NZ625041B2 - A method for accelerated testing of a membrane module - Google Patents
A method for accelerated testing of a membrane module Download PDFInfo
- Publication number
- NZ625041B2 NZ625041B2 NZ625041A NZ62504112A NZ625041B2 NZ 625041 B2 NZ625041 B2 NZ 625041B2 NZ 625041 A NZ625041 A NZ 625041A NZ 62504112 A NZ62504112 A NZ 62504112A NZ 625041 B2 NZ625041 B2 NZ 625041B2
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- New Zealand
- Prior art keywords
- membrane
- cycles
- testing
- membrane module
- filtration
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Links
- 239000012528 membrane Substances 0.000 title claims abstract description 230
- 230000035882 stress Effects 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 238000001914 filtration Methods 0.000 claims description 58
- 239000000835 fiber Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 8
- 230000004907 flux Effects 0.000 claims description 7
- 238000005336 cracking Methods 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims description 6
- 229940035295 Ting Drugs 0.000 claims description 3
- 238000009285 membrane fouling Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000875 corresponding Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims 1
- 239000000706 filtrate Substances 0.000 description 29
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000012466 permeate Substances 0.000 description 10
- 239000012530 fluid Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
- 230000001419 dependent Effects 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 230000004059 degradation Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000249 desinfective Effects 0.000 description 4
- 239000003295 industrial effluent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000009662 stress testing Methods 0.000 description 3
- 230000001702 transmitter Effects 0.000 description 3
- 241001182492 Nes Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011016 integrity testing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000750 progressive Effects 0.000 description 2
- 230000000717 retained Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229940112112 Capex Drugs 0.000 description 1
- 229910015798 MOS2 Inorganic materials 0.000 description 1
- 108060005042 MOS2 Proteins 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000001464 adherent Effects 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 241000902900 cellular organisms Species 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003278 mimic Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000001717 pathogenic Effects 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000003134 recirculating Effects 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005429 turbidity Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2315/00—Details relating to the membrane module operation
- B01D2315/06—Submerged-type; Immersion type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/04—Backflushing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
- B01D65/104—Detection of leaks in membrane apparatus or modules
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
- C02F2209/445—Filter life
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
Disclosed is a method for accelerated testing of a membrane module for resistance to cyclic stresses during operation of an industrial membrane separation process comprising loading at least one membrane module into a test cell of a test plant; conducting said industrial membrane separation process while subjecting said membrane module to cyclic stresses during a plurality of membrane operating cycles, each cycle being of significantly lesser duration than used for operation of said industrial membrane separation process in an operating plant; and testing said membrane module for component failure caused by said cyclic stresses. while subjecting said membrane module to cyclic stresses during a plurality of membrane operating cycles, each cycle being of significantly lesser duration than used for operation of said industrial membrane separation process in an operating plant; and testing said membrane module for component failure caused by said cyclic stresses.
Description
A METHOD FOR ACCELERATED TESTING OF A MEMBRANE MODULE
This invention relates to a method of accelerated g of a membrane
module.
Membrane processes are commonly used in industry for separating
components from fluid mixtures, whether the fluid is in liquid or gaseous form.
Membranes of semi-permeable material enable separation of ents as
follows. Some components of the fluid mixture permeate through the ne,
though at different rates. Other ents will not pass through the membrane
at all. Such components are said to be retained by the ne.
In the field of water ent, for example, membrane processes may be
used to purify an “effluent” water stream containing water in admixture with
contaminant components. Such industrial processes involve membrane
tion of the contaminant components from the effluent water, allowing the
treated water to be re-used by industry or discharged safely into the environment.
An example of such a process, advantageously involving a combination of
membrane separation processes (nanofiltration and e osmosis) is disclosed
in the Applicant’s WO 2010037156 “Process and Plant for Treating a Water
Stream”, the contents of which are hereby incorporated herein by nce.
Membrane processes may be used to achieve separation of substances in many
applications and process media including water treatment for desalination,
filtration and in membrane bioreactors, which are a specialised type of filtration
application.
Industrial application of membrane processes such as disclosed in WO
2010037156, requires suitable equipment in the form of membrane modules for
which s designs are ble: hollow fibre, tubular, spiral woundgand —
less commonly plate and frame. Hollow fibre membrane modules are often
red because hollow fibre membranes allow the highest membrane surface
area per unit volume of a vessel to accommodate them. A hollow fibre
membrane module typically comprises a bundle of the hollow membrane fibres
sometimes odated within a pressurisable housing or immersed in an
open tank configuration. A hollow fibre bundle extends between two opposed
headers or "pots" forming part of the module housing and the opposite ends of
each hollow fibre are potted and sealed within each “pot”, typically of polymer or
resin al (particularly epoxy or polyurethane resin), to form a tube sheet.
The ing design is analogous to a shell and tube heat exchanger. The fluid
to be treated is contacted with the hollow fibres such that components are
separated, with liquid lly passing inwards to the hollow centre of the fibre
under the action of a moderate pressure gradient, and the solids ing
outside the fibre.
Membrane separation ses often e a number of such
membrane modules operating in parallel. A number of such modules may
comprise a rack which is located, either in a pressurised system or submerged in
a tank style water treatment cell to which water for treatment has been introduced
to remove contaminants from the water, for example in a membrane bioreactor.
