the amine system known, which could be caused by
the compounds listed above.

2.5 Chloride level


The chloride content of the water has to be limited with respect to pitting corrosion and stress
corrosion cracking. The recommended maximum level of chlorides in make-up water is 1 to
2 ppm (wt.). Note that chlorides fed with the water accumulate over time.
aMDEA is a product free of any chlorides. Hence, chlorides can only get into the solution
from external sources, e.g. make-up water or leaking water coolers.
To be on the safe side the chloride level should be kept as close to zero as possible. It is
recommended to keep the level below 100 ppm (wt.). This is in accordance with the majority
of literature sources. Problems in amine units at this or a lower chloride level are unknown to
BASF. At higher levels the risk of localized corrosion increases. The customer has to decide
whether or not a special treatment of the amine solvent should be carried out in order to lower
the chloride content. This should be based on a thorough consideration of the cost involved
and the corrosion risk, which can be tolerated. At chloride levels above 500 ppm (wt.) a
treatment of the system is recommended.
For regenerating the solvent from chloride the temporary installation of a specialty filtration
system could be feasible, e.g. ion exchange, electrophoresis or side stream vacuum
distillation. All these techniques have been proven in a pilot scale plant by BASF. MPR
services offers an ion exchanger process which is commercially proven in operating aMDEA
units as well as in other amine systems. A similar process is offered by Eco-Tec who have
experience with various amine systems. A vacuum distillation process is, among others,
offered by CCR Technologies, Inc.

CONFIDENTIAL page 9 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

2.6 Solvent make-up


The annual solvent losses are approximately 5 to 10 % of the aMDEA premix inventory. The
solvent losses are mainly caused by mechanical reasons, such as pump leakage, cleaning and
replacement of filters or liquid entrainment in the off-gas streams. Hence, the losses depend
strongly on the frequency of maintenance measures and the equipment installed to avoid
entrainment.
The aMDEA premix can be used for solvent make-up. However, the concentration of the
activator system drops slowly over months of operation since the vapor pressure of the
activators are higher than that of MDEA. , which can be balanced by the addition of an
enriched aMDEA make-up solution consisting of 40 %(wt.) MDEA, 40 %(wt.) activators and
20 %(wt.) water . The activators make-up can be directly added to the solvent loop, e.g. on
the suction side of the lean solution pump.

2.7 Solvent storage of aMDEA-Premix


The premix can be stored a delivered in drums in a warehouse or in a dedicated storage tank.
In case the premix is stored for periods longer than three months in a storage tank, nitrogen
blanketing is recommended. The continuous contact with air turns the solvent color from light
yellow to brownish due to the formation of degradation products in the ppm-range. However,
while the absorption parameters of the aMDEA solvent are not altered, the foaming activity
can be somewhat higher.
The storage tank can be heated using a steam coil. In order to prevent degradation of the aMDEA
solution it has to be ensured that the aMDEA is properly diluted with water when the steam coil
is in operation, i.e. at least 10 % of water has to be added to the aMDEA premix. It has to be
checked from time to time whether the water content is still sufficient and the temperature in the
tank is not too high due to the successive evaporation of water. Without any water added to the
aMDEA premix, the temperature in the storage tank (especially the wall temperature of the
heating coil) could get too high, thus leading to degradation of the aMDEA. This is not the
case when hot water or condensate with a temperature not higher than 80°C is used as a heating
medium.
In the sump of the tank, sludge and particles are usually gathered. When solvent is pumped
from the tank to the amine unit, e.g. for make-up, it is recommended to use a filter. The
normal solution filters can be used for this purpose, provided that pumps, lines and valves are
installed accordingly.

2.8 Storage of used aMDEA Solution


IMPORTANT SAFETY NOTICE:

The storage tank used for storing the aMDEA solution has to be blanketed with nitrogen at all
times. In some specific cases other gases may be used for blanketing, too. Contact BASF in
case no nitrogen is available for tank blanketing.

The nitrogen blanketing is particularly important in hydrogen plants where residual hydrogen
or other flammable gases can be released from the solvent when the solvent is transferred from

CONFIDENTIAL page 10 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

the system to the storage tank. There is a high risk that these flammable gases form an
explosive mixture in the tank if it is not blanketed with nitrogen. There have been several
documented cases of tank explosions due to gas that has been released or flown back from the
absorber into the storage tank.

