*The

1 lth
Offshore South East Asia Conferenc.

OSEA96018
NATURAL GAS SWEETENING BY THE COMBINATION OF SEMI-PERMEABLE MEMBRANES
AND FIXED BED CHEMICAL ABSORBENTS
STEVE B HEINEMANN, BORAL ENERGY RESOURCES LTD
&
COLIN WOODWARD, ICIKATALCO

This
paper was prepared for
presentation
at
the
11
th Offshore South East Asia
Conference held in
Singapore,
24-27
September
1996.
This
paper
was selected
for presentation by
a programme committee following review of
information
in
an abstract. Contents
of
the paper have not
been reviewed by
OSEA and are
subject
to correction by the author(s).
The
material, as presented, does
not necessarily reflect any position of
the
Offshore
South
East Asia Conference or its
offiiers.

ABSTRACT I

The combination of a semi-permeable membrane

system with a fixed bed chemical absorbent has

been shown to be a convenient and reliable way to

meet sales gas specification. These technologies

are particularly suited to remote locations,

including offshore, where there are limitations on

space, weight and labour availability.

Boral
Energy Resources Ltd
has been operating a
26
MMscfd
natural gas processing plant at Beharra
Springs, Western Australia since 1993.
Carbon
dioxide is reduced to the required 4%
(max)
by the
membrane which also lowers the H2S
from
10
ppmv
to 5-6
ppmv.
Final polishing to the
required 3.0
ppmv
is provided by a non-regenerable
chemical absorbent.

INTRODUCTION (Ref
1)

The Beharra
Springs (BS)
gas field is situated in the
northern Perth Basin 350
km north of Perth and
approximately 1.6
km west of the West Australian
Natural Gas Pty Ltd (WANG) pipeline. (Figure 1)
The WANG pipeline runs from the Dongara
gas
field, which is about 25
km north of the Beharra
Springs field, south through Perth and the major
heavy industrial area of Kwinana,
to the Alcoa
alumina refinery at Pinjarra
some 80
km south of
Perth. The 14
inch, high pressure gas pipeline was

References
&
Illustrations at end
of
paper.

opened in 1971
to supply Perth and Kwinana
with
gas from the newly discovered Dongara
(1966)
gas
field operated by West Australian Petroleum Pty
Ltd
(WAPET).
In 1992
the maximum daily gas
transportation down the WANG line was
approximately 740,000
m3/d,
(26
MMscfd)
which
represented only 23
percent of total available
pipeline capacity.

The West Australian State Governments decision

to deregulate the natural gas market in 198
8
allowed producers to contract gas supplies directly
with consumers without transferring gas ownership
to the State Energy Commission of Western
Australia (SECWA).
Coupled with the low
utilisation of the WANG pipeline running through
the length of the North Perth Basin, this provided
potential gas explorers and developers with the
infrastructure and mechanisms necessary to market
and supply gas readily from
potential gas
developments in that region.

Gas consumption in the Perth region is dominated

by large industrial consumers situated in Kwinana
and other sites south of Perth. The most prolific
consumer is Alcoa of Australia Ltd
where more
than 200 TJ/d of gas is consumed in three alumina
refineries at Kwinana, Pinjarra and Wager-up.
Alcoa is the largest single industrial consumer of
gas in Australia and has the market power and
flexibility to take supplies from a range of gas
producers. (1
TJ
is approx
equivalent to 1 MMscf.)
i

NATURAL GAS SWEETENING BY THE COMBINATION OF . . . . . .

GSEA960
18

The three aspects: deregulation, pipeline capacity

field engineering study which reviewed the

and large potential consumers provided incentives

economics of
various processing options.
for an exploration programme in the EP320

Included in this study was a detailed comparison

Exploration permit immediately south of the

of the capital and operating costs of both amine

WAPET
production licences of the still-producing

treatment and membrane separation for the

Dongara
fields. This programme proved successful

removal of CO, from the gas stream. The

when in April 1990
Beharra
Springs #l
well

engineering study summarised the relative cost

(BS#l)
flowed at a rate of 240,000
m3/d
(8.5

comparisons as detailed in Table 2.