The water treatment cell is lly agitated by sparging air or other gas through
it and or by recirculating a liquid flow through it. Such agitation and or
recirculation prevents solids buildup on ne fibres that would impair
membrane treatment performance.
In an industrial plant, such as a waste water treatment plant (but not by
any means limited to such plant), the selected membrane modules are likely to
2O have a significant capital cost. At the same time, membrane service life of
several years is likely to be required. A constraint on membrane service life is
membrane module failure due to repeated cyclic stresses imposed on the hollow
fibre membranes and supporting components such as the pots during operation.
In normal operation, hollow fibre membranes are ted to filtration, relaxation
and pressure testing . Treated fluid must be extracted from the hollow fibre
membranes by means of a pressure differential. This can be by means of suction
in the case of submerged fibres, or by pressure difference in pressurised
systems. In each case, a pump or source of pressure difference is "on" during a
filtration cycle, which applies substantial bending forces and cyclic stresses on
3O the membrane module system, particularly at the pots in which opposed ends of
the hollow fibre membranes are sealed. The pots are also likely to be subjected
to other cyclic ical stresses such as periodic stresses in the reverse or
pressurised direction during a pressurisation cycle. Periods when the pump or
other source of pressure means is "off" are called relaxation cycles. Such
relaxation cycles may have the same on as filtration cycles or may be much
r. In water treatment plants, sludge removal operations, or backwashing,
may be conducted during relaxation cycles, for example through agitating mixed
liquor surrounding the hollow fibre membranes, shaking them to remove .
In addition, pressure integrity testing/pressure decay cycles may be
conducted in which the hollow fibre membranes are pressurised with compressed
air and dynamic behaviour is observed in order to assess membrane integrity and
absence of leaks. Decay or decline in pressure (for example) over a pre-set time
provides a direct measure of ity. Other pressure decay tests can use a
vacuum source and observe rate of increase of pressure. In either case, if the
decay gradient is too steep, particularly being steeper than a pre—determined
gradient consistent with membrane integrity, the membrane has unsatisfactory
integrity and is not fit for purpose.
Daily operation of a membrane separation process within a water
treatment plant may lly be designed to e, for e and without any
intent of limitation, over one hundred filtration cycles (about 14 minute design
cycle time) and one pressurisation cycle per day.
2O Over a period of time, the continuous imposition of cyclic stresses —
possibly in combination with corrosion/degradation caused by chemical agents for
example used for disinfection (for example sodium hypochlorite) — can lead to
damage to the membrane , particularly through cracking and fatigue
failure. If cracking, particularly at the pots or tubesheets, occurs the membrane
module is typically no longer serviceable. This is a very significant failure mode,
particularly in ne bioreactors, which can occur despite the membrane
material for the hollow fibres being ise correctly selected from the
perspective of mechanical properties (see, for example, ess, AE et al,
Mechanical analysis of hollow fibre membrane integrity in water reuse
3O ations, Desalination 180 (2005), 5-14). The reason is that separation of
fluid to be treated from treated fluid: for example mixed liquor (dirty water) from
clean water in the context of water treatment is no longer possible. The
ne module must be discarded.
As alluded to above, it may be several years before a membrane module
becomes unserviceable. However, the exact timing of failure (service life) is
uncertain and this makes planning and budgeting for a water or wastewater
treatment plant difficult. Such uncertainty also impacts selection of a membrane
module which is best suited for the ne separation process. All other
factors being equal, the plant designer will select a membrane module having the
longest service life. If it takes several years, for example 5 years or more, to
determine likely failure time, through statistical is, it is very ult for an
optimal selection to be made. Whilst manufacturer and brand provides a guide to
membrane module service life, greater certainty is required. The membrane
module manufacturer is not in an ideal position to provide an accurate service life
prediction (and likely will not e one). The reason is simple in many cases.
The specific operating nment for a particular industrial ne
tion process often cannot be reasonably replicated by a ne module
manufacturer ing its usual testing protocols. A real challenge for the
membrane module manufacturer is duplicating the often time variant
compositional nature, and - to a perhaps lesser extent - properties (such as
temperature) of fluids subjected to membrane separation. For example, effluent
subjected to membrane separation in a water treatment plant often has a highly
dynamic, that is time and/or seasonally variant, composition and flow rate.
Properties such as temperature may also vary with time and the nature of the
effluent being treated by the water treatment plant. ne module service
life predictions based on tests using sample, or synthetic, effluents of near-static
or near-constant composition is simply not sufficiently te for budgetting
purposes.
It is an object of the present invention to provide r accuracy of
prediction of membrane module service life than currently available.
3O With this object in view, the present invention provides a method for
accelerated testing of a membrane module for resistance to cyclic stresses during
operation of an industrial membrane separation process comprising loading at
least one membrane module into a test cell of a test plant; conducting said
ne separation process while subjecting said membrane module to cyclic
stresses during a plurality of membrane operating cycles, each cycle being of
significantly lesser duration than used for operation of said industrial membrane
tion process in an operating plant; and g said ne module for
ent failure caused by said cyclic stresses.
