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Processes
J.M. Klinkenbijl
M.L.Dillon
E.C. Heyman
Shell International Oil Products
Research & Technology Centre Amsterdam
Presented at
GPA Nashville TE meeting
2nd March 1999
Summary
Natural gas generally requires removal of H2S, CO2, COS, organic sulphur compounds, mercury and
water prior to liquefaction in order to meet product specifications, avoid blockages and to prevent
damage to process equipment. The cost of pre-treatment is dependent on the type and
concentrations of the contaminants in the natural gas.
Most of the operational base load LNG plants process feed gases with only low concentrations of
CO2, mercury and water as contaminants. This type of gas requires the ‘minimum’ of treating, often
comprising of a CO2 removal unit, molecular sieves for drying and a carbon bed for mercury
removal.
The Shell Sulfinol process is the most widely applied acid gas removal process, serving some 40%
of the installed base load LNG capacity, and has proven to be very reliable and cost effective.
When mercaptans are present in gas feed, the Shell Sulfinol process is strongly preferred as the
acid gas removal step, since it combines total CO2 and H2S removal with mercaptan removal up to
97%. Formulated MDEA solvents have a comparable capital cost to Sulfinol, but lack the
mercaptan removal capabilities, with one exception being the Flexsorb formulation (from Exxon)
also containing sulfolane. Revamp of a gas pre-treatment unit from limited mercaptan handling
capability to significant mercaptan handling capability can elegantly be done using an integrated
Sulfinol based concept.
The relative capital investment for acid gas removal in a LNG plant increases significantly with
increasing CO2 content. At 2 mol% CO2 the acid gas unit represents 6% of the processing
equipment cost but at 14 mol% CO2 it represents 15% of the processing equipment cost. The
capital cost for dehydration and mercury removal depend mainly on the natural gas throughput.
New developments such as membrane technologies are starting to be considered as an option for
bulk removal of CO2 but solvent absorption remains the only cost effective treatment process for
meeting LNG specifications. Further developments may change this in the future.
3. Liquefaction Pre-Treatment
3.1. Introduction
Pre-treatment upstream a liquefaction unit traditionally consists of an acid gas removal step, in
which CO2 and sulphur compounds (H2S, COS and mercaptans) are removed, a dehydration step
and a mercury removal step. Where there are limitations on the SO 2 emissions, the removed sulphur
components are recovered as elemental sulphur. Environmental limitations to hydrocarbon
emissions can require incineration of CO2 acid gas even in the absence of sulphur compounds.
Figure 1 shows a typical block diagram of a base load LNG train. The mercury removal step can be
positioned upstream of the acid gas removal or downstream of the dehydration step.
F e e d G a s S u p p l y
G a s R e c e i v i n g
& M e t e r i n g
C O 2
M e r c u r y S O 2
R e m o v a l I n c i n e r a t i o n
A c i d G a s S u l p h u r
R e m o v a l R e c o v e r y
F u e l g a s
S u l p h u r D i s p o s a l
D e h y d r a t i o n
U tilities
* H T F M e r c u r y
R e m o v a l
* Electricity
* W a t e r P r e - T r e a t m e n t S e c t i o n
* N i t r o g e n
H y d r o c a r b o n F r a c t i o n a t i o n
S e p a r a t i o n
L i q u e f a c t i o n N G L T r e a t m e n t
L N G S t o r a g e N G L S t o r a g e
L N G S h i p p i n g N G L P r o d u c t s
1000000
15
100000
ton
su
Amine + Claus ( + SCOT)
Eff lph
ect ur
so /d
f re ay
5t cove
on ry, t
sul urn
H2S concentration (ppmv)
ph dow
ur na
10000 /d nd
ay CO
2
100 SulFerox or
kg
Eff sul
1000
ect
s of
ph
ur Shell
wa /d
50
k ter
sa
ay Thiopaq
gs tur
ulp ati
hu on
r/
day
100
Disposable solids
and liquids Amine+SulFerox
or Thiopaq
10
0.01 0.1 1 10 100
Gas Flow (MMNm3/day)
typical base load LNG plants
3.6 Incineration
If the acid gas removal off-gas only contains CO2 it can be vented, however if H2S and/or
aromatics are present, even in small amounts, the gas must be sent to an incinerator to prevent
unsafe situations. The incinerator is normally of the thermal type, operating at about 800 oC, to
achieve nearly complete H2S combustion (< 10 ppmv). If a Claus and/or SCOT unit are used the
tail gas must also be incinerated. Modern adsorption materials also present the possibility of
removing low levels of H2S by fixed beds where it is permitted to vent the balance of the acid gas
stream.
