Journal of Membrane Science 154 (1999) 121±126

CO2 removal from synthetic natural gas for city gas use
Haruo Watanabe*
Harima Technical Center, Air Liquide Japan, Ltd., 16, Niijima, Harima-cho, Hyougo-pre., 675-0155, Japan

Received 1 April 1998; accepted 3 September 1998

Abstract

Membrane-based gas separation has been applied for carbon dioxide (CO2) removal from commercial city gas supply plants
in Japan. This paper provides the relationship between methane reforming process, design of two-stage membrane process and
their optimization. # 1999 Elsevier Science B.V. All rights reserved.

Keywords: Gas separations; Inorganic membrane; Carbon dioxide

1. Introduction cost made from LNG is higher when compared with

In Japan, various types of city gas supply produc-
tion plant have been put in use, such as LNG (lique®ed
natural gas) or LPG (lique®ed petroleum gas) evapora-
tion, LPG mixed with air and reforming of LPG or
naphtha. Most of the LNG has been imported and
stored in LNG bases to supply natural gas and to
distribute LNG by tank trucks to the LNG satellites.
Natural gas is one of the cleanest gases suitable to city
gas use because of its low level of emissions, low
carbon monoxide levels, its being lighter than air and
less likely to be involved in explosions and its high
caloric value. LNG's share was 75.7% of the domestic
city gas consumption in Japan in 1995 [1]. There are
eight LNG bases near big consumption areas in Japan,
but they are not well distributed geographically. In the
case of city gas plants which are very far from LNG
bases, for example 200 km from a LNG base, total gas
*Tel.: +1-905-525-9140; fax: +1-905-522-2509; e-mail:
haruo.watanabe@jp.airliquide.com
other gas reformed from LPG or naphtha. The cost of
transportation of LNG or construction of the pipelines
is very high. LPG or naphtha are available to supply to
city gas plants from near by re®neries or industrial
complexes by conventional transportation systems.
City gas plants based on LPG or naphtha high calori®c
synthetic natural gas (SNG) were required for the
country side. This new SNG should almost have the
same calorie output and burn rate as LNG: over
11 000 kcal/Nm3 and burn at over 35MCP. SNG made
without CO2 removal contains high CO2 content and
remains low in energy. So, it is necessary to combine
CO2 removal system with reforming system [2,3].
Using membranes for CO2 removal from SNG is very
competitive with alternative technologies such as PSA
(pressure swing adsorption) or liquid absorption
method.
Membranes have a clear advantage in terms of
compactness, not having moving parts and being noise
free. Two commercial SNG plants using hollow ®bers
membranes were started-up, the other two are under

0376-7388/99/$ ± see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0376-7388(98)00284-1
122 H. Watanabe / Journal of Membrane Science 154 (1999) 121±126
design and construction, and the others are under
consideration in Japan.
This paper provides design and optimization infor-
mation on two-stage membrane system.
The purpose of this paper is to explain practical
design considerations for engineers or researchers
working with membrane-based gas separations.
2. New SNG process
2.1. Gas production process (Fig. 1)
A new simpli®ed SNG ¯ow diagram combined with
a two-stage membrane system is shown in Fig. 1. LPG
or naphtha is heated up to the level of 300±4008C and
then transferred to ``DE-SULFUR TOWER'' to eliminate
sulfur compounds with the Nickel±Molybdenum(Ni-
mox) catalyst to protect the catalyst used in the down
steam reformer. Sulfur compounds are converted to
H2S at 300±4008C and then absorbed by zinc oxide
(ZnO) as follows:
RSH ‡ H2 @RH ‡ H2 S
ZnO ‡ H2 S@ZnS ‡ H2 O
and the gases are mixed with steam and heated to
5508C for reforming feed gases to methane [2,3]:
Cm Hn ‡ mH2 O@mCO ‡ …m ‡ n=2†H2
Cm Hn ‡ 2mH2 O@mCO2 ‡ …2m ‡ n†H2
Cm Hn ‡ …2m ÿ n=2†H2 @mCH4
CO ‡ 3H2 @CH4 ‡ H2 O
CO ‡ H2 O@CO2 ‡ H2
CO ‡ 3H2 @CH4 ‡ H2 O
2.2. Feed gas to membrane system
Typical composition of a new SNG gas stream is
shown as follows and is pressurized at a level of 7±
8 bar ab., which is to supply the product gases to
existing storage tanks.
Composition (mol%):
CH4 ˆ 74ÿ79; CO2 ˆ 18ÿ21; H2 ˆ 2ÿ4;
CO ˆ 0:03ÿ0:06; H2 O ˆ saturated:
It is necessary to reduce the CO2 content less than 2.5±
3.0 mol% from the above level to convert the gas into
high calorie and high burning velocity city gas.
2.3. Module and membrane process design
The schematic for a bore feed type module used in
this pilot test and at the commercial plants is shown in
Fig. 2. The module is made of polyimide hollow ®bers
by Medal (Delaware, USA) and its dimension is 6 in.
in diameter. At the same time, different kinds of
membrane processes, such as single-stage partial
recycle and two-stage process, were compared from
an economic view print [4]. About 5% of methane is
necessary as fuel for the reforming heat energy, so
95% of methane should be recovered as product. The
best design con®guration is found to be optimal not
only for the number of membrane modules, but also
for the output capacity of the recycle compressor.
2.4. Two-stage membrane system (Figs. 1 and 3)
The feed gas is sent into the ®rst membranes, and
then methane remains as a residue to be used as city
gas supply. The permeated gas from the ®rst mem-
branes contains about 18±20% of the methane from
the feed gas and its pressure is about 1 atm. It is then
boosted up by the recycle compressor to feed it to the
second membranes and recycle it as feed gas to the
®rst membranes. The optimized two-stage design is
found to recover enough methane to make it cost
ef®cient with a signi®cant reduction in investment
and compressor energy use.
3. Process design
3.1. A model of plant (Table 1 and Fig. 3)
The feed gas stream to the ®rst membrane has a
pressure of 7.4 bar ab., contains 19% CO2, and the
¯ow rate is 2500 Nm3/h for a middle size domestic
city. In this study, the following design conditions are
applicable for the design of common SNG plants:
 Feed gas pressure: 7±8 bar ab.
 Feed gas flow rate: 2000±6000 Nm3/H, where
Nm3/H±Nm3 means gas volume at 08C, 1 atm
pressure.
H. Watanabe / Journal of Membrane Science 154 (1999) 121±126 123