Such testing, which may usefully include imposing chemical treatments
similar to those used in the industrial membrane separation process (though
including testing under more aggressive chemical conditions), allows a mean
service life for the membrane module to be predicted, advantageously in a much
lesser timeframe than actual service life. Such information may be
advantageously employed to assist in membrane module selection and cost
budgeting for a membrane separation plant.
The method accelerates ne module testing because the test cycle
duration is significantly shorter than design duration, the duration to be used for
membrane operating cycles in the operating plant. Consequently, frequency of
membrane operating cycles applied during testing is significantly greater than the
design frequency, that is, the ncy at which stress cycles will be applied to
the membrane module in normal industrial service. industrial service is not
limited to commercial e. Practice of membrane tion processes as
part of a public utility is also included within the scope of industrial service.
Advantageously, the test plant forms part of, or is connected to, an actual
operating plant implementing the industrial membrane separation process. This
integration of test plant and operating plant enables testing of ne s
under actual industrial ing conditions, rather than simulated or synthetic
conditions in an artificial environment, addressing inaccuracies created by failure
to test membrane modules under dynamic compositional, property and flow rate
ions typically encountered in industrial plants. The results of testing are
substantially more reliable than tests performed distant from an operating plant
implementing said industrial membrane separation process, potentially on bench
or very small scale, with fluid s for membrane sing of near-constant
or static quality and rather than time variant quality.
Membrane operating cycles, which are typical and of particular though not
limiting importance, may comprise filtration cycles; relaxation cycles; and/or
pressure decay testing cycles in which the membranes of the membrane modules
are tested for leaks. That is, the membrane modules may only be subjected to
tion and relaxation cycles; or pressure decay testing cycles. Alternatively,
membrane modules may be subjected to both filtration and tion cycles and
pressure decay testing cycles. Filtration cycles correspond with s when
pump means forming part of the test cell are operated, or turned on, to apply
pressure (positive or negative) to a membrane. Relaxation cycles correspond
with periods when pump means forming part of the test cell are turned off.
Membrane cleaning operations, such as backwashing or sludge removal
operations, may be conducted during relaxation cycles. These cycles are
significantly rated over operating plant cycles for test purposes.
The test plant may include a plurality of test cells. in such cases, test cells
i5 may be operated in parallel with one test cell imposing different membrane
operating cycles and a different cyclic stress regime on membrane modules than
in another test cell. Chemical testing, to assess corrosion/degradation
phenomena, may also be practised in one or more test cells. Such parallel test
cell operation accelerates the collection of test data.
The frequency of filtration and relaxation cycles to which a membrane
module is subjected during testing is accelerated to a frequency which would
lly be icantly greater than the frequency of any pressure
decay/pressure integrity g cycles used in the operating plant, for example up
to and greater than 100 filtration cycles to 1 pressurisation cycle. This can induce
significant pressure shocks at pumps and valves which operating plants would
normally take steps to prevent (see, for e, Huisman, IH and Williams, K,
Autopsy and failure analysis of ultrafiltration membranes from a waste-water
treatment system, nation 165 (2004), 161-164)). The g method, in
st, is intended to purposefully induce such pressure shocks to increase
testing severity.
The membrane module to be tested conveniently comprises hollow fibre
membranes as such membranes are often selected for industrial membrane
separation processes for reasons described above. In this case, the ne
module comprises a housing accommodating a bundle of the hollow membrane
fibres, each hollow fibre ing between two opposed headers (also known as
pots) with the opposite ends of each hollow fibre being potted and sealed within a
header, typically of polymeric or resin, such as epoxy or polyurethane resin,
material. These pots or headers are critical components of the membrane
module. Component failure would be indicated; in particular, when cracking of a
pot or adhesion failure n the fibres normally retained in the pot, and the
pot, occurred during testing. The membrane module testing method may also be
applied to other membrane module types such as tubular, spiral wound and plate
and frame membrane module types.
During testing, a plurality or rack of membrane s may be loaded
into the test cell to enable simultaneous testing. The resulting increase in data
accelerates prediction of the likely time to failure (i.e. service life) of a membrane
module in service. The prediction of likely time to failure should not require any
complicated atical modelling.
The method may comprise subjecting each membrane module to a testing
cycle having a predetermined number of stress cycles to be imposed over a
predetermined period of time. The predetermined number of stress cycles may
correspond with required minimum service life (typically measured in years)
though this number of stress cycles will be imposed in a much shorter period (in
the order of weeks or months).
The membrane module testing method may be used for other purposes.
During testing, duration of a filtration cycle will be icantly r than during
normal service. Such extremely short filtration cycles may increase filtration flux
over normal service. Filtration flux during g may thus be ed and
ed with filtration flux during normal e.
Alternatively, or additionally, testing may be used to assess whether
resistance to membrane fouling is improved by r filtration cycle duration.
The membrane module testing method may be used to test membrane
modules and predict membrane module service life for a range of different
membrane separation processes. However, the testing method is particularly
ageous for industrial ses in which typical required membrane
service life has a duration of a plurality of years.
Liquid treatment processes, especially water treatment processes, are a
ularly important example of this ry of processes since membrane
separation processes are widely used for separation of inants from water.
