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Author and speaker:
Dr. Torsten Katz, BASF SE, Ludwigshafen Germany
Co‐author
Justin Hearn, BASF SE, Ludwigshafen Germany
Abstract
With its enormous capital demand, the LNG industry acts, by nature, in a conservative
environment. The perception is that a copy/paste approach minimizes the risk in building and
operating LNG units. On the other hand, natural gas compositions change from field to field and
the copy/paste approach in the process selection may lead to severe operational issues. This
paper deals with experiences from selected OASE™ Acid Gas Removal plants (AGRUs), which
condition gases with a low CO2 content as feed stock.
Whether the gas comes from a pipeline grid or from a dedicated field makes a difference to the
performance of the AGRU. Whereas pipeline gases usually have been dehydrated upstream,
they may contain traces of glycols but are low in water content. In contrast, gases coming from
a nearby field are often close to water saturation conditions. These two types of feed gas
sources can cause different operational issues: glycols – even though they may be present only
at ppbv level– will accumulate over time and thus affect the long‐term operability of the unit.
Failure to consider this during the design phase can lead to enormous operational issues. Plants
with too high water ingress, on the other hand, may require water bleeding – which leads to
increased solvent losses. BASF will explain the above effects by some reference experience.
Furthermore, plants with a low CO2 feed gas content can be difficult to operate under partial
load conditions. Increased heavy hydrocarbon co‐absorption can overload the acid off gas flare
system, or cause foaming in the AGRU regenerator. Poor CO2 removal due to too low
temperatures can also be challenging. Properly selected heat exchangers at the right process
locations play a crucial role for successful operation. The conclusion of the paper is a proposal
for an optimized process.
Introduction
The LNG industry faces a broad variety of raw natural gases as feed stock. Besides methane, the
gases contain further valuable components, such as ethane, propane, butane, and other
hydrocarbons including Benzene, Toluene, Ethylbenzene and Xylene (BTEX). However,
unwanted components such as water, nitrogen, carbon dioxide, hydrogen sulfide and other
trace sulfur components are also quite common. Before liquefaction, some conditioning is
required, to purify the gas and to fulfill LNG specifications.
The required conditioning steps depend strongly on the feed gas components, e.g. LNG plants
with H2S as an impurity may need a complete desulfurization package <1>, whereas gases with
CO2 as the only acid gas component do not require such package <2>. Gases which contain
Mercury require a Mercury removal step, those without Mercury may not. For the above
mentioned components, the appropriate process selection set‐up is well accepted in the
industry.
However, for the single process units such as mercury removal, acid gas removal and
liquefaction process there is a tendency to copy/paste designs of plants, which have previously
been built and started up successfully. The perception is that, ideally, modifications are kept at
the lowest level in order to minimize engineering costs and also to satisfy customer’s needs for
selecting proven technology. For the acid gas removal unit, where the CO2 content of the
natural gas shall be brought to the liquefaction specification, typically below 50 ppmv, the most
common plant setup in the industry is shown in Figure 1:
Figure 1: Common OASE® unit setup for acid gas removal in LNG applications
In the Absorber, the Feed gas is counter‐currently brought into contact with the aqueous OASE®
solution at pressures around 50‐70 bara. The OASE® solution reacts with CO2 and removes it in a
quantitative manner down to less than 50 ppmv in the treated gas. In addition to CO2, also a
minor part of other feed gas components are co‐absorbed, some of them are being flashed off
or skimmed off in the Flash vessel, which is usually operated at the fuel gas system pressure of
around 5‐10 bara. Only a minor quantity of CO2 is being released here. The major amount of CO2
is stripped off in the Regenerator column, which usually operates slightly above ambient
pressure. Part of the water in the acid off gas is condensed and recycled back to the unit.
Most of the OASE® units in the LNG industry are using this setup, and it was copied many times.
The question however is: is this also the best setup for treating feed gases with a low CO2
content? Over the past 10 years, more and more gases with a CO2 content lower than 2 vol%
are being liquefied, whereas this was less common in previous years.
Glycol as Feed gas contaminant:
Recently, more LNG plants which take their feed stock from a natural gas pipeline grid, have
been started up, or are under construction. A characteristic of these gases is that they undergo
a first conditioning step close to the production well and prior to feeding the gas to the pipeline
grid. Often glycol units, using e.g. TEG or DEG are being used as a dehydration step to reduce
the water content of the gas to pipeline specification of less than 7 pounds per million cubic
feet. Sind all glycols have a low but measurable vapor pressure, the gas will be glycol saturated
when it enters the pipeline. Depending on summer/winter or day/night temperature shifts, the
temperature of the gas leaving the glycol unit will vary. The higher the temperature at the glycol
unit top, the higher will be the glycol content in the natural gas. Liquid droplet entrainment will
further enhance the glycol content in the pipeline. Since glycol entering the pipeline at the front
end will sooner or later show up in the acid gas removal unit of the downstream LNG plant, this
contaminant must be considered in the design and operation of the LNG plant.
