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NEW MEMBRANE APPLICATIONS IN GAS PROCESSING

Kaaeid A. Lokhandwala and Marc L. Jacobs


Membrane Technology & Research, Inc.
Menlo Park, CA, U.S.A. 94025
650 328-2228

ABSTRACT

Polymeric membranes have developed into an important separation technology during the past
15 years. In the natural gas industry, the principal application of membranes is the separation of
carbon dioxide from natural gas. The membranes used in this application are made from rigid, glassy
polymers. Membrane Technology & Research, Inc. (MTR) has developed and commercialized a new
membrane-based process for the gas industry. The enabling technology of this process is a unique type
of rubbery membrane, which permeates condensable vapors, such as C3+ hydrocarbons, aromatics, and
water vapor, while rejecting the non-condensable gases, such as methane, ethane, nitrogen and
hydrogen. The process was first commercialized in 1990 and during the past 10 years, more than 50
systems have been installed in the chemical process industry worldwide. This unique rubbery
membrane is now being applied to the separation of C3+ hydrocarbons from methane in gas
processing. Test systems able to treat up to 5 MMSCFD of natural gas have been installed at gas
processing plants. Based on the performance of these units, design calculations for several larger
commercial projects have been developed, and the competitive niche of the technology has been
determined. The main applications are NGL recovery and dew-point control for associated natural gas,
and fuel gas conditioning for gas turbines and engines.
NEW MEMBRANE APPLICATIONS IN GAS PROCESSING

INTRODUCTION

Membrane processes for gas separation applications were introduced in the early 1970s. The
initial application was hydrogen recovery from purge streams in ammonia plants. Other applications
including O2/N2 separation and separation of CO2 from natural gas have been widely applied as well.
In the last decade, a different type of membrane material has been commercialized for the separation
and recovery of condensable hydrocarbons from non-condensable gases such as nitrogen, methane and
hydrogen. This paper describes this novel, membrane-based process and its applications in the natural
gas industry.

TECHNOLOGY DESCRIPTION

Composite Membrane

Figure 1 shows the cross section of the composite membrane produced by MTR for the
separation of heavy hydrocarbons from natural gas. The membrane consists of three layers: a support
fabric, a micro-porous polymeric support layer, and a selective rubbery polymer layer.

Selective Layer
Microporous
Support

Support
Fabric

Figure 1. Membrane Cross Section

Each layer plays an important part in the overall function of the membrane. The support fabric
characteristics are important in determining the support membrane structure, and together these layers
provide the overall mechanical strength of the membrane. The selective layer performs the separation.

Spiral-Wound Module

The membrane is packaged into a spiral-wound module as shown in Figure 2. The module
consists of a series of membrane envelopes. Each envelope contains two sheets of membrane
separated by a feed spacer. The permeate side of the membrane sheets are separated by a permeate
spacer. The entire assembly is rolled tightly around the central product tube. The modules are one
meter long and up to 8 inches in diameter.
Module housing

Feed flow Residue flow


Permeate flow
Feed flow Residue flow
Feed flow
Spacer
Membrane
Spacer
Permeate flow
after passing through
membrane

Figure 2 - Spiral-wound module

The spiral-wound module has one inlet and two outlets. One outlet is for the permeate stream,
which is enriched in heavy hydrocarbons (C3+). The other outlet is for the residue stream, which is
depleted in heavy hydrocarbons. The driving force for the separation is the difference in the feed and
permeate pressures.

Figure 3 - Schematic diagram of skid-mounted membrane system for removal of C3+ from natural gas.

The modules are inserted into the pressure vessels shown in Figure 3. This skid-mounted
membrane unit has two pressure vessels, or tubes, each containing up to four spiral-wound modules in
series. The unit can process from 2 to 5 MMSCFD of natural gas, depending on the feed conditions. To
add capacity, additional tubes can be installed on the same skid. The modular nature of membrane
systems offers unique advantages. These advantages include staging the capital investment and operating
over a wide range of flow rates (from 40 to 100% of design). The system contains no moving parts and
requires no operator attention.
APPLICATIONS
Due to the unique behavior of these rubbery membranes, a number of new applications in the gas
industry are being evaluated. These applications include:

Associated Gas Processing to Recover Oil Vapors


Wellhead Gas Conditioning for Btu and Dew-point Control
Fuel Gas Conditioning for Gas Engines and Turbines
Turbo-Expander Gas Plant Debottleneck
Propane Refrigeration Plant Debottleneck
Flare Gas Recovery
Vapor Recovery

Several of these applications are described in greater detail in the following sections as case
studies.