In addition, membrane modules for use in large volume water treatment plants
have a typically high capital cost. The testing method is especially suitable for
testing membrane modules to be used in membrane bioreactors, especially under
submerged conditions. For testing this application, test cell(s) are configured to
simulate membrane bioreactor(s) and membrane modules, typically comprising
hollow fibre membranes are submerged in mixed liquor in the test ).
The testing method may be applied to any waste water treatment
processes ing those where a membrane module will be subjected to a
temperature greater than about 2590, or even greater than 3090 and approaching
40%. At such temperatures, which may ularly be encountered with effluent
water s containing effluent from an industrial process, membrane module
operating temperature may be greater than the glass transition temperature of the
polymer or resin material of the headers of the membrane modules Thus the
g method may be applied at ent temperatures to assess dependence of
service life on service ing temperature.
Testing severity may also be increased by imposing various chemical
ents, such as sodium hypochlorite solutions typically used as disinfectants
in water treatment processes, at a plurality of solution strengths, for varying
durations so as to simulate the type of chemical attack and associated
degradation that might occur during normal use over a period of years. Such
chemical treatments could also be imposed where the membrane operating cycle
duration is the same as, or similar to, duration used in the operating plant.
An embodiment of the method of accelerated testing of a membrane
module in accordance with the present invention will now be described with
reference to the accompanying figures in which:
Fig. 1 is a tic process flowsheet for a water ent plant
ing a membrane module of type to be tested in accordance with the method
of testing of the invention.
Fig. 2 is a schematic illustration of a membrane module used in an
ultrafiltration stage of the water ent plant of Fig. 1.
Fig. 3 is a s flow m for a test plant for testing membrane
modules in accordance with the method of the present invention.
Fig. 4 is a schematic process flowsheet for a water treatment plant
ing a test plant for which the process flow diagram is provided as Fig. 3.
Referring now to Fig. 1, there is shown a water treatment plant 100
comprising two bic reactor stages (AFH and AR2) to produce treated water
and biogas, a portion of which may be combusted in a gas turbine to generate
power for the plant. Water treatment plant 100 treats up to 35 million litres of
waste water per day. ARt and AR2 supply pre-treated influent water to aeration
basins and membrane bioreactor (“MBR”) systems (AB1/MOSf and ABZ/MOS2).
The anaerobic reactors treat raw influent water which is a combination of
domestic nt and industrial effluent received from a Kraft process pulp and
paper mill through a dedicated waste line through a digestion process. This
effluent or waste water has contaminant ents as measured by a high
biochemical oxygen demand (”BOD”) and dissolved organic carbon (“DOC”)
content which provides a strong brown colouration to the waste water.
The treated effluent from the anaerobic reactor stages AW and AR2
passes to the aeration basins A81 and A82 respectively. These basins provide
aerobic digestion conditions to further treat the waste water. The mixed liquor
(“dirty water”) is recirculated from aeration basins A81 and A82 into ultrafiltration
(“UF”) membrane operating systems M081 and M082 each of which includes a
large number of membrane modules 40 as schematically illustrated in Fig. 2.
Water treatment plant 100 could comprise a large number of such UF membrane
operating systems (M08) and several thousand membrane modules 40 for UF
separation of the ent represented by high BOD. The resulting ultrafiltrate
or permeate has nearly undetectable levels of BOD. Each combined AB+MOS
system comprises a membrane bioreactor (“MBR”) and the ultrafiltrate may be
ed to as MBR filtrate or permeate.
MBR permeate is directed to nanofiltration process unit 20 for removing
DOC from the MBR permeate to e a water quality acceptable for feed to
reverse s (“RO”) process unit 30. The RO process unit 30 performs
desalination (especially removing te) and allows production of a water
stream that may be ed to the pulp and paper mill with benefit for the
process economics of that mill.
Fig. 2 shows a schematic, referenced at
1O http://www.separationprocesses.com/Membrane/MT_FigGen15.htm, of an
ultrafiltration (“UF”) ne module 40 suitable for use in the M081 and
M082 units. UF membrane module 40 is of hollow fibre type comprising a
bundle 44 of hollow fibre membranes 41 accommodated within a pressurisable
housing 46. Bundle 44 s between two vertically opposed headers or pots
42 and 43 forming part of the module housing 46. Headers 42 and 43 are of
epoxy resin. The opposite ends of each hollow fibre of bundle 44 are embedded
and sealed within headers 42 and 43 respectively. The resulting design of
membrane module 40 is analogous to a shell and tube heat exchanger with feed
mixed liquor 47 entering the housing 46 (shell side) ting the hollow fibre
membranes 41 with “clean” water, essentially free of BOD, permeating the
membranes 41 to enter the lumens 45 of membrane fibres to be recovered as a
permeate stream 49. Water relatively concentrated in BOD is recovered as a
retentate stream 48. The flow 51 of permeate stream 49 is counter-current to the
flow of the feed mixed liquor 47 through the housing 46.