A detailed glycol study at the In Salah sales gas plant in Algeria <3> shows that glycols from the
feed gas – even though it is present at only a 350 ppbv level ‐ will quantitatively accumulate in
the amine unit over time ‐ and will have an impact on the CO2 capture capacity. Since the In
Salah plant has no special glycol pre‐treatment step except for a basic slug catcher and liquid
entrainment prevention prior to sending the gas to the OASE® unit, throughput and
performance of the gas processing plant can only be maintained by intermittent solvent
bleeding and feeding (see Figure 2). At TEG concentrations > 5 wt%, partial solvent replacement
is required to maintain the gas capacity of this plant at the intended level.
Figure 2: TEG accumulation in the In Salah gas plant; measured values vs. total accumulation
due to vapor pressure ingress of TEG (red line)
A more favorable solution would be to install a water scrubber upstream of the CO2 Absorber to
minimize glycol ingress to the acid gas removal plant. Such scrubbers are in operation in various
LNG units and show positive operational experience. A disadvantage of this solution is the
disposal of the glycol‐contaminated wash water.
In recent years, several LNG AGRUs ran into such problems of glycol contamination. In one
extreme case an MEG content of up to 25 wt% in the solution was reported.
Next to dehydration units, glycols can also get into the feedgas, whenever used as hydrate
inhibitor in cold climate conditions, or off‐shore gas production. In these cases, MEG is often
used. Methanol is an alternative hydrate inhibitor, which does not have any detrimental effect
on the OASE® solution. It can be considered as feed gas component in the design phase; it is
possible to reduce its concentration to less than 1 ppmv in the treated gas.
Impact of feed gas water content on the AGRU design:
Contrary to LNG plants with feed gas from the pipeline grid, those plants with gas fields close by
may see a different challenge: often gases are water saturated at the inlet conditions into the
OASE® unit. For these plants, the water balance around the acid gas removal plant and the
downstream dehydration unit, which usually consist out of a cooler and a propane chiller
followed by a mole sieve, must be understood and considered in the design of the AGRU.
For all LNG AGRUs with a low Feed gas CO2 content, it is strongly recommended to recycle the
dehydration unit cooler and chiller condensate to either the HP‐Flash vessel (most common in
the industry) or as shown in Figure 5 to the absorber backwash section. Otherwise, the annual
OASE® solution loss can be as high as 1‐3 times of an initial amine fill volume of the AGRU. If the
dehydration unit water is recycled back to the Absorber backwash section, skimming in the
propane chiller knock out drum is essential (see Figure 5) to avoid heavy hydrocarbon induced
foaming in the Absorber. The installation of backwash trays in the Absorber top is not a must,
but they contribute to further reduction in annual OASE® solution consumption. Recycling of the
mole sieve condensate will not contribute to a reduction of OASE® solution loss, since this
stream is free of amines. But such recycle can further minimize the water make up
requirements.
Figure 3: AGRU water balance for a feed gas with low water content
For feed gases with low water content, this setup allows balancing the incoming and outgoing
water by the make‐up water supply (see Figure 3).
Contrary to this, for plants with water saturated feed gas with low CO2 content – in particular
for gas with a temperature of 20°C or higher –, the recycle of the amine contaminated cooler
and chiller condensate requires a water bleed stream from the system, to match the overall
water balance (see Figure 4). The amine free mole sieve water condensate is usually not
sufficient as water bleed, and an additional water bleed from the process is necessary.
Figure 4: AGRU water balance for a water saturated feed
Such a water bleed, however, has an impact on amine losses, since the water must be bled
either from the propane chiller or from the regenerator condenser reflux loop. Both streams
contain traces of amines (around 1000 ‐25000 ppmwt level, depending on the performance and
design of the backwash sections). To minimize such amine losses, and also to reduce the load on
the waste water treatment plant, BASF recommends the installation of 4‐6 backwash trays in
the regenerator overhead. Figure 5 illustrates the impact of the installed stripper backwash
trays on the relative annual OASE® solution loss.