MMscfd)
through a 32/64
inch choke from
a depth
of 3300
metres. Two subsequent wells within 2km

Capital cost included; detailed engineering,

of BS#l
flowed at rates in excess of 650,000
m3/d
purchase of skids, all interconnecting piping,
(23
MMmsfd).
The BS
gas emanates from

installation of skid, utilities, off-site and

gas-bearing sandstone near the top of the early

contingency (20%).
Operating costs included;
Permian Carynginia
formation from a depth of

maintenance, operation costs, chemical usage and

3500
metres.

losses, vent gas losses, fuel gas and overheads

(3
0%).

Some three months after the success of BS#l

, a

contract with Alcoa to supply 39,500 Terajoules

The study summarised the major disadvantage of

(TJ)
over an 11
year period to the alumina refineries

the amine process which comprises a series of

at Pinjarra
and Kwinana
was negotiated at a rate of

integrated processes as an operation with --)h

up to 15
TJ/D.
This contract was later extended

significant costs associated with fuel for

(1993)
to a total supply of 80,000
TJ
over the 11

powering rotating equipment, chemical costs

year period when reserves of greater than 60,000 TJ
(amine degradation), labour and maintenance
had been proven at gas rates up to 30
TJ/D.

costs. The process which involves scrubbing the

gas with an aqueous amine solution also requires
A production testing facility incorporating modified

an additional dehydration step such as glycol

existing well testing separators was installed. The

dehydration following the CO, removal.

gas contained 5-6%
carbon dioxide (CO,). No
facilities were installed to reduce CO2
levels in the

In contrast the use of membranes for CO,

gas. The operation of the testing facilities was

removal incorporates no rotating equipment

shut-down in February 199
1,
when analysis

relying only
on the partial pressure of CO*
to
indicated levels of hydrogen sulphide @I$)
of 8-
10

achieve the separation. As a consequence,

ppmv.
The WANG pipeline specification for H,S

operating and maintenance costs are low, the use

is 3.2
ppmv (max).

of process chemicals is avoided and the process is

inherently reliable in operation. Additional

PERMANENT FACILITIES DESIGN

advantages of the membrane process are its

ability to dehydrate further and to remove H2S
Wellhead
gas from Beharra Springs is wet and

from the gas stream.

corrosive owing to the presence of carbon dioxide
(5-6%)
and hydrogen sulphide (8-10 ppm). The
The DJB
engineering study recommended a
wellhead
gas composition is given in Table 1 along

process configuration including :

with the current WANG pipeline sales
specification. A permanent plant design

. Inlet gas cooling and separation

specification was developed based on the

. low temperature separation of water and

production of 10
TJ/d
normal, 15
TJ/d
maximum,

condensate utilising Joule Thomson

WANG specification sales gas.

expansion
. semi permeable membrane removal of
Davy McKee Pacific, later to become Davy John

COz,
H2S
and water
Brown (DJB),
carried out a Beharra
Springs gas

.
fixed bed technology for hydrogen
sulphide removal.
I

.
.

OSEA960
18

STEVE B HEINEMANN
&
COLIN WOODWARD
3

PLANT DESIGN AND CONSTRUCTION

were achieved. The debottle-neck

was also
associated with a relaxation of the carbon
August 1991
saw DJB
commence front end design

dioxide specification on the WANG pipeline

and process package specification for the BS
plant.

from 2.6%
to 4.0%.
Subsequent optimisation of
During the next four months, the process

heat exchange capacity allowed sales gas rates to

configuration was modified and optimised by the

be further increased to 28TJ/D

by early 1996.
package suppliers to minimise initial capital outlays

Total capital cost of the debottle-necking

and to improve plant flexibility. Detailed tender

facilities was about US $1.5

million. During
specifications for skid-mounted packages of process

1995
two 2000
HP compressors and associated
equipment including major long lead time items

facilities were installed at a cost of US $5.8

were sent for tender in September 1991.
The tender

million.
packages were let on a process specification basis
incorporating significant design responsibility with