An interesting recent development is the option of using the hydrocarbon containing CO2 off-gas as
fuel in steam boilers or furnaces. This concept can eliminate the need for an incinerator or allow for
a considerably smaller incineration unit.
With the increasing emphasis on reduction of greenhouse gas emission the option of acid gas re-
compression and subsequent re-injection is now being considered.
4. Cost
4.1. Introduction
The capital investment of a treating scheme is, of course, dependent on the type and concentrations
of the contaminants in the feed gas and environmental targets.
The costs of the dehydration and the mercury removal steps are mainly dependent on the gas
throughput. The water content of the feed gas to the dehydration unit will not vary significantly if
upstream cooling is applied to say about 20 oC. Dehydration can be significantly cheaper if a non-
aqueous solvent can be used. The size of the mercury removal bed is mainly determined by contact
time and hence throughput.
The H2S, CO2 and mercaptan content of the gas will greatly influence the cost of the acid gas
removal and the sulphur recovery units. Apart from the capital investment, the energy consumption,
In previous work [1] the conclusion was drawn that for large gas volumes containing less than 15-
20 mol% CO2 the Sulfinol process was more economical than pure physical processes.
Since 1996 several cases have been studied for the comparison of Sulfinol-D with alternative amine
processes. The alternative processes comprise a representative modified MDEA solvent and an
alternative mixed solvent. Results are shown below.
120
100
Relative costs
80
Capex
60
Opex
40
20
0
Alt Alt Sulfinol-
MDEA mixed D
solvent
120
100
Relative costs
80
Capex
60 Opex
40
20
0
Alt Alt Sulfinol-
MDEA mixed D
solvent
The formulated MDEA process figure is based on the most competitive MDEA based process as
determined by recently completed process comparison studies.
In the selection of the most attractive process, uncertainties in feed gas compositions (e.g. level of
sulphur) and future requirements can often shape the ultimate choice.
4.3. Feed Gas with H 2S, CO2 and Organic Sulphur Components
If, as in some recent projects, H2S and organic sulphur compounds are present in the feed gas to the
LNG plant the cost of the gas pre-treatment can increase significantly. Where organic sulphur
components are present, the Sulfinol process is often the preferred process as it combines H2S,
CO2, COS and mercaptans removal in one step. This cannot be achieved with aqueous amines. In
recent years this approach has been applied in the Shell Caroline plant [10], the Sexsmith gas plant
[9] and the Qatargas LNG plant [13]. If the H2S and CO2 content of the feed gas is high, the
mercaptans are removed without any additional cost. Only where the H2S and CO2 concentrations
are low, will mercaptans removal determine the size of the acid gas removal unit.
If there are restrictions on the SO 2 emissions, a sulphur recovery step is required. From figure 2 it
can be concluded that above about 500 ppmv H2S in the feed gas, a Claus unit is almost the
automatic choice. For a project producing 3 mtpa LNG, with 2 mol% CO2 and 2 mol% H2S in the
feed, the sulphur production is about 400 t/d. In this case the cost of the Claus unit is similar to the
cost of the acid gas removal unit. If the SO 2 emission limit cannot be met with just a Claus unit , a
SCOT unit can be used to improve the sulphur recovery efficiency to 99.9%. This will obviously
increase the overall cost. As a bonus the steam generated by the Claus unit may be sufficient to
make the total treating scheme almost self-supporting with respect to energy consumption.