2.9 Minimum solution temperature


At low temperatures, precipitation of the activator system from the aMDEA solution might
occur. The precipitation point depends on the concentration of the activator system and the
water content of the solution. Precipitation of the activators must be avoided, because
without a good mixing, it is difficult to re-dissolve the precipitated activators in the solution.
The minimum temperature of the solution has to be maintained high enough to avoid
precipitation of the activators.

BASF’s aMDEA should be kept above the following temperatures:

• aMDEA Enriched: above 20 °C (68 °F)


Below 20 °C (68 °F) the activators starts to precipitate and below -10 °C (14 °F) it
solidifies.

• aMDEA Premixes: above -20 °C (-4 °F)

• aMDEA Blends: above 15 °C (59 °F)


aMDEA blends containing 50 or 60% water have to be kept above 15°C to prevent
precipitation.

Although the aMDEA Premix can be stored at temperatures as low as -20 °C (-4 °F) the
liquid will become viscous as its temperature is lowered. For example, the aMDEA Premix is
flowable, but has a viscosity similar to honey at -20 °C (-4 °F).

CONFIDENTIAL page 11 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

3 Start-up procedure

3.1 Measures prior to start-up


Prior to the start-up of an aMDEA plant the following steps are required:
• Cleaning of the plant according to our cleaning procedure.
• Disconnecting the lines for pressurization of the absorber and the hp flash, e.g. by means
of blind flanges.
• Check for leaks.
• Filling in the aMDEA premix and water as described below in section 3.2.
• For synthesis gas applications the usual solution strength is 40 % (wt.) of amine. In other
applications a specification of 45 %(wt.) or 50%(wt.) is also possible. In all these cases the
tolerance range for the solution strength during operation is as follows:
target figure tolerance range
40 % (wt.) 37 to 45 % (wt.)
45 % (wt.) 42 to 50 % (wt.)
50 % (wt.) 46 to 55 % (wt.)
Note that during a test run the solution strength shall not be lower than the design figure.
• Prepare an initial charge of antifoam agent, which should be added to the system after the
circulating solvent is heated up, approximately one or two hours before gas shall be
charged to the system. The concentration of antifoam should be 50 ppm (wt.), i.e. per
100 m3 of solvent, 5 l of antifoam agent should be added.

3.2 Preparing the aMDEA solution


The dilution of the aMDEA premix can be carried out in a mixing tank or solution preparation
tank. If no mixing tank is available, the mixing can be carried out in the plant itself, using the
solvent circulation pumps. In this case it is recommended to charge a part of the required
amount of demineralized water to the system (e.g. 80 %) and add aMDEA premix while the
solution pumps are running. Avoid charging too much water. Usually, the solvent inventory is
not exactly known. If too much water was added initially, the solution could become too
diluted. Observe the levels in the columns while charging the solution and the premix,
respectively. At the end, the rest of the water, if required, can be added. Make sure to hit the
target figure for the solution strength.
The water used for diluting the premix must have a temperature of at least 20 °C (68 °F). A
higher temperature should be preferred and is recommended, e.g. 50 °C (122 °F), because the
viscosity of the solution is less at elevated temperature and a homogeneous mixture is
achieved more quickly.
At a temperature below 15 °C precipitation of the activators could occur. This applies to the
premix as well as to the diluted mixture. Refer to the physical properties manual for the
precipitation point, which is specific for each type of aMDEA and which depends on the
water content of the mixture.

CONFIDENTIAL page 12 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

The aMDEA premix is very viscous at low temperature. When ambient temperature is low it
might have to be preheated before charging it to the system. Make sure to empty the
containers or drums completely, i.e. without leaving any possibly-precipitated activators
behind.

3.3 Passivation step prior the very first start-up


If the acid gas removal unit will be operated with BASF’s aMDEA for the very first time a
passivation step has to be carried out. It is recommended to repeat the passivation step after
every regular inspection.
The start-up of the system should be performed according to the experience of the operating
staff. The following guidelines can be given:
• Establish the levels in the columns. The system must be under inert atmosphere.
• Introduce feed gas to the absorber and pressurize this column to the design
pressure.
• Start amine circulation at a low flow rate (approx. 50 % of design figure).
• If possible, bring the solution to its operating temperatures by feeding steam to the
reboiler and operating the lean solution coolers.
• Increase the circulation rate to 70 - 80 %.
• Establish the operating pressures and temperatures in the system.
• Add the initial charge of antifoam agent according to section 3.1.
• Increase the solvent circulation rate to 100%.
• If the gas used for pressurizing the absorber contains CO2, it will be absorbed by
the solvent and the pressure in the absorber will drop. Once the CO2 is removed
from the absorber the gas released as acid off gas contains pure hydrocarbons in
case natural gas is used for pressurizing the absorber or pure syngas (CO/H2), if
syngas is used for pressurizing the absorber. That means the acid off gas will have
a very high heating value and will be flammable/explosive.
• Check for foam activity.
• Check the solvent strength.
• Continue circulating the solvent for 3 consequent days.
• Afterwards, the solvent circulation can be either stopped or reduced to 50% design
flow rate. At 50% design flow rate the further start-up steps can be followed as
described below in chapter 3.4 .