During typical daily (24 hour duration) operation of membrane modules 40,
the bundle 44 of hollow fibre membranes 41 is subjected to about 110 filtration
cycles in which permeate 49 is recovered, whilst corresponding pump means are
operated, by suction from the hollow fibre membranes 41. Therefore, each
filtration cycle, which imposes the cyclic stress above described, has a design
3O duration of approximately 14 minutes. Following a filtration cycle, pump means is
turned off during a relaxation cycle (also of 14 minute design on). Sludge
removal ions are conducted throughout this 14 minute cycle time, but
particularly facilitated by the relaxation step, for example by agitating mixed liquor
surrounding hollow fibre membranes 41 to shake the membranes and remove
adherent sludge. The sludge so d is typically carried away by a
recirculation flow.
In a distinct testing cycle, med at lesser ncy than filtration and
relaxation cycles, the bundle 44 of hollow fibre membranes 41 is pressurised by
compressed air in a cycle called a pressure integrity testing (“PIT”) cycle or
pressure decay g (“PDT”) cycle which also imposes a cyclic stress on the
membrane modules 40. PIT or PDT testing is used to check whether hollow fibre
membranes 41 leak. In a PIT/PDT test, hollow fibre nes 41 are
pressurised to a predetermined pressure (for example 105 kPa) with compressed
air. Decay of the hollow fibre membrane 41 pressure with time indicates whether
leaks exist in the hollow fibre nes 41. Such leaks are issible since
they compromise the extremely high mechanical disinfection, and reduction in
biota ially pathogenic bacteria and protozoa) which is required during a
water treatment s.
The filtration and PIT/PDT cycles impose cyclic mechanical stresses on the
membrane module 40. In particular, the headers 42 and 43 of epoxy or
polyurethane resin are subjected to bending forces which will cause failure
through stress cracking. When such cracking occurs, mixed liquor will mix with
permeate and the membrane module 40 is no longer serviceable. Membrane
module 40 must then be replaced. Whilst it is ted that such failure will
occur at a mean service life of about 5 years (approximately 200000 filtration
cycles), there is considerable uncertainty over this and cost/capex budgeting for
replacement of membrane modules is y uncertain.
Fig. 3 shows schematic of a test plant 60, which — as shown in Fig. 4 —
forms part of an operating water treatment plant 100 located in and,
Victoria, Australia. Water treatment plant 100 has capacity to treat a very high
volume of aqueous effluent comprising domestic and industrial effluent
(particularly pulp effluent from a Kraft paper mill) having different and time variant
compositions, colour and temperature. For example, the domestic effluent
contains relatively low levels of sulphate whereas the industrial effluent contains
relatively high levels of sulphate and typically has a higher temperature.
The domestic and industrial effluents are mixed into a mixed liquor for
treatment within the water treatment plant 100. Having test plant 60 forming part
of operating treatment plant 100 enables testing of membrane s 40 under
rial operating conditions. So, the results of testing are more reliable than
tests performed distant from the water treatment plant 100, potentially on bench
or very small scale, with effluents of constant rather than time variant quality.
The test plant 60 is lled by the water treatment plant 100 control
system (PLC/SCADA control system).
Test plant 60 is used for implementing e g protocols in which
ne modules 40 are subjected to cyclic stresses during a plurality of
ne ing cycles, each cycle being of significantly lesser duration than
used for ultrafiltration using the MOS units; and testing the membrane s
40 for component failure caused by said cyclic stresses. In particular, the stress
cycles are imposed on the membrane modules 40 by the filtration (suction),
relaxation and pressurisation cycles described above. Such g allows a
mean service life for the membrane module 40 to be predicted by acceleration
mechanical stress testing in a period significantly less than estimated service life.
Such information may be advantageously employed to assist in membrane
module selection and cost budgeting for water treatment plant 100 and, in
particular, the UF membrane operating systems (MOS units exemplified by M081
and M082).
Test plant 60 includes two test cells 61 and 70, each configured as a
membrane bioreactor in which ne modules 40 are submerged while
conducting the ne separation process. Each test cell 61, 70 is loaded
with a rack of 16 membrane modules 40 for parallel testing, such testing involving
ultrafiltration of mixed liquor for removal of BOD as described above.
Simultaneous testing of a icant number of membrane modules 40 allows
3O data acquisition to be accelerated further as sample size is increased and mean
membrane module 40 service life can be predicted with greater accuracy. It is to
be understood that membrane modules 40 are not expected to fail at the same
time. Rather, different membrane modules 40 will have different endurance to
stress cycles and fatigue failure and the output of testing is typically a statistical
distribution of duration to failure, this tical bution having a mean
duration to failure.
Test cell 61 comprises three filtrate pumps 62 operable in parallel
dependent on the vacuum pressure that is required for the test cell 61. One or
more filtrate pumps 62 are therefore used dependent on the required operating
pressure. Higher suction pressures will require more of the pumping capacity to
be used. Filtrate pumps 62 operate to draw UF permeate, at a temperature about
3090, from a single rack of 16 membrane modules 40 located in test cell 61
during a filtration cycle. Filtrate is sent to test filtrate storage tank 64 A
submersible pump 66 in the filtrate storage tank 64 returns filtrate back to the test
cell 61 based upon liquid level in the filtrate storage tank 64. The required filtrate
pumps 62 e continuously. Filtrate flow is controlled by two actuated valves
68 and 69, conveniently of solenoid type.
