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DEG
Regeneration
Train-A
Inlet
Separator
AGRU
(CO2 removal)
Inlet Manifold
Dew Point
Control
Dehydration
CO2
Sales
Gas
to P/L
HC Liquid
CO2 to Atmosphere
Incineration
Stabilizer
Refrigerant
DEG solution
HC Liquid
Raw
Natural
Gas
Refrigeration
Recycle gas
Train-B
Train-C
NGL
Product
to export
48 m
5k
45
Krechba
CNDG
Gas Network
Phase 1 (2004)
Hassi RMel
Compression
Field Facility
Central Processing
Facility
38
60 km
24
13 km
Teg
24
62 km
Reg
Hassi
Moumene
Phase 2 (future)
In Salah
Garet el
Befinat
Gour
Mahmoud
Molecular mass
MEG
62.07 g/mol
197C, 387 F
16.9 cP
DEG
106.12 g/mol
244C; 471 F
35.7 cP
TEG
150.17 g/mol
285C; 545 F
49.0 cP
Due to its higher boiling point, TEG can be more easily regenerated to a higher purity, and hence achieves
better water removal and lower dew point than either DEG or MEG. A disadvantage of TEG is its higher
viscosity, which can make liquid handling in plants under low temperature conditions very difficult. In these
applications, DEG is the preferred glycol. The setup of a glycol dehydration plant looks as follows:
Case 2
CO2
9.62 vol%
1.75
N2
0.76 vol%
0.50
CH4
81.3 vol%
96.05
C2H6
6.10 vol%
1.30
C3+
2.14 vol%
0.40
H2O
varies
varies
25C
40C
77F
104F
59 bara
50 bara
856 psia
725 psia
Case 1 represents a CO2-rich gas, which is also rich in C2 and C3+ components, whereas Case 2 represents
a leaner gas, coming from a pipeline.
Figure 5 shows the glycol saturation concentration over the temperature range for gases with compositions
according to Case 1 and Case 2 for pressures of 50 and 70 bara (725 and 1015 psi). The values have been
determined by using the commercially available software Multi-Flash7 by using the cubic equation of state PR
(advanced). Even though the gases are quite different with respect to acid gas content and heavy
hydrocarbon content, neither of these two parameters has a substantial impact on the glycol solubility, at least
not for typical LNG feed gas conditions.
5
32F
100000
MEG
10000
DEG
1000
100
TEG
10
1
140F
104F
68F
10
20
30
40
temperature [C]
50
60
Figure 6: Comparison of the In Salah glycol built up with results according to Figure 5
The significantly higher ingress rate for Train 1 in December 2008 may be explained by additional entrainment
of liquid glycol droplets into the unit.
4. HOW GLYCOLS AFFECT THE PERFORMANCE OF AGRUS
If the glycol-contaminated gas is fed to an AGRU, traces of glycols also get into these units. In order to decide
whether or not glycols affect the performance of an AGRU, BASF made lab measurements with a 45 wt%
OASE purple solution by adding 15 wt% MEG, DEG or TEG .
As Figure 7 shows, glycols have a negative impact on the maximum (= equilibrium) CO2 capture capacity of
the solvent. For a given CO2 partial pressure (pCO2) in the gas phase, the measured CO2 equilibrium loadings
(Loading CO2) in the OASE solution are lower in the presence of glycols than for the glycol free solution.
Glycols replace water from the system, one of the major CO2 capture reaction components, and thereby
move the equilibrium of the bicarbonate formation reaction towards the un-protonated (left) side as shown for
the example of an MDEA containing solution:
MDEA + CO2 + H2O MDEAH+ + HCO3This leads to a reduced CO2 capture capacity.
p CO2
+ 15 wt% TEG
+ 15 wt% DEG
+ 15 wt% MEG
OASE
+ 15 wt%TEG
Viscosity
+ 15 wt%DEG
+ 15 wt% MEG
OASE
Temperature [C]
Figure 8: Impact of glycols on solution viscosity and temperature
The implementation of the measured equilibrium and viscosity data into BASFs in-house simulation tool
Chemasim allows us simulating the OASE process in the presence of glycols. In addition to the CO2 loading
and viscosity the model was updated for all other required physical properties (density, surface tension etc.)
as well as for the enthalpy model taking the impact of the glycols into account.