4 PROCESS CONFIGURATION
the process package supplier. (see Figure 2)

Shop fabrication and procurement

The gas from BS#l,

#2,
and #3
flows through a

commenced in November 199

1,
primarily in

manifold at a temperature of 50
-
70C
and a
Perth and Melbourne.

pressure of 12000
kPa
which has beer! !et
down,
.
Civil and site activities, including the

at the wellhead, from around 26000

kPa.
The
accommodation were completed by

manifold facility incorporates an underground

February 1992.

slug catcher for each incoming flowline. As

February and March 1992
saw the arrival on

wellhead
pressure decreases pressure will be
site of the various process packages which

supplemented up to 12000
kPa
by two gas
were skid-mounted and trucked to Beharra

engine driven reciprocating gas compressors.

Springs.
Commissioning activities commenced on

The incoming gas is cooled in a first gas-to-gas

1 May and the plant was successfully

heat exchanger to 32C

and is then introduced
commissioned on 10
May 1992
some

into the inlet separator where free water is

9 months after commencement of design.

removed. The inlet separator is equipped with

two sets of demisters
to ensure that droplets of
The facilities were completed on schedule and 12%

water/condensate are not entrained in the exiting

over budget at approximately US $7
million.

gas. The gas is further cooled to 5C

in a second
gas-to-gas heat exchanger. Both exchangers are
In early 1993
a major debottle-necking
design study

fully welded tube sheet shell and tube

was undertaken by DJB.

The aim of the study was

exchangers and have stainless steel tubes to

to increase plant throughout from lSTJ/D
to up to

prevent CO&S
corrosion in the wet well
25TJ/D to take advantage of the extended Alcoa

stream fluids.
contract. A design which incorporated an activated
carbon bed to remove traces of polycyclic
aromatic

The gas is then reduced in pressure from 12000

hydrocarbons (from the condensate) and lube oils

kPa
to 7000
kPa
using an expansion valve,
which could pass through the low temperature

which further cools the gas to -lOC,

and
separator at elevated gas velocities and two new
introduced into the low temperature separator.
fixedbed absorbent vessels to enhance H,S
removal

The condensate-water mix forms a hydrate

capacity was completed.

(hydrocarbon ice) which is separated from the

gas stream by centrifugal motion. The hydrate
A fabrication and design contract for the

collects in a water bath in the bottom section of

debottle-necking facilities was let in mid 1993
and

the separator and is removed from the three

by November of that year sales gas rates of 25TJ/D

phase separator as hydrocarbon condensate or

water. Gas leaving the low temperature
NATURAL GAS SWEETENING BY THE COMBINATION OF . . . . . . OSEA960
1s

separator passes through a proprietary design vane

pack (designed by Peerless MFG
Co), to minimise
further water hydrocarbon entrainment. The gas,
which is now free of liquid hydrocarbon and water
(to pipeline specification), is then passed back
through the two exchangers, increasing its
temperature back to 30C.

The gas passes to the pretreatment section of the

membrane plant where it passes through filter
coalescers
which act as a guard against residual free
water and the carbon bed to ensure that it is
completely free of residual heavy hydrocarbons and
lube oil. It is further heated by hot water to 50C
and passes into the membrane unit at a pressure of
7000
kPa.

The membrane unit contains 112

membrane
elements in 16
tubes, seven elements per tube. The
specific semi-permeable membrane is one which
the impurities CO1
and H2S
readily absorb into,
pass through and desorb
from the other side
(permeate), while hydrocarbon passes through the
membrane at a much slower rate. Details of
membrane separation processes are contained in
Section 5 below. Currently only 80%
of the
membranes are required to produce WANG
pipeline specification sales gas. The permeate gas
is sent at low pressure to fuel the gas-engined
compressors, power generation and the balance is
sent to a vertical flare. This permeate typically
contains about 30%
CO, and 100
ppm H,S. The
gas which does not pass through the membrane is
of sales gas quality for carbon dioxide and the H2S
has been reduced to 5-6
ppmv.