Test cell 61 is also configured to enable pressure decay/pressure ity
PIT”) testing, that is testing of the bundle 44 of hollow fibres for
impermissible leaks as above described. To that end, air compressor 63 supplies
compressed air through line 162 and automated control valve 163 to pressurise
membrane modules 40 when required during a T test. Alternatively,
compressed air may be supplied from the compressed air supply for water
treatment plant 10.
Test cell 70 operates identically to test cell 61 except that it is configured,
in accordance with membrane module 40 test strategy, not to perform PDT/PIT
testing. Test cell 70 therefore subjects its rack of 16 ne s 40 to
filtration and relaxation cycles only. Test cell 70 has three variable speed filtrate
pumps 72 (of progressive cavity type) le in el operable in parallel
dependent on the vacuum pressure that is ed for the test cell 70. One or
more filtrate pumps 72 are therefore used, dependent on the required operating
pressure, to draw filtrate from a single rack of 16 membrane modules 40 located
in test cell 70 during a filtration cycle. Filtrate is sent to filtrate e tank 74.
Submersible pump 66 in the filtrate storage tank 64 s filtrate back to the test
cell 70 based upon liquid level in the te storage tank 64. The required filtrate
pumps 72 operate uously with filtrate flow being controlled by two actuated
valves 78 and 79, conveniently of solenoid type.
Expected filtrate flow range from each rack is in the range 7.5 to 25 m3/h
and operating trans membrane pressure (TMP) during a filtration mode is 45 kPa.
Filtrate flow range to test cell 60 or 70 via submersible pump 64 may be up to 50
m3/h.
Test plant 60 may be operated, by way of example, as follows. Filtration
test cycle on for both test cells 60 may be pre-set at 10 seconds, this
duration being very significantly less than the 14 minutes period required in
normal service of water treatment plant 10. The filtration cycle duration is the
duration for which filtrate pumps 62 and 74 draw filtrate from the rack of
membrane modules 40. Filtrate pumps 62 and 74 are controlled to the t
duration for the filtration cycle. A tion cycle is followed by a relaxation test
cycle also having a pre-set duration. In this case, duration of the filtration and
relaxation cycles are the same and set at 10 seconds for g. This test cycle
duration is purely by way of example but it is significantly less than the about 14
minute duration of filtration and tion cycles during normal service of M081
and M082 of the water treatment plant 100. Consequently, the frequency of
stress cycles imposed on the membrane modules 40 is accelerated to ncy
being very significantly greater than during normal service of M081 and M082 of
water treatment plant 100.
During the filtration cycle (10 seconds duration for one test protocol),
actuation valve 68 is open and actuation valve 69 is closed. The three filtrate
pumps 62 are here operated to achieve a vacuum re of -45 kPa, measured
and controlled by pressure transmitter 67. Flow is also measured by flow meter
65 but will not be the lling parameter.
At the completion of the filtration cycle, actuation valve 69 will open and
mixed liquor will be drawn from the filtration storage tank 64 during a relaxation
3O cycle. 0.5 seconds later, actuation valve 68 will close. During the relaxation cycle
(10 seconds duration for one test protocol), filtrate pumps 62 operate at the same
speed as during the filtration cycle (that is pump speed remains on hold). A
different speed control program for filtrate pumps 62 could be adopted.
At the completion of the relaxation cycle, actuation valve 68 will open and
0.5 seconds later, actuation valve 69 will close. The intention is that at no time
are both actuation valves 68 and 69 closed and that when swapping from filtration
to relaxation and back that for a short period of time both actuation valves 68 and
69 are open. This is required as filtrate pumps 62 are progressive cavity type.
Further, the testing protocol is very aggressive by its nature and such short cycle
times put significant pressure on valves and pumps as well as, potentially, on the
1O membrane modules 40. Pressure shocks are quite likely in contrast with
operating plant. These pressure shocks can be ed intentionally to
se the test severity, or can be minimised to reduce it down to a level more
resembling normal operational pressure exposure. The test filtration and
relaxation cycle times are ore ideally to be selected to produce failure data
that is relevant to ting membrane module 40 service life and rather than
failure data that s simply from the testing regime.
Test cell 61 is also configured for PDT/PIT testing. At a time determined by
an operator of the test plant 60, te pumps 62 are turned off and a PDT is
performed by opening control valve 163 and ing compressed air through
2O line 162 for delivery to membrane modules 40. The PDT/PIT test mimics the test
as required, by regulation, for M081 and M082 of water treatment plant 100.
Compressed air is delivered to the membrane modules 40 for a pre—set
pressurisation duration (60 seconds for one testing protocol) in order to
pressurise the hollow fibre membranes 41. At completion of the pressurisation
duration (60 seconds), provided that a ient start pressure is obtained, the
PDT/PIT test begins. Control valve 163 is closed and drop in re of the
hollow fibre membranes 41 is measured over 60 seconds. This on is also
for example only. Different durations could be selected for g. The water
treatment plant 10 control system (SCADA network) records the results. At
3O conclusion of the PDT/PIT test, the test cell 61 may once again be returned to
testing during filtration and relaxation cycles. However, test cell 61 could also be
used simply to perform PDT/PIT tests to determine the influence of such testing
on membrane module 40 e failure. In this way, test plant 60 can test for the
most likely cause of membrane module 40 failure, cyclic stresses due to
filtration/relaxation cycles or cyclic stresses due to PDT/PIT testing or a
combination of the two types of cyclic stress. lf PDT/PIT testing is a cause of
failure, this has ations for use of such testing in water treatment plant 100.
