IPTC-18732-MS

A Technical Evaluation of Hybrid Membrane-Absorption Processes for Acid

Gas Removal

Michael Sclierf, Technischen Universität Müchen and The University of Queensland; Thomas E. Rufford, The
University of Queensland

Copyright 2016, International Petroleum Technology Conference

This paper was prepared for presentation at the International Petroleum Technology Conference held in Bangkok, Thailand, 14-16 November 2016.

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Abstract
This paper assesses two possible acid gas removal processes for CO2 removal onboard a floating LNG
facility: (1) the well-established amine absorption process, and (2) a membrane/amine absorption hybrid
process. The assessment considers process and economic aspects as well as sizing due to the on-board
application.
Process simulation models of each of the systems were developed in the Aspen Hysys (V8.6) software
package. Two different gas fields are assumed with Feed1 containing 10%/0% CO2/H2S and with Feed2
50%/1% CO2/H2S. The feed rate in each scenario was 590,000 Nm3/h and the sweet gas specification was
50 ppm CO2 and 4 ppm H2S. The amine absorption process modelled as the base case was a 50% MDEA
solution. The hybrid membrane/amine process featured a polymeric membrane unit implemented as a sub-
flowsheet and then the amine unit.
Our results suggest that for a very sour gas feed there may be advantages with a hybrid membrane/amine
process that allows the plant weight to be reduced by 80%, volume by 50%, investment costs by 70% and
annual operation costs by 40%. The most important disadvantage concerning the hybrid process is the high
methane slip which can be reduced by further development of membrane properties and process design.
The participation of the membrane unit increases generally with the percentage of acid gas in the feed. If the
boundary conditions are comparable to those used in this paper, it can be stated that the CO2 concentration
should be at least 10% for a proficient application of a hybrid process.
This study presents models to evaluate novel acid gas removal processes and describes suitable process
metrics that could be considered for floating LNG production facilities.
Key Words: acid gas removal, sour natural gas, membrane, hybrid process, floating LNG

Introduction
The development of sour unconventional and remote natural gas reserves can present new challenges to acid
gas removal that may require more efficient processes than conventional amine absorption technologies
2 IPTC-18732-MS

(Rufford et al. 2012). For example, if the gas field is located far from the mainland, as is the case for some
petroleum reserves off Australia’s north western coast, new technologies such as floating liquefied natural
gas (FLNG) that don’t require pipelines to shore or on-shore process plants may be the only economically
viable development option. Shell’s Prelude is one such project currently in development. The design of
FLNG plants introduces new challenges for acid gas removal units (AGRU) that may provide opportunities
for innovation to reduce the weight, footprint and energy consumption of AGRUs. For FLNG plants there
may also more stringent safety requirements than for an on-shore processing plant (Chan, Eaton, and
Buckles 2007).
In this paper we evaluated the potential of a hybrid membrane and amine absorption process for
deployment on FLNG for very sour natural gas feeds. Two gas feed scenarios were considered based on the
study by Roussanaly, Anantharaman, and Lindqvist (2014): a 10 % mole CO2 feed and a 50 % mole CO2
(see Table 1 for stream compositions and conditions).

Table 1—Feed compositions and conditions of two hypothetical natural gas streams with high CO2 concentrations.

Feed 1 Feed 2

Feed compositions in mole %

Methane 83 41
Ethane 5 4.5
Propane 2 3.5
CO2 10 50
H2S 0 1
H2O 0 0
N2 0 0

Feed properties

Temperature in °C 40 40

Pressure in bar 70 70

Volume flow in Nm /h3

590,000 590,000

Molar flow in kmol/h 24,950 24,950

Figure 1 indicates the two processes considered in this study: Case A the base case amine MDEA
absorption process and Case H the hybrid membrane-amine absorption process. The objective of each
process investigated was to purify the same feed gas properties to satisfy the LNG specifications of less
than 50 ppmv CO2 and less 4 ppmv H2S than. The scope of this study is limited to the acid gas removal
unit only and we do not consider the energy or equipment requirements of other units such as dehydration
units downstream of the acid gas removal unit.
IPTC-18732-MS 3

Figure 1—Illustration of two acid gas removal processes studied in this research project. The base case is a conventional
MDEA absorption process. The alternative reported in this paper is a hybrid polymeric mebrane-MDEA absorption process.

Methods
The base case methyl-di-ethanolamine (MDEA) process flowsheet was developed from the Aspen Hysys
V8.6 acid gas removal unit tutorial. The absorber column was modelled as a packed column. For each feed
scenario an optimization of the process conditions and equipment parameters was performed to minimize
energy usage and equipment costs. A summary of the optimized base case for the 10 % CO2 and 50 % CO2
feeds is shown in Table 2.