Dry gas exits the membrane unit at 45C

and is sent
to one of the two fixed bed H,S
absorption reactors.
(Details of the process are given in Section 6
below.) The H2S
content of gas passing through the
bed is reduced to effectively zero so, to avoid
unnecessary consumption of absorbent, only
sufficient gas is routed to the absorption unit to
bring the recombined gas H,Scomposition
to
within the pipeline specification (3.2 ppmv
maximum). The on-specification gas is then flow
controlled via a 1.6
km inlet pipeline to the WANG
pipeline meter station.

The condensate produced in the low temperature

separator is reduced in pressure from 7000
kPa
to 250
kPa
and the gas separated from the liquid
in the low pressure flash drum. The stabilised
condensate flows to the condensate storage tank
which has a capacity of 100
cubic metres.
Condensate production averages 6-8
m3/d.
Condensate is sent from BS
by road tanker to be
processed at the BP Refinery in Kwinana.

Water separated in the low temperature separator

and low pressure flash drum is passed via an API
gravity separator, which separates any traces of
condensate hydrocarbon, to the evaporation
ponds. The ponds have been lined with 2 mm
thick high density polyethylene (HDPE)
to
prevent possible contamination of the
environment and ground water.

In areas in the plant with low temperature and

high pressure, hydrates will form. To suppress
this formation at temperatures down to

15C
methanol is injected into the process streams. As
daily consumption is in the region of 900
litres,
methanol is stored in bulk on site.
5 INTRODUCTION TO MEMBRANES
(Ref
2)

Membranes are thin barriers that allow

preferential passage of certain molecules. Gas
separation membranes are predominantly
comprised of polymeric materials. Polymers
commonly employed for gas separation
membranes include cellulosic
derivatives,
polysulfone,
polyamides and polyimides.
These
membranes contain no holes or pores as would
typically be found in filter technology. Instead,
the separation relies on the principles that gases
dissolve in and diffuse through the membrane
polymers. Certain gases will pass through
(permeate) a membrane at a faster rate than other
gases due to a difference in the solubility
of the
gas in the polymer and the rate at which the gas
diffuses through the polymer membrane. The
difference in gas permeability rates through the
membrane provides the basis for the separation.
OSEA96018 STEVE B HEINEMANN & COLIN WOODWARD, ICI KATALCO

Gas membrane separation is a concentration-driven

process which, for gases, is directly related to the
pressure of the inlet gas and permeate streams. The
separation is actually driven by the component
partial pressure differences across the polymer
membrane. For example, for the separation of the
two gases carbon dioxide (CO,) and methane
(CH,): given a feed stream of COz and CH, at a
given pressure, CO2 the more permeable
component, will pass through the membrane to the
lower pressure side and exit as the permeate stream.

CH, remains on the high pressure side and exits as

the residue stream with essentially no pressure loss.

For a given temperature, pressure and feed

composition, the permeability of an individual
component through a polymer membrane is
constant. This permeability is expressed in units of
component gas flow rate per unit membrane surface
area per component partial pressure difference

across the membrane.

Membranes which incorporate the use of hollow

fibres to provide compact high surface area
performance ?re also available. The modular
design of the membrane elements means that the
membrane area can be adjusted to allow efficient
operation for wide ranges of feed flow rates,
pressures, temperatures and concentrations.

There are currently about 250 membrane-based

gas separation units world-wide, approximately

75% supplied by KMS. Many of these are

relatively small plants, operating virtually

unattended as at Beharra Springs. A particularly

interesting unit operates off-shore in the Gulf of

Thailand processing 540,000 m3/d (20 MMscfd)

of a feed gas, at 6800 kPa, containing 50% CO,

to produce a produc: gas with 15% CO>.

On-shore, two of the largest membrane units are

in Pakistan. at Qadirpur where a feed of 7

million m3/d (265 MMscfd) is treated to reduce
6.5% CO1 to 2% and at Kadanwari where 12.5%
CO2 is reduced to a sales gas specification of

= (Flow Rate) below 3%. The latter plant also contains a fixed

(Membrane Area)(ComponentdP)

The degree of separation of gas components is

defined by the selectivity of the membrane (ratio of
s of ABSORBENTS
rature, flow rate).
For a given membrane area and set of inlet and
Jermeate pressure, the selectivity of the membrane
NilI determine the operating efficiency or amount
md composition of the permeate gas.