Test cell 61 is returned to filtration/relaxation testing following removal of
air (typically though, due to the possibility of hollow fibre membrane 41 failure, not
always) from the hollow fibre membranes 41 of membrane modules 40 (see Fig.
2). in order to do this, solenoid valve 165 is opened and service water passed
1O through the venturi 164 to provide motive force. This differs from the protocol
used in water treatment plant 100 where a compressed air supply is used to
provide motive force to venturi(s) in M081 and M082. After a preset time,
solenoid valve 166 is opened and a vacuum is d to the hollow fibre
membranes 41. This vacuum removes excess air and draws an quid mixture
into line 167. This air-liquid mixture is then discharged into test cell 61. After a
t duration (60 seconds for example), solenoid valves 165 and 166 are
closed and test cell 61 is ready for restart of tion/relaxation cycle stress
testing.
Test cell 70 involves similar operation to test cell 61 except that PDT/PIT
2O testing is not performed. Test cell 70 may be used to test membrane modules 40
with different filtration/relaxation cycle duration (say 20 s test cycle
duration rather than 10 seconds) being used during testing. The actuating valves
78 and 79 are operated in the same manner as actuating valves 68 and 69.
re transmitter 77 takes the place of pressure transmitter 67 and flow meter
75 takes the place of flow meter 65.
An indicator of hollow fibre membrane 41 failure during filtration/relaxation
cycle testing is increased turbidity downstream of test cells 61 and 70. ity
is therefore monitored as an indicator of possible failure. Membrane modules 40
can then be inspected to assess r failure has occurred and location of any
cracks in the membrane module headers ("pots") 42 and 43.
Tests may involve testing with waste waters at different temperatures.
Though failure is less likely with domestic effluent water having temperature of
-2596, membrane module 40 g in that temperature range may be
conducted. Tests at higher temperature, and in particular in the temperature
range 30-3990 typical of conditions where the waste water contains waste water
from the Kraft process pulp mill are also performed. Membrane operating cycle
duration and frequency may be varied during testing dependent on waste water
temperature.
Testing severity in test cells 61, 70 may also be increased by imposing
various chemical treatments, for example sodium hypochlorite solutions typically
used as disinfectants in water treatment processes, at a plurality of solution
strengths, for varying durations so as to simulate the type of chemical attack and
associated degradation that might occur during normal use over a period of
years. Such chemical treatments could also be imposed in test cycles where the
membrane operating cycle duration is the same as, or similar to, duration used in
the ing plant.
Different membrane modules 40 will endure stress testing for ing
s. At the end of testing, a tical distribution of number of fatigue
failures of pots 42, 43 to time to failure can be ed and a mean time to failure
(equated to predicted service life e the number of test cycles to failure in
testing plant (duration of 20 seconds = 10 seconds tion/10 seconds
relaxation) can be compared with the about 200000 cycles equating with 5 years
service (or 40000 cycles per year)) of a membrane module 40 predicted using
conventional statistical techniques. A table showing conversion from testing
duration to predicted service life is as follows:
Table 1
Conversion — Accelerated Testing Duration to Service Life
Number of Cycles g Duration (weeks) Predicted Service Life
(weeks) (years)
50000 1.6 1.25
75000 2.4 1.88
100000 3.3 2.5
125000 41 3.1
150000 50 3.75
200000 6.6 5.0
As can be seen, mean service life can therefore be predicted in highly
accelerated manner in 6 to 7 weeks using test plant 60 (based on 100% plant
availability) rather than the 5 plus years it could take if membrane modules 40 are
tested in normal service of water treatment plant 10. Such accelerated testing
enables more confidence in membrane module 40 selection and ing for
water treatment plant 100, particularly in terms of membrane module 40
replacement costs.
Test plant 60 may be used for other purposes. Above was described an
extremely short filtration/relaxation cycle duration (10 seconds each for filtration
and relaxation). Such extremely short cycle duration may impact either positively
or negatively on membrane flux and membrane tion efficiency. Test plant
60 allows the effect of filtration/relaxation cycle duration on separation efficiency
to be investigated.
Alternatively, or additionally, testing plant 60 may be used to assess
whether resistance to membrane fouling is improved by r filtration cycle
duration. Fouling is a icant problem in many membrane separation
processes, particularly those used in waste water treatment, and most notably
within membrane bioreactors. If filtration cycle duration can be used to improve
resistance to fouling, and perhaps result in lowered usage of cleaning chemicals
or other fouling ents such as agitation and / or recirculation flow, this would
also have benefits for water treatment plant to economics, either by permitting
reduced initial capital investment, or ng increased hput capacity with
vely minor equipment modifications (fast acting valves, and more precise
controls etc).
cations and variations to the method for accelerated testing of a
membrane module described in this specification may be apparent to the skilled
reader of this sure. Such modifications and variations are deemed within the
scope of the present invention.