3.4 Regular start-up


The start-up of the system should be performed according to the experience of the operating
staff. The following guidelines can be given:
• Establish the levels in the columns. The system must be under inert atmosphere.
• Introduce feed gas to the absorber and pressurize this column to the design
pressure.
• Start amine circulation at a low flow rate (approx. 50 % of design figure).

CONFIDENTIAL page 13 / 29
BASF SE aMDEA Handbook
CZA/ML - E 100 Part III
67056 Ludwigshafen, Germany Revision 3.0, June 2008

• If the gas used for pressurizing the absorber contains CO2, it will be absorbed by
the solvent and the pressure in the absorber will drop. Once the CO2 is removed
from the absorber the gas released as acid off gas contains pure hydrocarbons in
case natural gas is used for pressurizing the absorber or pure syngas (CO/H2), if
syngas is used for pressurizing the absorber. That means the acid off gas will have
a very high heating value and will even be flammable/explosive.
• Bring the solution to its operating temperatures by feeding steam to the reboiler
and operating the lean solution coolers.
• Add the initial charge of antifoam agent according to section 3.1.
• Start feeding gas at < 30 % rate.
• Establish the operating pressures and temperatures in the system.
• Start-up the reflux pumps after a condensate level has been established.
• Slowly increase the plant capacity by 5 % to 10 % steps (both gas and liquid
streams).
• During start-up the liquid flow rate should always be 20 % higher than the amount
required for the current feed gas rate.
• Check for foam activity.
• Afterwards, antifoam agent should be added as necessary or according to the
recommendation in section 4.4. The initial charge of antifoam is usually sufficient
for the first couple of days.
• Check the solvent strength.

3.5 Time required for start-up


The time for starting up the cold plant depends essentially on the time for heating-up the
solvent and the equipment, which is specific for each particular plant. A rough calculation can
be performed on the basis of the reboiler heat duty, the solvent inventory and the weight of
the equipment.

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4 Operating instructions

4.1 CO2 slip


The CO2 and/or H2S slip is the most important design and operating parameter in an acid gas
removal unit. A high CO2 or H2S slip can have one or more of the following reasons:
• feed gas composition, temperature or pressure out of spec
• feed gas pressure too low
• solvent circulation rate too low
• feed gas rate too high
• lean solution temperature too low
• lean solution temperature too high
• activator concentration insufficient
• insufficient regeneration of solvent
• foaming tendency too high
• mechanical damage or plugging of columns, distributors etc.
Unless there is major damage to the packing or internals in the regenerator (e.g. collapsed
support grid, plugged distributor, etc.), the regeneration of the solvent should be sufficient as
long as the stripper overhead temperature is not too much lower than the design temperature.
Too low a solvent circulation rate can lead to a breakthrough of acid gas. In Figure 2 an
example is shown where the gas rate is steadily increased at a constant liquid flow rate.

Figure 2: CO2 breakthrough due to thermodynamic limitation of the system (example)


Finally, a point is reached, where the current solvent circulation rate is no longer sufficient to
meet the CO2 spec. A further increase in the gas rate leads to a steep increase in the CO2 slip.
The same might also happen when the plant is at its thermodynamic limit and other operating
parameters are changed. At any rate, a steep increase of the CO2 slip, as shown in Figure 2, is
an indication that the possible loading capacity of the solvent is exceeded.
The content of the activators in the solution drops slightly over time. If no other operating
parameters are changed, the decreasing activators concentration leads to an increase of the

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CO2 slip. The effect is shown in Figure 3. Up to a certain degree a lack of activators can be
balanced by a slightly increased solvent circulation rate. Finally, make-up of the activator
system is required, see section 2.6 of this Handbook.

CO2 breakthrough
kinetic limitation
1400

1200
CO2 conc. [ppm (v/v)]

1000

800

600 => more


activators
400
needed
200

0
0 2 4 6 8 10 12

Operating time [months]

Figure 3: Increased CO2 slip due to kinetic limitation of the system (example)

In section 5 of this Handbook the effect of a variation of the numerous operating parameters
on the performance of the system is discussed. The adjustment of the solution flow rate,
which is one of the major operating parameters, is described in section 4.2.