Fig. 1. Flow diagram of SNG plant.

124 H. Watanabe / Journal of Membrane Science 154 (1999) 121±126

Fig. 2. Bore-feed type membrane module.

 Average feed gas composition (mol%)
CH4 ˆ 74ÿ79; CO2 ˆ 18ÿ21; H2 ˆ 2ÿ4;
CO ˆ 0:03ÿ0:06; H2 O ˆ saturated:
The trans-membrane pressure between feed and
permeate stream is about 6±7 bar. This is a low-
pressure gas separation compared to natural gas sweet-
ening or hydrogen recovery at a re®nery. It means that
a large number of modules is necessary for a SNG
plant. The cost of the modules per one SNG plant is to
be reduced not only by improving permeation rate in
membrane but also by total cost reduction of manu-
facturing of modules. Refer to 1 of Section 6.
3.2. Membrane process
A model of a ¯ow diagram for a middle sized
commercial plant is shown in Table 1 and Fig. 3.
The feed gas is shown as stream 1 supplied from
the gas production plant and product gas is shown
as stream 3. In this case, recovery of methane is
calculated as 96.6%. Stream 6 is off-gas which is
used for fuel in the heater and steam boiler. Refer
to Fig. 1.
4. Design of membrane process and optimization
4.1. Design of membrane process
As it is illustrated in Section 2, fuel is necessary to
heat feed gas for reforming LPG or naphtha into
usable methane. This ratio is about 4±5% of the feed
gas methane at stream 1. This means that a methane
recovery rate should be higher than 95±96% of the
methane. Methane permeated from the ®rst mem-

Table 1

Stream number

1 2 3 4 5 6 7
Composition (mol.%)
CH4 77.6 79.28 97.26 41.94 41.94 10.45 89.22
CO2 19.0 17.85 2.50 49.23 49.23 74.13 10.07
H2 3.35 3.00 0.17 8.79 8.79 15.41 0.64
CO 0.05 0.053 0.06 0.04 0.04 0.02 0.08
Flow rate (Nm3/H) 2500 2869 1927 942 942 573 369
Pressure (bar ab.) 7.4 7.4 6.7 1.01 8.5 1.51 7.70
Temperature (8C) 40±50 30 30 30 30 30 30
 H. Watanabe / Journal of Membrane Science 154 (1999) 121±126 125

Fig. 3.