Claims (27)
1. A method for rated testing of a membrane module for resistance to cyclic stresses during operation of an industrial membrane separation process comprising loading at least one membrane module into a test cell of a test plant; conducting said rial membrane separation process while ting said membrane module to cyclic stresses during a plurality of membrane operating cycles, each cycle being of significantly lesser duration than used for operation of said industrial membrane separation process in an operating plant; and testing said membrane module for component failure caused by said cyclic stresses. 10
2. A method of claim 1 wherein said test plant forms part of, or is connected to, an operating plant enting said industrial membrane separation process.
3. A method of claim 1 or 2 wherein said testing allows a mean service life for the ne module to be predicted in a much lesser timeframe than actual service life. 15
4. A method of claim 3 wherein frequency of membrane operating cycles d during testing is significantly greater than the design frequency being the frequency at which stress cycles will be applied to the membrane module in normal industrial service.
5. A method of any one of the preceding claims wherein said membrane 20 operating cycles comprise filtration cycles; relaxation cycles; and/or pressure decay testing cycles in which the membranes of the ne modules are tested for leaks.
6. A method of claim 5 wherein said membrane modules are only subjected to filtration and relaxation cycles; or pressure decay testing cycles. 25
7. method of claim 5 wherein ne s are subjected to both filtration and relaxation cycles and pressure decay g cycles.
8. A method of claim 6 or 7 wherein filtration cycles correspond with periods when pump means forming part of the test cell are turned on to apply pressure to membrane; and tion cycles correspond with periods when said pump means forming part of the test cell are turned off.
9. A method of any one of the preceding claims wherein said testing plant includes a plurality of test cells.
10. A method of claim 9 wherein said test cells are operated in parallel with one test cell imposing different membrane operating cycles and a different cyclic stress regime on membrane modules than in another test cell. 1O
11. A method of any one of claims 5 to 10 wherein the frequency of filtration and relaxation cycles to which a membrane module is subjected during testing is accelerated to be significantly greater than the ncy of any pressure decay/pressure ity testing cycles
12. A method of any one of the preceding claims wherein said ne 15 module to be tested comprises a housing accommodating a bundle of hollow fibre membrane fibres, each hollow fibre extending n two opposed pots with the opposite ends of each hollow fibre being potted and sealed within said pots and component failure is ted when cracking of a pot occurs during testing.
13. A method of any one of the ing claims wherein a plurality or rack of 20 membrane modules is loaded into the test cell to enable simultaneous g.
14. A method of any one of the preceding claims wherein each membrane module is subjected to a testing cycle having a predetermined number of stress cycles to be imposed over a predetermined period of time, said predetermined number of stress cycles corresponding with required minimum design service life. 25
15. A method of claim 14 wherein said minimum design service life is measured in years and said predetermined number of stress cycles is imposed in a much shorter period in the order of weeks or months.
16. A method of any one of claims 5 to 15 wherein duration of a filtration cycle is significantly shorter than during normal service.
17. A method of claim 16 wherein said significantly shorter tion cycle duration increases filtration flux over normal service.
18. A method of claim 17 wherein filtration flux during testing is measured and compared with tion flux during normal e
19. A method of any one of claims 5 to 18 wherein testing is used to assess whether ance to membrane fouling is improved by shorter filtration cycle duration. 1O
20. A method of any one of the preceding claims including imposing chemical treatments on the membrane module at a plurality of solution strengths for varying duration.
21. A method of claim 20 wherein said chemical treatments are d during membrane operating cycles having duration the same as, or r to, 15 duration in said operating plant.
22. A method of any one of the preceding claims wherein said industrial membrane separation process requires a membrane service life of duration of a plurality of years.
23. A method of claim 22 wherein said industrial membrane separation 20 process is a liquid treatment process, preferably a water treatment process.
24. A method of claim 23 wherein said test cell is ured to simulate a membrane bioreactor with said membrane module being submerged in mixed liquor within said test cell.
25. A method of claim 23 or 24 n said water treatment process is a waste water treatment process where a membrane module will be subjected to an operating temperature greater than about 25°C, or even greater than 30°C.
26. A method of any one of claims 23 to 25 where said membrane module comprises pots made of r al and said membrane module operating temperature is greater than the glass transition temperature of said polymer material.
27. A method of any one of claims 23 to 26 wherein said testing method is applied at different temperatures to assess dependence of membrane module 10 service life on service operating temperature. L GIPPSLAND REGION WATER CORPORATION WATERMARK PATENT AND TRADE MARKS ATTORNEYS P35095NZPC Biogas Water Biogas Water
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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AU2011904915 | 2011-11-25 | ||
AU2011904915A AU2011904915A0 (en) | 2011-11-25 | A method of testing a membrane module | |
PCT/AU2012/001447 WO2013075177A1 (en) | 2011-11-25 | 2012-11-26 | A method for accelerated testing of a membrane module |
Publications (2)
Publication Number | Publication Date |
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NZ625041A NZ625041A (en) | 2015-04-24 |
NZ625041B2 true NZ625041B2 (en) | 2015-07-28 |
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