Figure 5: OASE® solution loss mitigation measures for an AGRU with water saturated feed gas
at 35°C, 1 vol% CO2
Absorber temperature control
The chemisorption reaction of CO2 in the Absorber is an exothermic reaction, i.e. where heat is
released. This heat of reaction leaves the Absorber either with the exiting treated gas, or the
rich amine solution, or with both exiting streams. Since both streams are “competing” to drive
the heat of reaction out of the Absorber, a temperature “bulge” can form. Natural gas AGRUs
with a large amount of CO2 (4 vol% and more) are clearly dominated by the heat capacity
stream (mass flow rate times specific heat capacity) of the OASE® solution and not by the feed
gas. If, however, only small amounts of CO2 have to be removed from the natural gas, relatively
small solvent flow rates are required. As a consequence, the gas flow dominates the
temperatures within the Absorber.
Figure 6 shows how the Absorber temperature profiles for gas‐ and liquid phase change, if the
CO2 content at the inlet gas drops from 2 vol% to 0.2 vol%. It was assumed that the pumps
operate at 100% of the design flow rate for the 2 vol% CO2 case, whereas for the 0.7 and 0.2
vol% CO2 cases, the lower turndown flow rate of 50% was assumed. Feed gas temperature is
8°C.
Figure 6: Absorber temperature profiles for various CO2 feed gas concentrations
The red marked areas in the temperature diagram indicate conditions, where the OASE®
solution can precipitate (see Figure 7).
Figure 7: Precipitation of the OASE® solution at temperatures < 15°C
Such temperatures must be avoided and often require the installation of a feed gas preheater
(see Figure 8). It has to be ensured that the gas entering the Absorber stays above 15°C at all
times – during partial load conditions and also for feed gases with a much lower than design CO2
content, during summer or winter and day or night conditions.
For treating of low CO2‐containing feed gases, the lean solution cooler typically has only a
minor, often negligible, impact on the AGRU operation. This is simply due to the fact that the
heat capacity stream of the OASE® solution for these applications is usually much smaller than
that of the gas flow. If the lean solution cooler is not required for the operating conditions with
the highest CO2 content in the feed gas and the highest gas flow rate, it could be skipped
completely, if not needed for start‐up and turn‐down.
On the other hand, a bypass control around the lean side of the solvent/solvent exchanger (see
Figure 8) is usually necessary. This bypass provides the operational flexibility to ensure that the
lean amine temperature always stays a defined temperature difference above the feed gas
temperature – also during partial load conditions of the plant, or in cases with lower‐than‐
design CO2 content in the feed gas. This point is important in order not to fall below the heavy
hydrocarbon dew point within the absorber.
Minimizing hydrocarbon co‐absorption
Another point, which is special for AGRUs with low CO2 containing feed gas is the handling of co‐
absorbed hydrocarbons. In general, the OASE® solution is designed in a way that the amount of
co‐absorbed hydrocarbons in the Absorber is very low. If a plant is operated close to design
conditions, CO2 purities > 99.4 vol% in the acid off gas (dry basis) can easily be achieved. If,
however, the process is being operated at lower‐than‐design feed gas CO2 content, the solution
will increasingly pick‐up hydrocarbons, which are finally released in the regeneration part of the
plant.
Table 1 shows for two feed gas cases (one with 2 vol% CO2, one with 0.2 vol% CO2), how the
composition of the acid off gas changes:
Table 1: Feed gas and Acid of gas concentrations (dry basis) for two different feed gases
Instead of 99.41 vol% acid off gas purity (Case 1), the lower acid gas containing feed gas (Case 2)
will result in an acid off gas purity of only 95.05 vol%. The consideration is based on the same
overall gas flow rate and a 50% reduced OASE® circulation rate in Case 2. For many plants, this is
the lowest achievable liquid flow rate due to pump constraints. A lower feed gas flow rate, e.g.
during start‐up or shutdown conditions, would increase the co‐absorption effect and lead to
even higher hydrocarbon content in the acid off gas.
A high hydrocarbon co‐absorption and a correspondingly high hydrocarbon content in the acid
off gas has several negative consequences for the plant performance:
The acid off‐gas will have a high caloric value; in the presence of BTEX, BASF customers
already observed the destruction of the flare tips due to too high incineration
temperatures
If BTEX are present, their emissions to atmosphere may reach unacceptable levels and
may violate air permits
Foaming can become an issue; BASF has seen this in several LNG AGRUs, in particular
during partial load conditions. At first glance, this looks somewhat surprising, since the
hydraulic load of the columns is very low under such conditions, but foaming is often
caused by the formation of a liquid hydrocarbon phase.
o Foaming can start in the absorber sump for plants with C6+ components due to
exceeding the liquid/liquid solubility line in the bottom part of the absorber. The
C6+ solubility in the OASE® solution is in the one‐digit ppm‐wt range and over‐
circulation of the amine solution, by e.g. partial load operations, can easily result
in such concentrations.
o Another area, where foaming can start is the regenerator reflux drum: Heavy
hydrocarbons are stripped off by the regenerator and partly condensed in the
condenser. This can lead to a concentration increase of the heavies in the
regenerator reflux loop and may ultimately form an organic liquid layer on top of
the reflux drum. If this layer is not skimmed‐off correctly, it will trigger
periodically severe foaming in the regenerator, which has been observed in a
couple of our reference plants.