As explained before in chapter 3, the cost of a Claus unit increases with decreasing H2S content of
the acid gas feed. Figure 3 gives an impression of the capital cost of a sulphur recovery unit as
function of the H2S content of the feed [2]. H2S enrichment of the Claus feed gas can be
economical, especially if the enrichment is combined with a SCOT unit. The enrichment absorber
and the SCOT absorber then share the same regenerator and solvent cascading is possible. This
type of enrichment scheme will be applied in a new LNG project. Other enrichment schemes have
been discussed before [2] and have been applied in e.g. the NAM Emmen Sulfinol-M plant [11].
It is very important for these applications that already in an early stage a good feed characterisation
is made. The lowest foreseen H2S/CO2 ratio in the feed gas and the mercaptan content are critical
to the final process selection [9] and developing the most cost effective design.
1.8
1.6
1.5
1.4
1.3
1.2
1.1
1
0 10 20 30 40 50 60 70 80 90 100
% H2S in feed to Claus unit
Figure 3. Effect of H2S content of Claus feed on the relative cost of a Claus plant.
To illustrate the effect of H2S on the costs of a pre-treating section, the example represented in
table 2 has been used with the addition of a 90 t/sd sulphur removal requirement. The adaptations in
the line-up foresee in an enrichment section and a sulphur recovery unit. In view of expected
environmental constraints a 99.9 % sulphur recovery has been taken in account. The results are
represented in table 3.
Table 3. Capital cost of the pre-treatment section relative to the total cost of the processing units for
a typical LNG train (~3 mtpa LNG) with the addition of 90 t/d H2S removal capacity.
2 % CO 2 in feed 11 % CO 2 in feed 14 % CO 2 in feed
Mercury Removal (%) 1.1 0.8 0.8
Dehydration (%) 4.3 3.3 3.3
H 2 S/CO 2 removal unit (%) 10.5 17.7 19.3
Comparing table 2 and 3 leads to the conclusion that the cost share for the gas treating step
substantially increases with the addition of H2S removal capacity. Contributing factors are the need
for enrichment (in this example) and the sulphur recovery.
The effect of H2S removal on the gas treating processes is illustrated below for a typical aqueous
MDEA (Adip) solvent and a mixed solvent. It should be realised that again the feed gas composition
is of major importance.
120
100
Relative costs
80
Capex
60
Opex
40
20
0
Alt mixed Aqueous
solvent MDEA
200
180
160
Relative costs
140
120 Capex
100
80 Opex
60
40
20
0
Alt mixed Aqueous Alt mixed Aqueous
solvent MDEA solvent + MDEA +
enrichment enrichment
5. Developments in Pre-Treatment
Membrane separation is based on thin barriers which allow preferential passage of components to
separate multi-component feeds. The driving force for permeation is the difference in partial
pressure between the feed gas and the permeate side of the membrane. Selectivity is achieved by
differences is permeation rates. Membrane units for natural gas processing are commercially being
used for CO2 / H2O removal to pipeline specification [15], production of CO2 for Enhanced Oil
Recovery (EOR), unloading of existing treating plants, concentration of natural gas liquids.
The use of membranes in large volume natural gas applications for e.g. CO2 removal is still
restricted by the relatively high hydrocarbon losses and the fact that membranes do not have the
same economy of scale as many other processes due to their modular nature. Current developments
are therefore in improved permeance, reducing the required membrane area, and in improved
CH4/CO2 selectivity to further reduce the hydrocarbon losses with the permeate. Inorganic
membranes are an example of recent developments in this area [7].
Membranes can be economically used in the bulk CO2 removal step for natural gases containing
high concentrations of CO2. Amine processes using partial flash regeneration, such as Sulfinol-M or
MDEA, are the most economical solution for large volumes of natural gas containing less than about
15 mol% CO2 [6]. Above 15 mol%, a bulk CO2 removal step upstream of the amine unit can be
attractive. Membranes can also be attractive for debottlenecking of existing CO2 removal plants, as
long as the permeate can be used as fuel.