4.2 Adjustment of solution flow rate


The solution flow rate has to be adjusted in a way that the treated gas specification is met.
Overcirculation is possible at the expense of higher energy consumption. The required solvent
circulation rate depends strongly on the feed gas conditions, namely on feed gas flow rate,
feed gas pressure and acid gas content in the feed gas. In a first approach, it can be assumed
that the required solution flow rate is proportional to the amount of acid gas to be scrubbed, at
least as long as the CO2 and H2S partial pressures do not deviate too much from the design
figures. A fine tuning of the solution flow rate might be required when the CO2 and H2S
partial pressures are changed.
Note that the activator system of the solution strongly influences the absorption kinetics and,
consequently, the CO2 loading which can be achieved in the absorber bottom. Please refer to
section 5.8 of this Handbook.
When adjusting the solution flow rate, the hydraulic limitations of the plant have to be
considered, see section 4.7 below.

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4.3 Foaming problems


Reasons for foaming are impurities in the system. Typical compounds, which cause foaming,
are:
• oil, fat or grease, e.g. from insufficiently cleaned vessels or column packing
• heavy hydrocarbons or long chained organic acids entering with the feed gas
• dust from low temperature shift catalyst
• particles like rust, charcoal, etc.
• contaminants in make-up water.
H2S has been experienced to suppress foaming. Hence, in plants containing H2S in the feed
gas, the foaming tendency might be significantly lower.
Indications for a high foam activity are:
• High differential pressure in the columns
• Difficulties in controlling the bottom levels
• High hydrocarbon content (natural gas plants) or high H2 content (syngas plants) in the
acid off-gas
• High aMDEA-content in the reflux condensate or in knock-out drums
• Results of the foam test outside specified range
• suddenly increased CO2 slip
While the first five indications are fairly specific, an increased CO2 slip can have other
reasons as well. It is up to the experience of the operators to judge the indications for foaming
correctly and take the appropriate measures accordingly. Based on the specific experience in
each plant, the way foaming is detected might be different, since there are no two units in the
world operating identically. Nevertheless, the indications as listed above are quite typical.
In case of less severe foaming problems, high levels in the columns can decrease gas
entrainment into the liquid stream. However, we strongly recommend to keep the levels
below the gas inlet nozzles. Otherwise, increased foaming and poor performance of the
columns cannot be ruled out.

4.4 Antifoam agent


4.4.1 General recommendations for antifoam dosage
Antifoam agents are normally silicone, glycol or alcohol based. In BASF’s aMDEA reference
plants many different types of antifoam agents are successfully in operation. Still most
aMDEA reference plants use AmerelTM 1500. A good alternative antifoam agent is SAG
from GE, because it is water soluble and therefore, it can be easier handled at plant site.
However, some operating plants report excellent results with glycol based antifoam agents
(e.g. Pluronic) or even with mixtures of glycol and silicone based antifoam agents. Alcohol
based antifoam agents show very good performance in lab test and in some reference plants.
To prevent foaming, a regular dosing of antifoam agent is recommended, e.g. once per shift or
once per day. It can be carried out continuously, batchwise or only when increased foaming
activity is indicated. . The antifoam dosing rate depends strongly on the plant size, current
operating capacity (hydraulic load) and the impurities contained in the solution.
For the initial start-up a first charge of antifoam is recommended, which is specific for the
type of antifoam agent used. During a plant shutdown, i.e. when the solution pumps were

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stopped, the antifoam agent contained in the solution might precipitate. To avoid foaming
problems after starting up again, about one third of the initial amount of antifoam should be
added.
A detrimental effect on the performance of the system caused by excessive dosage of
antifoam agent has not yet been experienced. This applies to Amerel™ 1500, Pluronic and
SAG. Also laboratory tests could not reliably prove that an overdose of antifoam would result
in foaming problems as believed earlier. Reports claiming a relationship between excessive
antifoam still exist, but they might refer to specific types of antifoam agents other than the
ones used in aMDEA plants. Nevertheless, continuous high overdosage of antifoam over a
longer period of time should be avoided since it might lead to rapid plugging of the side
stream filter. Instead, the real reason for the high antifoam requirement should be traced in
order to look for a way to avoid the problem.