FIELD TEST RESULTS AND DISCUSSION

This new membrane-based process has been field tested at the locations listed in Table I below.

Table I Field Test Summary

Site E Year Flow Rate Application


Chevron Lost Hills Facility 97-98 3.0 MMSCFD Associated Gas Dew-point Control
Lost Hills, CA
Norcen Explorer 96-97 3.0 MMSCFD Dehydration and Dew-point Control
Patterson, LA
Shell E&P 96 0.1 MMSCFD Acid Gas Separation
Bryans Mill, Texas
Mobil 99-00 2.5 MMSCFD Fuel Gas Conditioning
Qua Iboe Terminal, Nigeria

In addition to the field tests listed above, the U.S. Department of Energy (DOE) recently awarded a
$1.3 million contract to MTR to demonstrate NGL recovery and dew-point control at BP-Amocos Gas
Plant in Pascagoula, MS. Other participants in this demonstration include Chevron, Texaco, Statoil, and
the Gas Research Institute. The test will be conducted from July 2000 to September 2001.

Lost Hills Results and Discussion

The membrane test system was commissioned in September 1997. The system was operated
during two periods: from start-up to January 1998 and from April 1998 through July 1998. During the
initial period, parametric tests were carried out to obtain performance data over a range of operating
conditions. During the latter period, the system was operated at essentially fixed conditions, to determine
long-term performance.
The membrane skid was installed downstream of a set of reciprocating compressors and their air-
cooled aftercoolers. The feed gas flow rate varied from 2.5 to 3.0 MMSCFD, feed pressure from 380 to
450 psia, and feed temperature from 80 to 125oF. Figure 4 shows a photograph of the system at the site.

Figure 4 - Photograph of Membrane System at Chevron Gas Processing Plant, Lost Hills, CA.

Figures 5 and 6 show the results obtained in this test. Figure 5 shows the feed and permeate flow-
rate as a function of time. The data shows that although the feed flow rate varied depending on the feed
conditions at the plant, the permeate stream was steady and essentially unchanged during the period of the
test. This result indicates that the membrane is stable under those gas conditions.

Figure 6 shows the removal rates of the various components in the feed gas as a function of time.
Removal rates are relatively modest because the test was performed to determine the membrane stability
and not necessarily to demonstrate high removal rates of C3+ hydrocarbons. In the test we observed
propane removal of 50 to 60%, butane removal of 60 to 70%, hexane removal of 70 to 80% and octane
removal of more than 90%.
Operating Time (Days)
0 20 40 60 80 89
1400

1200

1000
Flow Rate (scfm)

800

600

400

200

0
4/20 5/10 5/30 6/19 7/9 7/29
Time (Date)
Figure 5. Feed and Permeate Flow Rates Variations During the Field Test at Lost Hills, CA.

100

90 C8

80 C6
Percent Removal (%)

70
C5
60 C4
C3
50

40

30

20

10
11/16/97 1/5/98 2/24/98 4/15/98 6/4/98 7/24/98
Date

Figure 6 - Membrane System Removal Rates

Since heavy hydrocarbons contribute most to the hydrocarbon dew-point of natural gas, the
removal of these components will lower the dew-point. For the duration of the test, the hydrocarbon dew-
point of the feed and residue streams of the membrane system is shown in Figure 7. The figure shows that
the feed dew-point and the feed temperature are close, indicating that the feed is nearly saturated with
hydrocarbons. The gas exiting the air-cooled heat exchanger in the plant was fully saturated and in many
cases entered the membrane system as a partially liquid stream. Any condensed liquids were separated in
a two-phase separator and a coalescing filter upstream of the membrane modules. Due to the removal of
the heavy hydrocarbons, the processed gas exiting the membrane system had a lower dew-point. Typical
dew-point depression in this test was between 40-50oF.