5. CASE STUDY
To estimate the impact of glycols on the performance of a full absorption/desorption process, AGRUs with
LNG spec (50 ppmv CO2 slip at the absorber overhead) according to Case 1 and Case 2 (Table 2) were
simulated. Simplified flow schemes of the two plants are shown in Figure 9 and Figure 10:
Figure 11: Absorber liquid temperature and CO2 gas phase concentration
profiles in presence of MEG for Case 1 (CO2-rich gas) conditions
With increasing MEG content, the liquid temperature and the CO2 gas phase profile move upwards, indicating
that eventually the CO2 will break through. The plant is capable of dealing with MEG concentrations in the
solution loop of up to 9.2 wt%. If MEG accumulates to higher values, the plant no longer meets its CO2 spec
as shown by the CO2 breakthrough curve for MEG-contaminated amine in Figure 12, left hand side.
Figure 12: Case 1 (CO2-rich gas) breakthrough curves and corresponding glycol content in feed gas
The temperature and CO2 concentration profiles of DEG and TEG-contaminated amine solutions for the Case
1 study show similar characteristics as for MEG. CO2 breakthrough however, already occurs at 8 wt% for
DEG and 7.4 wt% for TEG, as show in Figure 12 (left hand side), too.
On the right hand side, Figure 12 shows the glycol feed gas concentrations which cause accumulation of the
different glycols in the solution. In order to avoid CO2 breakthrough, glycol concentrations in the feed gas
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have to stay below 350 ppbv (MEG), 19 ppbv (DEG) or 2.3 ppbv (TEG). Any higher glycol content in the feed
gas will lead to CO2 breakthrough over the long term.
Figure 11 and Figure 12 present the results of the Case 2 study (low CO2 content in feed gas). Changes in
the temperature profile for MEG-contaminated OASE solution are less distinct; the impact on the CO2 profile
however is still significant. The plant already produces off-spec CO2 above 3 wt% of MEG in the OASE
solution.
Figure 13: Absorber liquid temperature and CO2 gas phase concentration profiles in
presence of MEG for Case 2 (CO2-lean gas) conditions
Interestingly, there is no difference in the maximum acceptable glycol content in the amine solution (Figure
14) for all types of glycols. This goes back to the viscosity-increasing effects of the glycols, which for higher
temperatures in the range of 60 to 90C (140F 194F) affect the mass transfer almost equally for all three
glycol types (see Figure 8).
Figure 14: Case 2 (CO2-lean gas) breakthrough curves and corresponding glycol content in feed gas
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The maximum acceptable glycol contents in the feed gas are 280 ppbv (MEG), 210 ppbv (DEG) and 53 ppbv
(TEG).
A further comparison between Case 1 (CO2-rich gas) and Case 2 (CO2-lean gas) shows that a potential DEG
or TEG contamination of the feed gas is more severe for the CO2-rich gas. This can be explained by a
discussion of the temperature profiles: For Case 1 (CO2-rich gas) the treated gas outlet temperature almost
equals the lean amine inlet temperature into the absorber. Thus the treated gas is relatively cold and does not
allow significant quantities of glycols to be emitted. However, Case 2 (CO2-lean gas) has a temperature bulge
in the top of the absorber column and the heat of the CO2 absorption-reaction leads to a strong increase of
the exiting gas phase temperatures compared to the incoming lean amine temperature. This causes higher
glycol vapor-pressure losses thus the plant can accept higher glycol content in the feed gas than applications
with higher CO2 content in the feed gas (Case 1).