4.4.2 Amerel™ 1500


The antifoam agent Amerel™ 1500 is produced by the Drew Ameroid Company. It is widely
used in many aMDEA plants as a defoamer. This antifoam agent can also be ordered through
BASF.
Amerel™ 1500 is a suspension of surface-modified SiO2 in silicone oil. It has to be stirred
thoroughly before being added to the solution, since only the mixture is effective, not the
single compounds. A preferred location for adding Amerel™ 1500 is the suction side of the
solution pump.
Typical dosage rates of Amerel™ 1500 are as follows:
• Natural gas: 1000 ml/day for a plant capacity of 350,000 Nm3/h
• Synthesis gas: 100 ml/day for a plant capacity of 100,000 Nm3/h
Note that the figures mentioned above are only a rough estimate. The actual demand of
antifoam might be higher or lower. During foaming problems an increased antifoam dosage
rate might be required. In such a case it is better to dose the antifoam in smaller quantities
several times a day rather than dosing a large quantity in one shot. In any case the antifoam
dosage to the unit has to be optimized individually for each plant.
For the initial start-up an antifoam content in the solution of about 50 ppm (wt.) is
recommended. Hence, the amount to be added initially depends on the solution inventory.

4.4.3 Other antifoam agents


Alternative antifoam agents could be Pluronic PE 10100 and SAG 7133 (in Europe: SAG
10). Pluronic PE 10100 is a glycol-based defoamer manufactured by BASF. SAG 7133 is a
silicone-based emulsion in water. It is manufacured by GE. This antifoam mixture is
particularly suited to those systems where entrainment of heavy hydrocarbons with the feed
gas is possible, i.e. in natural gas treating units.
The hese antifoam agents can be diluted with water or condensate. A mixture with water
(three parts of water and one part of defoamer) forms an emulsion, which is stable for two
days. It is easily pumpable. The emulsion can be further diluted with water. Due to the water
content of the product the dosage rate is higher than for Amerel 1500™. Particularly for
plants with larger sized equipment for antifoam addition the application is easier.

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GE recommends to add the antifoam continuously to the discharge side of the solution pump,
in order to avoid shear forces, which could lead to a smaller and less efficient droplet size.
However, according to BASF's experience the agent is also effective when charged to the
suction side of the solution pump.
Typical dosage rate of the undiluted antifoam Pluronic or SAG is as follows:
• Natural gas: 1000 ml/day for a plant capacity of 100,000 Nm3/h
Note that the figure mentioned above is only a rough estimate. The actual demand of antifoam
might be higher or lower. During foaming problems an increased antifoam dosage rate might
be required. In such a case it is better to dose the antifoam in smaller quantities several times
a day rather than dosing a large quantity in one shot. In any case the antifoam dosage to the
unit has to be optimized individually for each plant.
For the initial start-up an antifoam content in the solution of about 50 ppm (wt.) is
recommended. Hence, the amount to be added initially depends on the solution inventory.

4.5 Filter operation


The filter deactivates the antifoam agent by the mechanical removal of the antifoam agent.
Therefore, the sidestream to the filter should not be higher than actually required. Higher
filter flow rates do not have any detrimental effect besides eventually higher antifoam
consumption and the requirement of more frequent filter exchanges. In case antifoam types
containing solid particles are used, it is therefore, not recommended to filter 100% of the
solution.
The required amount of antifoam could, however, be lower at higher filtration rate, if the
solvent becomes cleaner and if therefore, the overall foaming tendency drops.

4.6 Regular solvent Analyses


Solvent samples should preferably be taken from the lean solution line downstream the lean
solution cooler. Further samples from other locations can be taken as required. Regular
analyses can be carried out according to the experience of the operational staff. BASF
recommends the following regular analyses (see Solvent Analysis Manual for BASF’s
aMDEA Process).
• Once per day: water content,
solvent strength
• Three times per week: foam test

4.7 Reduced load operation


Within limits given by the plant hydraulics, the solution flow rate can be reduced in
proportion to the feed gas rate. The limits are given by the design of column internals (first of
all liquid distributors), pumps, heat exchangers, etc. A typical design range for distributors is
70 to 120 %, unless otherwise specified. Hence, the distributors typically define the lowest
liquid flow rate whereas the pumps often define the upper limit. It should be mentioned that a
distributor designed for 70 % of liquid load might still work even considerably below 70 %.
Anyhow, a too low liquid loading can lead to maldistribution of the liquid. A breakthrough of

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67056 Ludwigshafen, Germany Revision 3.0, June 2008

CO2 in the absorber and a poor regeneration in the stripper are possible consequences. A
liquid load less than 10 m3/m2/h can lead to maldistribution in the packing with the same
effect of poor plant performance. Considering a possible reduced plant operation a design
with a liquid load below 20 m3/m2/h should be avoided. In case of doubt please contact
BASF's aMDEA group.