Another area of interest is the use of membrane technology for LNG floaters, where movement can
be significant. A disadvantage of conventional technology is that the internals, such as acid gas
absorber trays and packing are sensitive to movements [8]. Several research institutes, such as GRI
(USA) and TNO (Netherlands), are developing membrane alternatives for absorber trays, which
are less sensitive to movement. An added advantage of the membrane contactor is the reduction of
heavy hydrocarbon co-absorption, while the absence of direct gas-solvent contact removes the risk
of foaming.
6. Technology Selection
Simple rules for the selection of the most effective LNG pre-treatment technology are difficult to
arrive at given the array of possibilities in feed gas conditions and resultant requirements for one or
7. Conclusion
Up until recently the levels of CO2 and sulphur encountered in most LNG developments have
allowed a fairly open selection of solvent based pre-treatment technology although preference has
most often been given to well proven technologies. However with increased sulphur levels,
mercaptans and more extreme operating requirements the available choices for a cost effective
integrated treating package narrow dramatically. Use of the Shell Sulfinol technology can be the
decidedly more attractive option in these cases. It is critical that each new gas development undergo
a rigorous selection study to identify the most cost effective and fit for purpose treating package.
8. References
[1] Klein, J.P., Verloop, J., The purification of Natural Gas prior to liquefaction, Paper presented at the Second Iranian
Congress of Chemical Engineering, Tehran, 11th-14th May 1975
[2] McEwan, M.C., Marmin, A., Developments in LNG Treating, Proceedings of LNG-6 Kyoto April 1980 Vol.II Appendix
Paper 3.
[3] Peebles, M.W.H., Natural Gas Fundamentals, Shell International Gas Limited, 1992
[4] Avidan, A.A., et al., LNG links remote supplies and markets, Oil & Gas Journal, June 1997,pp 54-59
[5] Bellow, E.J., et al., Technology advances keeping LNG cost-competitive, Oil & Gas Journal, June 1997, pp 74-78.
[6] McKee, R.I., et al., CO2 removal: membrane plus amine, Hydrocarbon Processes, April 1991, pp 63-65
[7] Minutes Gas Utilisation Research Forum, June 1997, Copenhagen, Denmark.
[8] Naklie, M..M., Design advanced for large-scale economic, floating LNG plant, Oil & Gas Journal, June 1997, pp 66-69
[9] Johnston, A.L., Moore, B.K., Balancing cost with process, resident and regulatory needs, Laurence Reid Gas Conditioning
Conference paper, March 1997.
[10] Cheng, N. et al., Shell Canada’s Caroline Gas Plant reaches smooth operation, Laurence Reid Gas Conditioning
Conference paper, March 1997
[11] Taylor, N.A., et al., Gas-desulfurisation plant handles wide range of sour gas compositions, Oil & Gas Journal, August
1991, pp 57-59
[12] Wetzels, M.L.J.A., et al., The SCOT Process: still very much alive nearly twenty years after its first introduction,
Western Research Seminar, November 1990, Budapest.
[13] Oil & Gas Special: Natural gas in the Middle East, February 1997, pp 49-64
[14] Holmes, E.S. et al., Process Improvements in acid gas and mercury removal, AIChE 1994 Spring National Meeting,
Atlanta, April 1994
[15] Cook, P.J., Losin, M.S., Membranes provide cost-effective natural gas processing, Hydrocarbon Processing, April 1995,
pp 79-84
[16] Abdul Redha Abdul Rahman, Qatar Liquefied Gas Co., Doha, Qatar & Masayuki Ishikura, Chiyoda Corp., Yokohama,
Japan, 1’LNG from giant North field: Qatar Gas LNG, 1998 presented LNG 12 conference, Perth, May 1998
[17] Clarke D.S., Sibal P.W., Gas Treating Alternatives for LNG Plants, GPA, March 16-18, 1998, Dallas Texas