The combination of the maximum allowable glycol content in the feed gas, according to the heat and mass
balances of Case 1 and Case 2 (Figure 12 and Figure 14), with the glycol vapor pressure of the feed gases
(Figure 5) allows for the determination of the maximum temperature under which a DEG or TEG unit, or MEG
injection, can be operated (or more precisely: where the glycol dewpoint of the incoming feed gas into the
AGRU absorber lies) without causing production of off-spec CO2.
Figure 15: Maximum glycol dewpoint temperature for AGRU absorber feed gas
Figure 15 shows that the following:
A gas according to Case 1 (CO2-rich gas) must have a DEG dewpoint of < 1C/34F or TEG dewpoint
of < 4C/39F, without causing production of off-spec. treated gas in the AGRU.
A gas according to Case 2 (CO2-lean gas) can have a DEG dewpoint of < 20C/86F or TEG dewpoint
of < 35C/95F, without causing production of off-spec. treated gas in the AGRU.
MEG treatment of the gas upstream the AGRU absorber will cause off-spec production for Case 1 and
Case 2 for relevant MEG dewpoint temperatures > 0C / 32F.
To treat gases with glycol dewpoint temperatures above the values according to FIGURE 15, additional glycol
mitigation measures are necessary to allow production of on-spec CO2 in the long term.
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Figure 17: Performance of the removal of MEG (1 ppmv in feed gas) for Case1 using a water wash
Option 7:
Another option to avoid getting glycols into amine operated AGRUs is to replace them by alternative
processes. Instead of MEG, methanol offers an alternative, which due to its lower boiling point is much easier
to handle in an AGRU than MEG. In other applications, glycols have been replaced by adsorption processes
operating with silica gels such as Sorbead. Next to dehydration, they also allow recovering natural gas
liquids (NGL), which for some applications increases their attractiveness. They also facilitate the operation of
pipelines, since glycol fouling is not an issue any more.
7. SUMMARY
Glycols in natural gas applications are widely used for hydrate suppression or dehydration purposes. Even
though they have relatively low vapor pressures, traces of glycols will end up in the natural gas. Gas phase
concentrations between several ppbv up to several hundred ppmv are possible. The use of demisters can
only reduce liquid entrainment of glycols into the natural gas. Gas phase losses, however, will always
contribute significantly to the overall glycol losses.
In most natural gas applications, glycols are being used downstream of AGRUs, some companies however
operate glycol units upstream of AGURs. For these applications it is important to know the glycol dewpoint of
the natural gas at the AGRU inlet in order to determine the absolute glycol ingress to the amine units. Major
quantities of the incoming glycols will accumulate in the amine units up to significant concentrations (> 15
wt%), since glycols are heavy boiling components and do not easily leave the system. They have a negative
impact on the acid gas capture capacity and on the absorption kinetics and thus may limit the treatment
capacity of a natural gas conditioning plant.
To mitigate the effects of glycols, several countermeasures are possible. These range from accepting
glycols in the feed to the AGRU and considering extra design margins to the AGRU, bleeding part of the
glycol-containing solvent or avoiding significant glycol ingress to the units. This can be done either by
applying a water-wash step upstream of the AGRU or by replacing glycol processes by alternatives, such as
methanol (hydrate inhibition) or silica gels (dehydration). Reclaiming of glycol contaminated amine is another
possible but costly mean.
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In any case, the knowledge that the natural gas to be treated in an AGRU will contain glycols, requires
adequate glycol mitigation measures to avoid running into operational surprises, once the AGRU is in
operation for several years.
REFERENCES
1. NaturalGas.Org: http://www.naturalgas.org/naturalgas/processing_ng.asp
2. Tanaka K., Fujimura Y., Katz T., Spuhl O.: HiPACT Advanced CO2 capture technology for green
natural gas exploration; LRGCC conference proceedings 2010
3. Schroeter R.W. et al.: Investigation Considerations on CO2 Removal at the In Salah Gas Plant
HiPACT ; LRGCC conference proceedings 2012
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