4.8 Pressure drop in columns


The usual pressure drop in columns furnished with packed beds is in the range of 1 to
1.5 mbar per meter of packing (0.12 to 0.18 inches of water gauge per foot of packing. A
much higher pressure drop than 2 mbar/m (0.24 inches of water gauge per foot of packing)
might indicate an increased foam activity. As a rule of thumb it can be assumed that the
pressure drop is proportional to the plant load to the power of two.
In tray columns the pressure drop consists of two major parts: a static and a dynamic pressure
drop. The static pressure drop depends on the weir height. Per cm of weir height the static
pressure drop is approximately 1 mbar (1" of water gauge per inch of weir height). This
figure is almost independent of the plant load. The dynamic pressure drop is normally in the
range of 0.5 to 3 mbar per tray. This part of the total pressure drop depends strongly on the
gas load. An increased foam activity might be indicated by a pressure drop lower than usual.

4.9 Environmental aspects


The aMDEA process can be operated virtually without any significant effluent stream. The
only effluent streams arise during the cleaning procedure or during filter exchange.
In case of a design with excess water (too high feed gas temperature), a part of the reflux
condensate would have to be drained. This stream typically contains amines in the range of
0.1 to 1 % (wt.). Depending on design and operating conditions, particularly plant load and
foaming tendency, higher figures are possible.
aMDEA solution is non-toxic and biodegradable and can, therefore, easily be disposed of by
biological wastewater treatment or by incineration. Under usual process conditions the
lifetime of aMDEA solvent is unlimited.
The emissions of amines due to their vapor pressure are very small. They depend of course on
operating conditions like temperature and pressure. They can be reduced by installing
backwash trays. It has to be stressed that the vast majority of solvent losses are not caused by
the amine vapor pressure but by entrainment of small solution droplets, e.g. in case of
foaming problems, or for mechanical reasons.

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BASF SE aMDEA Handbook
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67056 Ludwigshafen, Germany Revision 3.0, June 2008

5 Effects of a variation of operating parameters

5.1 General Aspects


The influence of the different operating parameters on the performance of the system is
briefly discussed in the sections below. As an example, a single stage unit with stripper
regeneration is considered. However, the majority of the dependencies mentioned below are
valid in general, so that the given rules are also valid for other plant configurations. The
interactions between the various operating parameters might be fairly complex. Hence, it will
not always be easy to foresee the results if several parameters are changed simultaneously.
For this reason, the influence of a variation of only one parameter at a time is discussed
below.

5.2 Solvent circulation rate


A lower solvent circulation rate leads to a closer approach to equilibrium in the absorber and
consequently to a smaller driving force for acid gas absorption. The result is a higher slip of
CO2 or H2S, but also a lower energy consumption. Depending on the application and up to a
certain degree a slightly higher CO2 slip can often be tolerated. Hence, by adjusting the
solution flow rate the energy consumption of the system can be optimized. See also
section 4.2 of this Handbook.

5.3 Lean solution temperature


A lean solution temperature higher than design has the following effects on the acid gas
removal system:
• higher temperature in absorber bottom
• higher absorption velocity
• lower CO2 loading capacity
• higher water content in treated gas
• lower efficiency of solvent heat exchanger
• higher temperature in the flash section (hp flash or lp flash) if applicable
A solution temperature, which is above the design value, leads to a lower CO2 loading of the
solvent, but the absorption velocity increases and vice versa. Since both effects are contrary,
the overall influence of the temperature is rather small. For this reason a variation of the lean
solution temperature is usually possible within wide limits, e.g. between 40 and 60 °C,
depending on design and operating conditions. Hence, the operating temperature is rather
uncritical and can be balanced by adjusting the solvent circulation rate. Nevertheless, it
should be noted that limits do exist.

5.4 Feed gas temperature


A feed gas temperature higher than design leads to a higher temperature in the bottom of the
absorber. However, in most cases the influence is only small. The influence can be significant
only in cases where gas with very little acid gas content is treated.

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In applications where the feed gas is saturated with water, the water input with the feed gas
might increase significantly with higher temperature. In such a case the amount of make-up
water has to be adjusted. It might even be required to drain condensate from the regenerator
reflux drum to fulfil water balance of the unit, it the feed gas temperature is too high.