I 1e membrane elements at BS are of the

Spiral-wound cellulose acetate type and were

upplied by Grace, now Kvaemer, Membrane

i ystems (KMS). Feed gas is introduced to one face
0 f the membrane module where it travels between
irldividual membrane envelopes. The feed channel
SIracer is designed to promote mixing of the gas as
it travels along the membrane surface. The more

zrmeable gases pass through the membrane into

P
tl-le centre of the membrane envelope and then
?iral around to the steel permeate tube and exit as

Sl
tl le low pressure permeate stream. The product gas

e:Kits at theother end of the module with essentially

nco pressure drop.
bed absorbent unit to polish the H,S content of
the sales gas to below the required 3.8 ppm.

6 INTRODUCTION TO FIXED BED

Fixed beds of chemical absorbents, knqwn

generically as zinc oxides, have been used for
several decades to remove part per million levels
of H2S from hydrocarbon feedstocks such as
naphtha and natural gas upstream of steam
reformers in ammonia, methanol and hydrogen
plants. The sulphur removal, which is required
to avoid catalyst poisoning, is normally preceded
by hydrogenation of mercaptans and other
organic sulphur compounds. It typically
operates at a process temperature of 350400C.

The physical and chemical properties of high

temperature zinc oxides are such that, although
the chemical reaction is the same

ZnO + HIZnS + H,O

at lower temperatures, e.g., below lOOC, the
kinetics of the H,S removal reaction are
NATURAL GAS SWEETENING BY THE COMBINATION OF . . . . . .

GSEA960
18

much less favourable. Consequently the rate of

Other applications of this range of absorbents

reaction and also the ultimate sulphur loading

include removal of COS

from liquid

capacity are much lower and high temperature

hydrocarbons including propane and LPG

and of

absorbents are economically unattractive for

mercury from hydrocarbon gases and liquids.

potential applications at, or near, ambient

Although mercury occurs only in certain gas

temperature.

fields, its removal is essential to protect sensitive

low temperature equipment and for

Beginning in the mid 1980s

ICI Katalco
has

environmental reasons. Use of a

developed a range of absorbents, marketed under

non-regenerable
fixed bed chemical absorbent

the PUR4SPECTM
trademark, which enables

has several advantages and its absorption

cost-effective removal of H2S

from hydrocarbons

capacity will be so high that the initial loading

ranging from natural gas to jet fuel at temperatures

may be sufficient for a 20-30

year plant

from 0-150C
and pressures from
atmospheric to

operating life.

12000
kPa.
Some of the largest installations

sweeten natural gas to pipeline standard for

7
OPERATING HISTORY AND

Petronas
Gas Bhd
at Kertih,
Malaysia and for

PERFORMANCE

British Gas at Barrow (Ref

3)
and Mobil North Sea

at St Fergus
(Ref
4)
in the UK. The total

The plant operating staff are from an agency.

processing capacity of these systems for natural gas

Two men are on 24

hour duty, 14
days on/ 14

treating is currently over 100

million m3/d
(4
billion

days off. A third man works days only. Their

scfd).

permanent presence is supplemented by

occasional visits by a Perth-based manager.

Fixed beds have many operating advantages in

terms of reliability, flexibility, minimal

SEMI-PERMEABLE MEMBRANES

maintenance, etc
but their application can be

constrained by their non-regenerable

nature which

Ongoing performance of semi-permeable

means that absorbent is consumed in direct

membranes is monitored by tracking the

proportion to the rate of impurity removal. This

deterioration of individual component

normally limits their use to removal of ppm
levels

permeabilities
over time. Under normal
of H2S
but means that they are ideally suited to