160

140

120
Hydrocarbon Dewpoint (oF)

Feed Gas Temperatures

100
Dewpoint of Feed Gas

80

60
Dewpoint of Conditioned Gas
40

20

0
8/8/97 9/27/97 11/16/97 1/5/98 2/24/98 4/15/98 6/4/98 7/24/98
Date

Figure 7. Feed and Conditioned Gas Dew-points

Mobil Qua Iboe Terminal System Results and Discussion

In 1998, Mobil Corporation purchased a system for installation at their Qua Iboe oil terminal in
Nigeria to condition fuel for a gas turbine. The system began operation in July 1999. A photograph of the
system is shown in Figure 8.
Figure 8 - Photograph of Gas Turbine Fuel Gas Conditioning Unit

The Mobil system consists of four pressure vessels, each containing a single 8-inch spiral-wound
module. The unit was designed to operate with one train of 4 modules in series, or with 2 trains in parallel,
each train containing 2 modules in series. The feed stream enters the system through a filter separator with
a coalescing element to remove any entrained liquids. The gas from this filter enters the membrane
modules. The membrane removes the heavy hydrocarbons and lowers the dew-point of the residue gas. In
this system, the permeate stream is sent to the flare system, but the stream can also be routed back to the
process to recover additional liquids. Table II shows the feed conditions and separation performance of
the membrane system.

Table II Feed Conditions and Hydrocarbon Removal Rates

Component Feed Composition % Removal


Propane 12.11 68
i-Butane 2.31 72
n-Butane 3.71 81
i-Pentane 0.88 85
n-Pentane 0.61 88
Hexane 0.17 89
Heptanes+ 0.31 92
Feed Pressure (psig) 205
Feed Flow rate (MMSCFD) 1.46
Feed Temperature (oF) 82
Feed Dew-point (oF) 82
Residue Dew-point (oF) 20

The feed gas to the membrane system comes from the after-cooler of a gas turbine fuel gas
compressor. The feed gas is saturated at 82oF while the residue gas is depleted in the heavy components
and has a dew-point of 20oF. The permeate stream operates at atmospheric pressure. Table II shows that a
significant amount of the heavy hydrocarbons are removed in the membrane system.

APPLICATION CASE STUDIES

Case 1. Wellhead Natural Gas Conditioning/Dewpoint Control

Hydrocarbon dew-point control is required for virtually all natural gas that is produced.
Conventional dew-point control methods include propane refrigeration and adsorption. The cost and
complexity of these processes make them unattractive for processing natural gas at remote locations,
on off-shore platforms, or when the feed throughputs are less than 25 MMSCFD. In most off-shore
applications, refrigeration systems are unattractive because of their weight and footprint requirements.
Membrane systems offer small footprints, simplicity, efficiency, and low cost for these dew-point
control applications.

Figure 9 shows a flow schematic of a raw, low-pressure natural gas stream at 250 psia boosted
to pipeline pressure of 1,000 psia. The gas from the compressor after-cooler enters a phase separator.
The gas exiting the phase separator is saturated and has a dew-point of approximately 95oF. To avoid
condensation of liquid in the pipeline, the gas must be conditioned. In this example, the membrane
system treats the high-pressure gas by preferentially permeating the heavy hydrocarbons and reduces
the hydrocarbon dew point of the feed stream. The permeate stream, enriched in heavy hydrocarbons,
is recycled to the inlet of the booster compressor. The heavy hydrocarbons are recovered in the phase
separator upon recompression. The residue stream exiting the membrane system will meet the desired
pipeline hydrocarbon dew-point specification, which in this case is 15oF. Thus, the membrane system
not only processes the gas stream to meet dew point specifications, but also recovers the heavy
hydrocarbons. The membrane system is passive and requires no rotating equipment. In applications
where feed compression is either existing or is required for other reasons, membrane systems can be
integrated into the overall compression system, eliminating the need for additional rotating equipment.
Furthermore, since water is very permeable, the membrane system can also dehydrate natural gas to
pipeline specifications, eliminating the need for a glycol absorber.

