HIGH PRESSURE GAS SWEETENING WITH AMINES FOR REDUCING CO 2 EMISSIONS

Gelein de Koeijer * , Even Solbraa

Statoil ASA, Research & Technology, N-7005 Trondheim, Norway

ABSTRACT

Natural gas sweetening is currently needed when the CO2 content of the well stream is too high for meeting the customer contract
specifications or transport requirements. But in combination with geological storage, it is also a measure for reducing the global CO2 emissions.
The aim of this article is to present the recent developments on natural gas sweetening with amine solutions for reducing CO2 emissions. During
the last five years, an experimental and modelling effort has been done to better understand and predict the CO2 capture capacity of
alkonolamines at high pressures. First, data of the equilibrium conditions were measured experimentally with real natural gas at the appropriate
pressures and temperatures. Next, these data were used in combination with irreversible thermodynamics and advanced activity models to
establish a model of the plant. Finally, the model was used to give better insight in the CO2 capture plant on the Statoil operated gas platform
Sleipner in the North Sea. Most importantly, it was experimentally observed that pressure has a significant and non-linear effect on the
absorption capacity of the amines. The absorption capacity decreases with increasing pressure at constant CO2 partial pressure or mole fraction.
This is a non-desirable property, and can lead to lack of driving force for CO2 capture in the absorber column. Moreover, mass and heat transfer
behaviour and the effects of several additives to the amine solution were investigated experimentally with real natural gas at the appropriate
pressures and temperatures.

At Sleipner Statoil uses this technology already since 1996. The Statoil operated LNG project Snøhvit in Northern Norway and the
BP-Sonatrach-Statoil operated gas field In Salah in Algeria will follow soon. Until now, all CO2 is stored in an aquifer. But in the case oil and CO2
rich natural gas fields are close together, the captured CO2 could be used for Increased Oil Recovery (IOR). Concluding, natural gas sweetening
is a first global application of capture & storage technology, and a promising technology for further reducing emissions of greenhouse gases in
the near future.

INTRODUCTION

One of the possibilities to stabilize the CO2 emissions is to capture the CO2 from the emission sources, and store it safely in geological
formations, like aquifers and oil & gas reservoirs. Currently large research & development efforts are underway for establishing the technology
needed, e.g. CCP [8] and CO2 Store [9]. An early application of CO2 capture & storage technology is at natural gas sweetening, i.e. removal of the
naturally occurring acid forming gas CO2 (and H2 S). CO2 is mostly removed for reaching the customer defined specification on the calorific
value. The specification varies from region to region. In the North Sea the maximum CO2 content delivered to the customer is 2.5%. But in
Liquefied Natural Gas (LNG) production CO2 need to be removed deeply (max 50 ppmv) in order to enable liquefaction. All CO2 capture
processes from natural gas have in common that the gas customer pays them. So, this makes the CO2 from natural gas sweetening among the
cheapest available for geological storage, together with the CO2 from ammonia and hydrogen production. The financial balance would even be
better if the CO2 could be used for Increased Oil Recovery (IOR).

Since 1996, the Norwegian oil & gas company Statoil operates the world’s first large-scale offshore CO2 capture plant, at which the CO2 is
stored in a nearby aquifer. Moreover, Statoil is operator of the Snøhvit LNG project (Northern Norway) and partner in the jointly operated
BP-Sonatrach-Statoil project in In Salah (Algeria). Both projects will soon apply CO2 capture and storage technology from natural gas [7]. Since
the Sleipner plant was decided to be built offshore on a separate platform, the design and building had several extra challenging constraints.
These constraints led to a low-weight and compact design. The CO2 compression and injection process is described by Baklid et al. [4] and Torp
at al. [13], while this article will focus on the capture. Due to the compact design, it has been demanding to keep a stable operation. But the
specifications were always met by mixing CO2 lean gas from other wells. Statoil Research & Technology started an experimental and modelling
investigation aimed at better understanding and predicting high pressure CO2 capture mechanisms. This work lead to the knowledge and
insight, which has been actively used to obtain stable operation at the Sleipner CO2 capture plant. The aim of this article is to present the recent
developments on CO2 capture from natural gas, based on the above-mentioned research efforts. It involved experiments with genuine natural
gas under realistic pressures and temperatures. One the most important experimental observations was that pressure has a significant effect on
the absorption capacity of the amines – absorption capacity decreases with increasing pressure.