Table 2—Optimized parameters for Base Case MDEA process in each feed scenario

Feed 1 Feed 2

CO2 mole % 10 50
Base case Hybrid Base Case Hybrid
3
Solvent rate, m /h 1258 1160 4105 1360

Column diameter, m 10 10 15 10
Reboiler duty factor, Btu/gallean solvent 880 880 880 880
Number of stripper stages 7 7 7 7
Feed stage in stripper 1 1 2 2

In the hybrid process flow sheet the membrane separation unit was designed upstream of the amine
absorption unit. The membrane in this study is a cellulose acetate membrane which is the most commonly
used membrane for acid gas removal in the industry (Niu and Rangaiah 2014). There are reports of CO2/
CH4 selectivities of up to 35 for cellulose acetate membranes in the literature, but for this study we took a
more conservative selectivity value of 15 under normal plant operating conditions. The membrane unit was
implemented in Aspen Hysys as a user defined subflowsheet. The amine unit section of the hybrid process
was set-up with similar parameters as the Base Case.
The process metrics used to evaluate the performance of the hybrid process relative to the MDEA process
were based on indicators presented by Roussanaly, Anantharaman, and Lindqvist (2014). These metrics
included methane slip (MS), relative energy demand (RED), dry equipment weight, dry install equipment
4 IPTC-18732-MS

weight, total plant volume, equipment cost, installed cost and operational costs. The economic parameters
were estimated with the Aspen Process Economic Analyser.

Results and Discussion

First, it should be stated that in our study a membrane unit alone could not achieve the required purification
of the natural gas down to the 50 ppmv CO2 specification. This result was as expected. Instead, membrane
units may be most useful to remove bulk CO2 from the gas feed and than allow reduction in the size of the
amine scrubber required to achieve the deep removal of CO2. The fraction of CO2 removed in the membrane
unit has a large effect on the operational costs of the hybrid process and we investigated this factor by varying
the area of the membrane unit. Figure 2 illustrates this effect on operating costs for Feed1 containing 10
%mole CO2. The most significant change to the operating conditions when the membrane unit is introduced
is that the required solvent rate in the amine unit can be reduced as shown in Table 2. The advantage of
the hybrid system is shown to be greatest for Feed2 (50 % CO2) with the required solvent rate dropping
from 4105 m3/h to 1360 m3/h.

Figure 2—Sensitivity of operating cost to the fraction of CO2 removed in the membrane
separation unit upstream of the MDEA scrubber for a sour gas containing 10 %mole CO2.

Figure 3 summarises the key performance indicators of the hybrid case for Feed1 and hybrid case for
Feed2 realtive to the MDEA base case. For Feed1 there are no significant differences in the performance of
the hybrid case over the base case, so at feed CO2 concentrations up to 10 % there may be little advantage
in a hybrid process. Furthermore, due to the selectivity of the membrane the hybrid process at 10 % CO2
exhibitied a methane slip of almost 3.5 times more than the MDEA process (not shown Figure 3 due to scale
of other metrics); this slip is loss of product and also impacts on the energy efficiency of the process.
IPTC-18732-MS 5

Figure 3—Spider plot of key performance metrics for the MDEA base case, Hybrid
case Feed 1 and Hybrid Case Feed 2. Methane slip is not shown on this figure.

For Feed2 the hybrid membrane-absorption process also shows significant methane slip, but the other
metrics in Figure 3 shown that the methane loss is offset by energy savings in the solvent recirculation pump
and reboiler duty of the amine process. Also, the reduction in solvent rate required for the hybrid Feed2
case leads to a significant reduction in the weight and volume of the AGRU. The operational costs for the
hybrid process treating Feed2 is 40 % less than the MDEA base case.

Conclusions
1. A hybrid membrane – absorption process with a cellulose acetate membrane and MDEA as the solvent
in the scrubber can be designed to treat sour natural gas feeds to the LNG plant feed specification
of 50 ppmv CO2.
2. For a feed containing 10 % CO2 there was no apparent advantage for the hybrid process over a
conventional amine process. In fact, the methane slip through the membrane reduced the process
performance.
3. At very high CO2 concentrations (Feed2 = 50%mole CO2) the bulk separation of CO2 from the feed
gas in a membrane unit upstream of the amine scrubber shows potential to reduce the weight by 80
% and volume by 50 % of the AGRU significantly, and reduce energy costs by up to 30 %.

Acknowledgement
This research was funded by the Australian Research Council (DE140100569). Mr Schlierf received
additional travel funding from TUM.

Reference
Chan, I., A. Eaton, J. Buckles. Safety-based acid gas treating system for a floating LNG plant. Vol. 2, 894–900.
Niu, Mark Wendou, G. P. Rangaiah. 2014. Retrofitting amine absorption process for natural gas sweetening via
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www.sciencedirect.com/science/article/pii/S175058361400245X.
Roussanaly, S., R. Anantharaman, K. Lindqvist. 2014. Multi-criteria analyses of two solvent and one low-temperature
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