operation membranes become slowly

providing a final polishing stage downstream of a

compressed owing to the high differential

roughing stage in which the bulk of the impurity

pressure across the membranes (circa 7000

kPa).
is removed. Furthermore, the che
d removal

As the active membrane surface is compressed,

reaction is capable of reducing H2S
to a very low

diffusion of gases become more difficult

and
outlet level, e.g., 0.01
ppm,so,
by accurate

permeability is reduced. Contamination of

analytical measurement and flexible control of the
membrane surfaces will also result in significant
process gas bypass ratio, it is possible to control the

reduction in permeability. Typical life cycle

H2S
content of the export gas very closely e.g., to

length for cellulose spiral-wound membranes is

0.1
ppmv.
This ensures that the product gas
2-4
years. Performance of the membranes at
specification is always met while minimising

Beharra
Springs is detailed in Figure 3 which
absorbent consumption. These features made the

plots CO, and H2S

permeability and gas sales
fixed bed absorbent system the method of choice at

against time.
Beharra
Springs and its subsequent
more-than-satisfactory performance has vindicated
its selection.

PURASPEt?
is a trademark of the ICI Group of Companies.
I

OSEA96018
STEVE B HEINEMANN
&
COLIN WOODWARD
7

The initial set of membranes exhibited very rapid Performance of the second batch
of membrane
deterioration in permeability for both CO, and HIS
has significantly exceeded expectations. It is
to such an extent that within four months of intended to trial the newer type
hollow fibre
operation Beharra
Springs gas sales were polyimide
membranes in the latter part of 1996
significantly curtailed. Analysis of the poor which the manufacturers claim will
reduce
performing membranes indicated severe overall methane losses.
contamination of the membrane surface with
polycyclic
hydrocarbons (PCAs).
This FIXED BED ABSORBENTS
contamination also resulted in physical damage to
the membranes. The PCAs
were traced to The PURASPEC
fixed bed absorbent system at
carryover of condensate from the low temperature BS
consists of two equal-sized reactors piped in
separator in the 1
O-20
ppb
range. Additional a lead-lag series configuration. From
pretreatment facilities were installed including commissioning in November 1993
until August
enhanced activated carbon adsorption. 1995,
the unit was operated in this manner. Gas
analyses then showed that the absorbent in the
A new set of 112
membranes was installed in lead (A) reactor was fully loaded with sulphur so
October 1992
and these membranes have been in it was taken off-line and emptied. Analyses of
service ever since. Apart from the initial reduction the discharged absorbent
showed its sulphur
in permeability from the as new status in the first content to be close to 200
kg/m3.
There was no
months, permeability has remained essentially evidence of any adverse effect from
carryover
constant in the 3%
years to date. Operating and deposition of PCAs.
Gas was now directed
experience has confirmed that : to the B reactor and, because the sulphur removal
reaction zone was contained well within one bed,
i increased temperatures increase permeability the A reactor was left off-line. The
B reactor
and hence the membranes are operating at the was taken off-line and emptied in
January 1996
maximum sustainable temperature consistent since when the unit has been running
with only
with allowable membrane design the A reactor in service. The H2S
content of the
temperatures. export gas is controlled to 3.1
f
0.1
ppmv
by
manual adjustment of the bypass valve with
ii increased gas velocities at the membrane reference to regular analytical checks.

upper surface lead to higher permeabilities.

It
can be postulated that this effect may be 8 CONCLUSIONS
because the more turbulent gas velocities
counteract boundary layer effects. The Beharra
Springs gas production and
processing facility has been a technical and
The ability to increase gas velocities is currently commercial success. It now
operates reliably
restricted by maximum allowable pressure drop in with very low operating and
maintenance costs
the membrane units between the feed inlet and and is expected to continue to export
up to
residue outlet (max 230 kPa). This pressure drop 760,000
m3/d
(28 MMscfd) consistently.
has increased with time due to activated carbon dust
deposition in gas passages of the membrane units. 9 ACKNOWLEDGEMENTS
Additional particulate filtration was installed
in1995 to minimise this source of contamination. The authors thank Kvaemer
Membrane Systems
for their contributions to this work and the
managements of Boral
Energy Resources Ltd
and ICI K&talc0
for permission to publish this
paper.