SLEIPNER CO2 CAPTURE PLANT

Natural gas sweetening can be done in several ways. The most common ones are absorption with an alkanolamine or methanol, with and
without activators. At Sleipner an alkanolamine absorption process was chosen, which is schematically illustrated in Figure 1. The total gas
production from the Sleipner West field is typically 22.5 MSm3 /day. The gas from the Sleipner West field has a CO2 content between 4 and 9
mole percent. The absorption process reduces the CO2 content in the natural gas to 2.5%. The CO2 is removed in two parallel absorbers towers
using methyldiethanolamine (MDEA) operating at around 100 bara and 70°C. Afterward, the pressure is reduced in Pelton turbines. The
co-absorbed hydrocarbons and some CO2 are stripped off in the first flash drum, operating at approximately 15 bara and 70°C, and re-circulated
into the natural gas feed. Most of the regeneration of the amine is done in the second flash drum, operating at a pressure between 1.1 and 1.2
bar. 10% of the amine is fully regenerated in an amine stripper column operating at 120°C and 1.0 bar. The Sleipner amine solution is an aqueous
mixture with about 45wt% MDEA. The semi-lean loading (mol CO2 /mol MDEA in the amine sent to the absorbers) varies around 0.3, and the rich
loading around 0.6. No activator is currently added to the amine. The total amine circulation rate varies around 3300 m3 /hour.

HIGH-PRESSURE CO2 CAPTURE FROM NATURAL GAS

Experiments and Model

The CO2 content and hydrocarbon solubility in the amine solution were measured under different operational conditions in a high-pressure
equilibrium cell. Equilibrium properties can be measured with high accuracy up to high pressures (0-600 bar) and temperatures (-50-200°C). The
measurement conditions in this work varied between 1-200 bara and 40-80°C. In recent experiments, fresh amine has been compared to spent
amine (with organic acids/heat stable salts). The addition of an activator to the amine has also been evaluated. Absorption rate (kinetic)
measurements have been performed up to 200 bar pressure in a high-pressure falling film absorber.

The measurements were used for constructing a thermodynamic and kinetic model of a CO2 capture process at high pressures.
Thermodynamic properties were calculated with an electrolyte equation of state. Mass and heat transfer were modelled with the theory of
irreversible thermodynamics. The required amine circulation rate is the dominating factor in the design of an amine plant. A common way to
calculate the required amine circulation rate is the method based on approach to equilibrium. A typically design can be 80% to equilibrium –
which means that the amine loading is 80% compared to the equilibrium value. The equilibrium loading is calculated by a model (e.g. Kent
Eisenberg) or measured in the laboratory. The circulation rate becomes in these common models only a function of the loading. Moreover, most
of the models and experimental data are developed for low-pressure applications, where it is assumed that the equilibrium is only dependent on
the CO2 partial pressure in the gas. In this work, non-equilibrium models were used including the high-pressure effects, and the circulation rate
was a function of pressure, temperature and loading. For more details on the experiments and models we refer to Solbraa [12], Addicks [1] and
Addicks et al [2].

Results of the model

The thermodynamic model developed in this work was used to evaluate the effect of system pressure on the capacity of MDEA solutions. It
was observed that methane has a considerable effect on the fugacity of CO2 in high-pressure natural gas systems. For a given partial pressure of
CO2 in the natural gas, the calculations show a decreased CO2 absorption capacity of aqueous MDEA solutions at increased natural gas system
pressure. In Figure 2 the equilibrium partial pressure of CO2 for a 50wt% MDEA solution at 70°C is given for low and high pressures (0.1-200 bar)
where methane is the inert gas. We see that the equilibrium partial pressure of CO2 in the gas is increased at high system pressures.

Figure 1: Simplified flow diagram of the Sleipner CO2 capture plant

Natural gas
Rich amine
Natural gas
Lean amine
with 2.5% CO 2 Semi-lean amine 95 % CO 2
to customer CO 2 to compression
H2O and injection

Cooler
Natural gas Pump Cooler
with 4 -9 %
CO 2 Absorber
Absorber A B Stripper
Reboiler

Turbine Recycle 2nd flash

drum
1st flash
drum
Heater

2
Figure 2: Partial pressure of CO2 a solution as function of CO2 loading of 50wt% MDEA at 70°C [12].

As can be seen in Figure 2, for a given partial pressure of CO2 , the CO2 capacity of aqueous MDEA solutions will decrease with increased
natural gas system pressure. The decrease in CO2 capturing capacity of the solvent can be evaluated by comparing to the capacity for a
low-pressure system with H2 O and without methane. This has been done in Figure 3 for the same conditions as Figure 2. From the figure we see
that the capacity reduction of the 50wt% MDEA solution at 70°C is significant and non-linear. To illustrate this in another perspective, the four
diamonds give the decreases at the same CO2 mole fraction of 0.05, but at different pressures. The four diamonds show that also with constant
mole fraction the CO2 capturing capacity decreases with increasing pressure. A partial pressure CO2 around 2 bar and a 100 bar total pressure is
an important point, since the CO2 capture specifications are often close to this point. The decrease at this particular point is estimated to be
20%. But we find an even more reduced capacity up to 35% at 200 bara.