5.5 Feed gas pressure


If the feed gas pressure is lower than designed, the performance of the absorption process will
be reduced due to the lower partial pressure of CO2 and H2S resulting in a lower driving force
for the absorption. This can be balanced by a higher solvent circulation rate, which is,
however, at the cost of a higher specific energy consumption of the process. The hydraulic
limits of the columns have to be considered. An absorber pressure higher than design is
beneficial for the acid gas absorption.

5.6 Stripper overhead pressure


The stripper (or lp flash) overhead pressure influences the regeneration of solvent only
slightly. A pressure higher than designed means:
• higher stripper temperature (top and bottom)
• lower driving temperature difference in reboiler
• higher efficiency of solvent heat exchanger
• slightly lower vapor content in stripper overhead
• slightly lower condenser duty
• lower hydraulic load of the column.
A higher stripper overhead pressure leads to a higher temperature difference between rich and
lean solution and consequently to a higher heat transfer rate in the solvent heat exchanger.
The overall effect of a variation of the overhead pressure is rather small.

5.7 Reboiler duty


A higher reboiler duty than designed has the following effects on the system:
• higher energy consumption
• higher stripper overhead temperature
• higher condenser duty
• higher vapor content in stripper overhead
• higher hydraulic load due to higher vapor load of the stripper and consequently higher
liquid load.
A higher vapor load of the stripper can lead to increased entrainment or even flooding. The
hydraulic limits of the column have to be considered.
A higher reboiler duty than designed leads only to a slightly better regeneration of the lean
solvent. Hence, in case of a single stage unit the capacity cannot be raised by increasing the
reboiler duty. However, in a two-stage system, the overall plant capacity can be raised, at
least by a few per cent, by increasing the reboiler duty. This is due to a better regeneration of
the semi-lean solution. The effect is limited because the temperature of the semi-lean solution
increases at the same time.

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5.8 Solution strength


A solution strength higher than the design figure has the following effects:
• increased solution viscosity
• reduced mass transfer properties
• higher solution hold-up in the packing
• higher pressure drop
• weak performance in case of a lack of water.
It is recommended to keep the solution strength within the range given in section 2.2. Within
these limits the effects listed above are rather small. However, it has to be stressed that the
figures as given in section 2.2 are not operational limits. A solution strength of up to
60 %(wt.) or even 65 %(wt.) is possible without major detrimental effects. On the other hand
there is usually no benefit when the solution strength is much higher than the design value.
Above 65 or 70 %(wt.) of total amines the lack of water will lead to decreasing solvent
performance. At any rate it is better to deviate from the target figure to a higher than to a
lower concentration.
A solution strength lower than design has the following effects:
• risk of corrosion due to insufficient passivation
• reduced CO2 loading capacity
• higher solvent circulation rate required
• increased energy consumption
• higher CO2 slip.
A decreasing solution strength not only leads to a lower absorption capacity, but also includes
an increasing corrosion risk due to a falling pH value. This particularly applies to synthesis
gas application where the formation of formic acid is encountered to some extent. Hence, it is
recommended to keep the solution strength higher than 37 %. It is hardly possible to give a
lower limit for a concentration below which corrosion starts. However, the risk increases with
reducing solution strength and becomes particularly evident at concentrations below
30 %(wt.) of total amines.

5.9 Concentration of activator system


A higher content of acitivators means primarily a higher heat requirement for regeneration or
a higher residual CO2 loading of lean solution. Besides this, there is no detrimental effect. On
the other hand, a higher content of activators does not have a positive effect, except for
special cases, e.g. capacity increase of existing units. Hence, a much higher concentration of
the activator system than designed should be avoided.
A low content of activators leads sooner or later to a higher CO2 content in the treated gas.
This indicates an insufficient absorption rate and addition of activators should be considered.
To a certain extent, a low content of activators can be balanced by an increased solution flow
rate.

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67056 Ludwigshafen, Germany Revision 3.0, June 2008