In order to mitigate the negative impact of increased hydrocarbon co‐absorption, the following
countermeasures are proposed (see Figure 8):
To reduce the hydrocarbon content in the acid off gas under lower‐than‐design or partial
load conditions, it is important to design the column internals and the pumps with a low
liquid turndown ratio. A/B/C/D pumps are proposed which allow to adjust 25% of the
design liquid flow rate. This measure will have a significant impact on minimizing the co‐
absorbed hydrocarbons. For AGRUs with low CO2 containing gases, this is of particular
importance, since minor absolute reductions in the CO2 content (e.g. from 2 vol% to 1
vol%) in combination with partial gas load of e.g. 50% lead to a total CO2 freight
reduction in the feed gas of 75%. For gases with a higher CO2 feed gas content, this
effect would be much less pronounced.
The flash drum should be operated at elevated temperature. It is therefore
recommended to move the solvent/solvent heat exchange on the rich side partly, or
completely, to a point upstream of the HP‐Flash vessel. The latter one is only possible for
plants with a low CO2 feed gas content. The amount of flash gas, which is released while
heating the rich amine solution is usually very small for such plants. In plants with higher
CO2 feed gas content, the installation of the cross exchanger upstream of the HP‐Flash
drum (rich side) would result in unacceptable CO2 flashing. On top, the above discussed
feed gas heater (as required as a precipitation countermeasure above) also contributes
to an increase in the rich amine solution temperature. BASF uses this setup successfully
in one of its own synthesis gas AGRUs since several years.
The incineration device in the acid off gas line must be capable of handling high
hydrocarbons emissions under all circumstances. Venting of the acid off gas to
atmosphere, with or without inappropriate incineration, is a severe HAZOP concern:
BASF has seen several customers in the sales gas business having explosive incidents:
during partial load operation the explosive composition of the acid off gas was ignited by
lightning, and caused severe damage to the regenerator top internals.
Good hydrocarbon skimming devices in the absorber, the HP‐Flash drum and in the
reflux condenser knock out drum are essential; skimming is only possible if adequate
skimming boxes and level controllers for the aqueous and organic phase are installed.
Figure 8: Plant with optimized heat exchanger set‐up and skimming locations
With these modifications, the hydrocarbon emissions of the acid off gas in the above discussed
plant can be reduced from about 5 vol% (Case 1) to 2.1 vol% (Case 3) as shown in Table 2.
Table 2: Acid off gas concentrations (dry basis) for standard and optimized design at feed gas
conditions according to Case 2 (see Table 1)
The selected measures minimize hydrocarbon losses and ensure that the majority of the co‐
absorbed hydrocarbons are being released with the HP‐Flash gas.
Summary:
For designing and operating LNG AGRUs, which treat low CO2 containing feed gases (< 2 vol%), a
copy/paste approach from plants with higher CO2 content bears certain risks. Depending on the
feed gas source (pipeline gas, dedicated field) traces of glycols or a high water content must be
considered in the design of the absorber and regenerator overhead condenser and backwash
system. This is important to avoid running into operational issues, which ultimately will always
result in high amine make‐up rates. It was also shown that a correct understanding of the
absorber temperature profile under all possible operating conditions including, partial load
cases during start‐up or shutdown, is necessary to avoid precipitation of the OASE ® solution
components. Closely related to this, an improved heat exchanger control concept for the overall
AGRU allows minimizing co‐absorption of hydrocarbons and reduces the risk of hydrocarbon‐
induced foaming.
Literature:
<1> T. Tork, M. Weiss; Natural Gas Sweetening; Hydrocarbon Engineering, May 2003
<2> R. Safruddin; Twenty Year Experience in Controlling Corrosion in Amine Unit of Badak LNG
Plant, 00497 NACE Conference Paper, 2000
<3> T. Katz, G. Sieder, J. Hearn; How Glycols affect the Acid Gas Removal Process, LRGCC
conference proceedings 2013, Oklahoma, US