Analysis of reaction kinetics was based on data from the high-pressure falling film absorber. The reaction kinetics of CO2 with MDEA was
shown to be relatively unaffected by the total pressure when nitrogen was used as inert gas [1]. However, it was important that the effects of
thermodynamic and kinetic non-ideality in the gas and liquid phase were modelled in a consistent way.
Practical Implications

In a practical situation, the partial pressure of CO2 in the natural gas will be proportional to the total pressure. In these situations we can see
from Figure 2 that the CO2 capturing capacity of the MDEA solution will increase at rising total pressures. However, the increased capacity is
not as large as we would expect from the higher CO2 partial pressure in the gas. Moreover, the increase varies non-linear with the partial
pressure. The pressure effects can be modelled correctly by using suitable thermodynamic models for the liquid and gas phase. However, in
many simulation programs used for amine plant design this effect is not accounted for.

The effect of increased system pressure can lead to a lower driving force for CO2 absorption than we could expect from low-pressure data.
This is illustrated in Figure 4. The equilibrium line will move close to operational line when the system pressure is increased, as indicated by the
arrow. This could in extreme cases lead to situations where the absorber operates close to equilibrium. This will typically happen in the hottest
parts of the absorber. Operation close to equilibrium can lead to unstable operation of the alkanolamine process. The amine circulation rate is
the dominating factor in the design of an amine plant. It is therefore important that this rate is calculated as accurate as possible. A common way
is to use a simple approach-to-equilibrium method, where the selected approach-to-equilibrium can be based on experience. From the above
results it is demonstrated that a simple design based solely on low-pressure data can lead to significant errors. It important to take into account
the high pressure effect which will give a reduced capacity of the amine. The circulation rate found from low-pressure data or models should be
corrected by accurate modelling, as demonstrated in figure 3. A too low circulation rate can lead to a natural gas product inconsistent with the
specifications, and possibly also to instabilities in the operation of the plant.

3
 Experimental data have shown that the addition of an activator to MDEA will have a limited, or even negative effect, on the cyclic capacity of
bulk CO2 removal plants operating at high temperatures and pressures. The positive effects of enhanced capacity and kinetics are often
negligible compared to decreased desorption in flash regeneration. However, for deep CO2 removal with total regeneration of the amine, the
addition of an activator is crucial.

PCO2 Higher
[bara] pressure
Operating line line

Equilibrium

Loading [mol CO 2/mol MDEA]

Figure 3: Relative CO2 removal capacity relative to low-pressure capacity in per cent at high pressures for a 50wt% MDEA solution at 70°C [12].
The diamonds are at constant CO2 mole fraction of 0.05.

Figure 4: The effect of increased system pressure on the operational and the temperature corrected equilibrium line of an alkonolamine process.
DISCUSSION

Sleipner

The thermodynamic model presented in this paper was used to evaluate the operational possibilities for improving the Sleipner CO2 removal
plant. It was shown that the operation was closer to equilibrium than previously thought. Addition of an activator to the Sleipner amine is
questionable, because of the low or possible negative effect on cyclic capacity. Exploiting the Statoil Research Centre’s laboratory facilities has
given insight and experience on how to operate high pressure CO2 capture plants. This has been actively used to obtain stable operation at the
Sleipner CO2 removal plant. The reasons for the negative effect of high-pressure on the amine capacity can be many. The most important
physical phenomena that are known to influence the equilibrium loading at high pressure are:
• The fugacity of CO2 in the gas will influence the equilibrium capacity. At high pressure the fugacity will typically be considerably lower
than the partial pressure of CO2 .
• The pointing correction (molar volume of CO2 in liquid) for CO2 will also influence the amine capacity.
• The solubility of hydrocarbons in the liquid will influence for example the dielectric constant of the amine. Components with high
solubility (e.g. aromatic hydrocarbons) will be the most important.
• All reactants and products will be influenced by the pressure, and consequently influence the CO2 absorption capacity.

Irreversible thermodynamics and advanced equations of state were actively used. This work is a typical example where without the use of these
more complex theories, it would have been not possible to draw the conclusions. The traditional theories were not sufficient anymore to explain
and improve the complex operation of high-pressure CO2 capture processes.