6 Shut-down and de-inventorying procedure

6.1 Measures prior to an inspection


Prior to an inspection or a turnaround of an aMDEA unit the following shut-down procedure
is recommended:
• If the circulating volume of the operating solvent is larger than the storage tank
capacity, it will be necessary to either use an external tank, like a frac tank, or to
concentrate the solvent. : This can be achieved, if prior to the shutdown, feeding
make-up water is stopped and, if applicable, stop recycling overhead condensate to
the regenerator, thus concentrating the aMDEA solvent to a higher strength than
the usual operating figure. Let the levels in the vessels and columns drop as far as
possible. The maximum concentration should not exceed 60 % (wt.) of
amines.Stop the feed gas to the absorber (contactor) and continue to circulate the
solvent at the normal flow rate for 2 to 3 hours. During this time, the stripper
should continue to be operated at the normal operating pressure and temperature to
degas the solvent. This ensures that the absorbed CO2 and /or H2S are removed
from the solvent. During this step, the pressure in the absorber will constantly
decline. First the CO2 and / or H2S will be removed. After that, gases like H2, CO,
N2, and CH4 will be picked up by the solvent. The absorber pressure should be
lowered to below that of the available nitrogen supply as soon a possible. An
appropriate pressure in the absorber has to be maintained preferably by using
nitrogen at a pressure of 3 to 5 bar (g). The nitrogen padding is required for a
couple of reasons.
• To provide sufficient free flow of liquid from the absorber to the stripper
(regenerator).
• As the CO2 and /or H2S are removed from the solvent, the solubilities of other
gases (H2, CO, N2, CH4, for example) will increase. By not removing the process
gas pressure from the absorber the solvent will be loaded up with a flammable
gas. The heating value of the acid off gas will increase and the acid off gas will
even become flammable/explosive.
• This gas will degas from the solution and potentially form an explosive mixture in
the vapor space above the solvent (in the acid off gas or when lead into in the
storage tank), unless that vapor space is sufficiently purged with N2.
• Stop the feed gas, while the solvent is still pumped around for 2 to 3 hours at
process temperature for degassing. Thereby, an appropriate pressure in the
absorber has to be maintained. Preferably, nitrogen at a pressure of 3 to 5 bar (g)
should be used for keeping the absorber pressure. If no natural gas or syngas is
used for maintaining the absorber pressure, the acid off gas will be pure
hydrocarbons or syngas. The heating value of the acid off gas will increase and the
acid off gas will even become flammable/explosive.
• Cool down the solvent by turning off the steam to the reboiler and continue
circulation until the solution leaving the stripper cools to 65°C (150 °F). As the
stripper cools down, it is possible to have backflow of air into the stripper from the

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CO2 and H2S vent line. The use of a nitrogen purge on the stripper at this time
should be considered.
• Drain the aMDEA solvent to the storage tank.
• Wait as long as possible to insure that most of the aMDEA® solution has trickled
off the column internals. Rushing this step will result in higher aMDEA® losses,
so it must be balanced with the time available for the shutdown. Typically, this
can take up to 24 hours to insure low solvent losses. The required time depends on
the type of column internals.
• Before opening the absorber and HP-flash column, flushing with nitrogen is
required to replace flammable gases. This can be accomplished efficiently by
pressurizing the columns 3 times with nitrogen to 3 to 5 bar g (50 psig) and
releasing the pressure afterwards to the flare or to a safe location. The LP-flash
and stripper column do not require flushing with nitrogen, if the solvent circulation
without feed gas during the acid gas degassing of the solvent and cooling down of
the equipment were carried out under nitrogen pressure in the absorber.
• Open the manholes for ventilation and install an air blower for blowing air through
the columns.
• Check for liquid in the vessel sump. If present, drain the bottom section again.
• Make sure that the O2 content inside the vessels is high enough to enter without
breathing apparatus.
• Check for toxic gases such as CO or H2S, where applicable, before entering the
columns.
• In case the treating gas contains H2S, see chapter 6.2 for special precautions
before entering the columns.
• Entry into a confined space must be performed following the plants confined space
entry procedures. The inspection of the equipment can be done following normal
personnel protection measures. Follow the guidelines in the MSDS for exposure to
aMDEA®.
• aMDEA solution is not flammable. Therefore, with regard to the aMDEA solvent,
no special precautions have to be taken for hot work, i.e. welding inside the
columns.
• Obey the safety rules, guidelines and regulations issued for the specific plant.
• In case there will be no opening of equipment or no de-inventorying of the vessels
and no inspecting of the unit, then the shutdown procedure can be reduced to the
required extend.
1. Gas release into storage tank
Make sure that no gas is released into the tank, where it could potentially cause
hazards. It is recommended to flush the columns with nitrogen and to release the
pressure to the flare or a safe location before draining the system. The absorber should
be isolated with block valves, in order to avoid a backflow of solution or gas while the
absorber is under feed gas pressure. This is particularly important when the storage
tank is – contrary to BASF's recommendation - not blanketed with nitrogen. There
have been a number of documented cases of tank explosions due to the back flow of
process gases into a storage tank.
2. Not opening or not de-inventorying the vessels or not inspecting the unit:
The shutdown procedure can be reduced to the required extend.

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