Table 2 5. Property of membrane, quality control and

Selectivity Flow rate at Compressor
(CO2/CH4) stream 5 (Nm3/h) Output (kw)
25 1044 135
31 942 122
36 891 115
branes is to be recovered by second membranes as
residue gas. The capacity of recycle compressor is
designed according to the ¯ow rate shown as stream 4
and feed pressure to the second membranes. At the
same time, it is important for optimization to recover
the minimum volume of from stream 5 in order to
reduce energy use by the recycle compressor. Excess
recovery of methane means the loss of energy and the
unbalancing of the process.
4.2. Optimization and results
Table 2 shows the relationship between CO2/CH4
selectivity, ¯ow rate of the recycle compressor and its
energy consumption as in Section 3. The methane
recovery is optimized to 96.6% for each case by
controlling the ¯ow rate of recycled gas to reduce
energy consumption. The above results show that the
high CO2/CH4 selectivity reduces the energy of the
recycle compressor. On the other hand, a bigger
recycle compressor is necessary to keep recovery of
methane at the same level in case of membrane with a
smaller CO2/CH4 selectivity.
related patents
5.1. Property of membrane: Selectivity vs
permeability
As it is described in Section 4, high CO2/CH4
selectivity is not only important to reduce recycle
compressor energy use, but also it is a valuable
property for membrane makers in appealing to city
gas suppliers. The gas suppliers will require mem-
branes of high selectivity and high permeability to
reduce running cost and to recover investment cost.
5.2. Quality control of bundles
Most city gas suppliers have redundant systems as
they deliver a public utility. The same rule shall be
applied to membrane system. More than 50±60 units
of 6 in. modules, as per Sections 2 and 3, need to be
installed doubly in number and in parallel for a middle
sized city gas plant. The membrane system will
decline in performance if there is a large mix in the
distribution between permeability and selectivity of
the modules.
ISO9002 standards will need to be required of
membrane makers which supply many modules for
these projects.
5.3. Patent information
Patent related to SNG processing and plant combi-
nations with membranes have been applied for by
126 H. Watanabe / Journal of Membrane Science 154 (1999) 121±126
Mitsubishi Kako Ki (Tokyo, Japan) [5], and for mem-
branes by Air Liquide Medal (Delware, USA) [6].
6. Conclusion
Design of the membrane process for commercial
plants has been done to data with the data from a pilot
plant and simulations. The ®rst long running pilot tests
have carefully done for three months at a city gas
plant. Feed gas was kept 308C and the permeability
declined by 2±3%, stabilizing after 1000 h from the
initial start-up. However, CO2/CH4 selectivity has
been shown to be of negligible variability.There is
an additional bene®t to this process. Gas bleed at
stream 5 can not only fuel the plant, but can also
be used in processing at the ``DE-SUPHER TOWER'' as it is
high in hydrogen. See the gas extraction from delivery
to the compressor line shown in Fig. 1. The results of
the study suggest that the two-stage membrane sys-
tems should be designed carefully. The speci®c con-
clusions are listed below.
1. Higher CO2/CH4 selectivity and permeability
reduces the running and investment costs. Devel-
opments of a separation layer thickness down to
Ê and gains in manufacturing cost such
300±500A
as ®ber-spinning and ®ber-processing technology
and automated bundle-forming process have been
done by the membrane makers [7]. Development
by membrane makers to increase CO 2/CH4
selectivity is underway.
2. Optimization from an engineering view point is
also important to reduce investment cost and
energy cost for SNG plants.
Acknowledgements
This work was supported by Plant maker ± Tokyo
Gas Engineering Co., Ltd. (Tokyo, Japan), Plant
department of Mitsubishi Kakko Ki Co., Ltd. (Yoko-
hama, Japan) and by Membrane maker ± Air Liquide
Medal (Delaware, USA), started as a joint venture of
Du Pont, USA and Air Liquide, France.
I sincerely thank them for their cooperative work
and technical assistance. SNG plants using mem-
branes could not have been commercialized in Japan
without their help. This is the ®rst time that a mem-
brane-based SNG reforming system has been used at a
public utility.
References
[1] Home page of The Japan Gas Association, 1-15-12,
Toranomon, Tokyo, http://www.gas.or.facts/genryo.html
[2] A. Obuchi, H. Taniguchi, SNG plant used membrane for CO2
removal, The Piping Engineering, 86±90, July 1995, 6-3-26,
Komagome, Tokyo; htt.//www.takarabune.or.jp/nikko/
[3] Technical instruction for high calorie city gas production
process, June 1994, The Japan Gas Association, See [1].
[4] R.W. Spillman, M.G. Barrett, T.E. Cooley, Gas Membrane
Process Optimization, AlChE Meeting in New Oreleans, 9
March 1988.
[5] A. Obuchi, H. Taniguchi, City gas production, JP Patent No.
2584716 (other related patents and publications).
[6] O.M.Ekiner, R.A. Hayyes, P. Manos, Novel multi-component
fluid separation membranes, US Patent 5, 085, 676.
[7] I.C. Roman, R.W. Ubersax, Membranes for Gas Separation:
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Production, Davos (Switzerland), October 1997.