Table III Comparison of Membrane System with Propane Refrigeration

Installed Cost Processing Cost*


Process
($MM) ($/inlet MSCF)
Propane Refrigeration 1.6 0.165
Membrane 1.1 0.098
* Includes Capital Cost

As shown in Table III, membrane systems have lower capital and processing costs for
hydrocarbon dew-point control applications. Other advantages include no moving parts, minimal or no
operator supervision, small footprint, and low weight.
C3+ enriched gas

To High Pressure
Pipeline

Raw 1000 psia


o
95 F Hydrocarbon
Natural Gas o
M embrane Dewpoint: 15 F
System 1000 psia

250 psia
6 M M SCFD Booster
Compressor

10562 gpd
Stabilizer NGL
250 psia

Figure 9. Wellhead Gas Conditioning Dew-point Control

Case 2. Processing associated gas from oil production facilities

By processing associated gas, the production of light hydrocarbon liquids from oil platforms is
increased above the amount achieved by simple flash stabilization of the produced oil and
recompression of the associated gas. The use of a membrane system within an oil-field gas processing
train increases the concentration of condensable hydrocarbons within the processing train, thereby
increasing the recovery of hydrocarbon liquids. Appropriate placement of the membrane system
within the processing train can result in as much as 5% higher oil production with small increases in
the compression requirements of the associated gas. Membrane systems in this application will exhibit
very rapid pay-back times. The compact, modular, and low-maintenance characteristics of membrane
systems make these applications particularly suitable to offshore facilities.

Figure 10 shows a typical platform processing train for production of oil and gas from a
reservoir fluid mixture. The reservoir fluid, containing the oil and entrained vapors and gases, enters
the first separator vessel in which bulk separation of oil, water, and gas occurs. The pressure of the oil
phase is subsequently lowered in a set of separator vessels operating at progressively lower pressures.
In Figure 9, these pressures are 315 psia, 70 psia, and atmospheric pressure. The pressure reduction
releases the lighter entrained gases and vapors from the heavy oil. The evolved gases are compressed
in three compressors to the pipeline pressure of 1,000 psia. In the process of compression and cooling,
additional hydrocarbon liquids are condensed in the compressor after-coolers and are recovered in the
separator vessels. The pressure and temperature of the separator vessels determine the total oil
produced in such a train. To increase oil production, these operating conditions would have to be
changed. However, in most cases these variables are usually predetermined either by pipeline
conditions or the ambient temperature.
Associated
Gas Compressed
Gas
47 M M SCFD
Associated
Gas

Membrane
Well-head System
Crude
1015 psia

250 psia
Crude to
Storage
15 psia
315 psia

Figure 10 - Recovery of hydrocarbons from associated gas

Incorporating a membrane system within the same process can substantially increase the total
oil production with a small increase in the compressor horsepower requirement. The membrane
system can be placed at different points within the flow scheme. One such location is shown in Figure
10. Here, the membrane system treats the gas evolved from the separator vessel after the second
compressor (whose suction pressure is 70 psia). The discharge pressure of the compressor is increased
by about 20 psi to compensate for pressure drop in the membrane system. The membrane system will
preferentially permeate the heavy hydrocarbons, resulting in two streams. The permeate stream is sent
to the separator vessel operating at 70 psia, as shown in the figure. The residue stream is added to the
feed stream of the first compressor. Recycling the permeate stream sets up a loop in which the content
of the lighter hydrocarbon gases (such as methane and ethane) is reduced. Condensation of the heavy
hydrocarbons into the oil phase is increased in the separator vessel at 70 psia and in the second
compressor after-cooler. Table IV shows the impact of the membrane system on the oil production
and compression requirements.

Table IV Performance of Membrane System for Platform Associated Gas Application

Incremental Oil Incremental Power


Case
Production (bbl/day) (hp)
No Membrane - -
With Membrane 870 472

Table IV shows that inclusion of the membrane system in the platform oil processing train can
significantly increase oil production. The pay-back time for the membrane system is less than 6
months. Other operational advantages include small footprint and weight, no moving parts, and
minimal installation cost. In addition, if the membrane system is placed on the final gas line, it can be
designed to meet the pipeline hydrocarbon and water dew-point specifications.

CONCLUSIONS
The new membrane-based process developed by MTR has opened up new applications in the
gas processing industry. The process is well suited for NGL recovery and dew-point control for
associated gas, and for conditioning fuel gas used in gas engines and turbines. Furthermore, the
process may be used to de-bottleneck existing gas plants.

Membrane systems have many significant advantages over other conventional gas treating
technologies. Due to the simple nature of the process and minimal control needs, the systems can be
operated without supervision. In many cases, rotating equipment is not required. The units are very
versatile and are designed to process a wide range of feed conditions. Over 100 years of cumulative
operating experience in the chemical process industry has proven that the systems are reliable and have
high on-stream time. With very compact footprint and low weight, membrane systems are well suited
for off-shore applications.