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Snøhvit and In Salah

Sleipner will soon not be the only site where CO2 capture technology is used solely for avoiding CO2 emissions. The Snøhvit and In Salah [7]
projects have already been decided upon and will become operational soon, while more projects are being proposed or announced all over the
world, e.g. the ChevronTexaco operated project on the Gorgon field in Australia, and the Gaz de France operated K12B gas field on the Dutch
sector of the North Sea. They have a lot in common, but also large differences. The local geology, environment, gas composition, specifications
and other constraints lead to different solutions. At Snøhvit, the CO2 will be captured with an MDEA solution, but with 100 % thermal
generation in a stripper. In contrast to the Sleipner plant, an activator will be added to the MDEA solution in order to deeply remove CO2 below
50 ppmv. This activator is needed to overcome the kinetic limitations (which are not present for removal to 2%). Another difference with Sleipner
is that the CO2 is dried with adsorbents before it enters the pipeline. This is done for being 100% sure that corrosion in the pipeline by the
presence of free water is avoided. Since the Sleipner injection equipment sizes were far smaller, they could be made with stainless steel, which
was deemed not possible at Snøhvit. The CO2 will be transported via a 150 km pipeline back to the gas field, where it is injected into an aquifer
(Tubåen formation) below the gas field with a dense caprock in between.

Driscoll et al. [10] describes the CO2 capture plant at In Salah, which is also based on amines. It has some resemblance with the Sleipner plant,
but has no hydrocarbon recycle, and a low-pressure flash drum that is integrated with the stripper. Moreover, cooling is a bigger challenge in
the Algerian desert than at the North Sea. Mostly air-cooling is used in the desert, while more effective seawater cooling can be used at the
North Sea. Similarly to Snøhvit, the CO2 at In Salah will be dried. Glycol drying was chosen for In Salah. The CO2 will be stored in the same
geological structure as the gas, but on a safe distance.

Potential for Increased Oil Recovery

In the case oil and CO2 rich natural gas fields are close together, using the captured CO2 for Increased Oil Recovery (IOR) is an attractive
option, since the extra oil creates extra income. CO2 for IOR could increase the oil recovery significantly, but the amount is dependent on the oil
field [11]. A more detailed study on the CO2 -IOR potential of the Statoil operated Gullfaks field in the North Sea is done by Agustsson at al. [5].
In order to make CO2 from natural gas viable for IOR, the production schedules of the gas field and oil field need to match. Injection of CO2 into
an oil field is regarded to be most productive during the so-called tertiary recovery (primary recovery: natural pressure, secondary recovery:
water flooding), i.e. at the end of the oil field’s lifetime. On the other side, the gas field produces mostly most of its CO2 at the beginning of its
lifetime, i.e. when gas production is highest. So generally speaking, the CO2 production of a new gas field needs to be matched with the CO2
requirement of a relatively old oil field. The most probable way of transporting the CO2 from gas to oilfield are pipelines, see also Berger et al. [6].
Cryogenic ships [5] seem less likely, since it requires more equipment than pipelines for relatively short (offshore-to-offshore) transport.
Furthermore, the oil field and gas field need facilities for exporting and importing CO2 . Finally, the injected CO2 will return partially via the oil
producing wells, and needs to be recycled by re-injection into the oil field. This will require extra equipment. For the moment, the CO2 is stored in
an aquifer at Sleipner, Snøhvit and In Salah. But for future projects with CO2 capture from natural gas, CO2 -IOR could be an option, and possibly
a profitable one.

CONCLUSIONS
High-pressure natural gas sweetening is a first global application of CO2 capture & storage technology, and a promising technology for
further reducing emissions of greenhouse gases in the near future. The main reason is that the CO2 is relatively cheap, and gas fields are near
CO2 storage locations. The Statoil operated gas platform Sleipner uses this technology already since 1996. The Statoil operated LNG project
Snøhvit in Northern Norway and the BP-Sonatrach-Statoil operated gas field In Salah in Algeria will follow soon. All three projects use amine
absorption for the CO2 capture process, but their designs are different due to different composition, gas specifications, surroundings and
geology. For future projects with CO2 capture from natural gas, CO2 -IOR could be an option. This development has formed the basis for
research on this topic at Statoil, which has lead to an increased knowledge and understanding. Summarizing, the following was observed:
• For a given partial pressure CO2 or mole fraction, the capacity of MDEA solutions is lowered at increasing pressures. The capacity
reduction is non-linear and can be 20% at 100 bara total pressure
• For a specified natural gas, the capacity of MDEA solutions will increase with increasing gas stream pressures. This increase is not as
high as we would expect from only consideration of the increased partial pressure of CO2 .
• The reaction kinetics is not considerably affected by the total pressure
These observations can have considerable implications for the design and operation of high-pressure CO2 capture plants.
ACKNOWLEDGEMENTS

Statoil ASA is thanked for giving Gelein de Koeijer and Even Solbraa the possibility to write this article.

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