EP0881941A1 - Membrane filtration element - Google Patents
Membrane filtration elementInfo
- Publication number
- EP0881941A1 EP0881941A1 EP97904651A EP97904651A EP0881941A1 EP 0881941 A1 EP0881941 A1 EP 0881941A1 EP 97904651 A EP97904651 A EP 97904651A EP 97904651 A EP97904651 A EP 97904651A EP 0881941 A1 EP0881941 A1 EP 0881941A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- flow duct
- flow
- membrane filtration
- filtration element
- element according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 238000005374 membrane filtration Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 26
- 239000012466 permeate Substances 0.000 claims abstract description 13
- 239000012530 fluid Substances 0.000 claims abstract description 12
- 239000012465 retentate Substances 0.000 claims abstract description 6
- 230000007423 decrease Effects 0.000 claims description 2
- 238000012856 packing Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
Classifications
-
- 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
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/025—Bobbin units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/027—Twinned or braided type modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
- B01D63/068—Tubular membrane modules with flexible membrane tubes
-
- 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
- B01D2321/20—By influencing the flow
- B01D2321/2008—By influencing the flow statically
- B01D2321/2016—Static mixers; Turbulence generators
Definitions
- the invention relates to a membrane filtration element comprising at least one flow duct having a membrane wall, a housing enclosing the flow duct, a fluid supply which is connected to one end of the flow duct, a retentate discharge connected to the other end of the flow duct and a permeate discharge connected to the housing, the flow duct extending helically around an imaginary axis.
- a membrane filtration element of this type is disclosed in US-A-5 202 023.
- This known membrane filtration element employs a plurality of hollow fibre membranes as flow ducts.
- one end of the hollow fibre membranes is supplied with a liquid which, as it flows through the hollow fibre membranes, partially escapes through the membrane walls and is thus separated into a permeate, to be collected in the housing, and a retentate, to be discharged at the other end of the hollow fibre membranes .
- the bundle hollow fibres is wrapped helically over a cylindri ⁇ cal core to obtain a short cylindrical configuration.
- the object of the invention is to provide an improved membrane filtration element which makes a higher packing density of the flow ducts possible and in which the membrane wall does not rapidly oul. Fouling of the membrane wall reduces the permeate yield. Fouling of the membrane wall occurs particularly if the flow in the flow ducts is laminar or not very turbulent, since the substances accumulating at the membrane walls are not removed effectively in that case. While highly turbulent flows in the flow ducts do result in more effective removal of these substances, the energy consumption in terms of permeate produced per membrane surface unit area is then very high, however.
- this object is achieved by a membrane filtration element of the abovementioned type wherein the shape of the helix formed by the flow duct is such that, if an axial main stream is established in the flow duct, a secondary flow is produced whose flow direction is substantially transverse to the direction of the main stream, and that the ratio c/a is less than 2.4, where a is the hydraulic radius of the flow duct and c is the radius of the helix.
- Figure 1 is a schematic sectional view of a membrane filtration housing containing a helically extending flow duct
- Figure 2 is a side view of an embodiment of a helical flow duct
- Figure 3 is a cross-section of the flow duct of Figure 2, a secondary flow being depicted therein;
- Figure 4 is a side-view of three parallel helical flow ducts having a common axis;
- Figure 5 is a side-view of three twisted flow ducts
- Figure 6 is a cross-section of the twisted flow ducts of Figure 5.
- Figure 7 is a side view of two parallel and both helically and spirally extending flow ducts having a common axis.
- a membrane filtration element depicted in Figure 1 comprises a helically extending flow duct 10 which is accommodated in an encasing housing 11. At one end of the flow duct 10 a fluid can be supplied, here indicated by the arrow 12.
- the flow duct 10 has a membrane wall, and a portion of the fluid flowing through the flow duct 10 escapes through the membrane wall and thus passes into the housing 11 from which it can be discharged via a permeate discharge, here indicated by the arrow 13. That part of the fluid which is retained by the membrane wall and is also referred to as retentate exits at the other end of the flow duct 10, as indicated here by the arrow 14.
- Figure 2 depicts a helically extending flow duct 20 with the dimensions a, b and c, which are of particular interest; a here is the radius of the flow duct, 2 ⁇ rb is the pitch of the windings and c is the radius of the helix. If the ratio between a, b and c stays within certain limits, an axial main flow through the flow duct 20 will produce a secondary flow in the flow duct.
- Re is the Reynolds number of the axial main flow, based on the internal diameter of the duct and the axial flow velocity prevailing in the duct.
- the secondary flow has the effect of stabilizing the flow, the transition point from laminar to turbulent flow in a helical flow duct consequently being at a higher Re number than in a straight flow duct. Moreover, the thickness of the hydrodynamic boundary layer is reduced. As a result, better mixing of the boundary layer with the fluid takes place and mass transfer proceeds more rapidly.
- the secondary flow is formed here by two vortices 31 having opposite directions of rotation, which are substantially transverse to the direction of the main stream.
- the vortices 31 have the same circumference. This is achieved if in particular the following condition is met :
- the one vortex will be larger than the other vortex.
- Four different zones can be distinguished across the cross-section shown of the flow duct: two zones A where the two vortices 31 flow along the membrane wall 32; a zone B which is situated between the points where the respective vortices 31 detach from the membrane wall 32; a zone C which is situated between the points where the respective vortices 31 attach to the membrane wall 32; and a zone D which is situated in the central section of the flow duct .
- a high packing density can be achieved if the value of the ratio c/a is smaller than 2.4. Such a small value is possible by making the pitch of the helix greater than the diameter of the flow duct (space between the windings) . Preferably, 0,1 ⁇ c/a ⁇ 1.5 and more preferably 1 ⁇ c/a ⁇ 1.5.
- Figures 5 and 6 depict an embodiment thereof, which can be fabricated by three flow ducts 50, 51, 52 being twined or twisted round one another. Of course, the number of flow ducts may be varied. The flow ducts support each other which improves the stability. In Figure 7, flow ducts 70 and 71 extend both helically and spirally.
- the helix diameter decreases from the top downwards.
- a plurality of such flow ducts to be nested inside one another in a simple manner.
- a flow duct having an oval cross-sectional shape In that case too a flow duct is obtained in which a helical shape extending around an imaginary axis can be discerned.
- the parameter a is the hydraulic radius which is defined as 2A/1, where A is the cross- sectional area of the flow duct and 1 is the circumference of the flow duct.
- the hydraulic radius is of course equal to the radius.
- the secondary flow can be generated by a flow duct which has an oval shape and is twisted solely around its centre line. In this case the ratio c/a is zero.
- the membrane filtration element according to the invention can thus be used, thanks to the helically wound flow duct, to obtain a high permeate yield in conjunction with low energy consumption and a high packing density.
- a plurality of membrane filtration elements are connected in series. Supplying the retentate from the one element in turn as a fluid to the next element makes it possible to achieve more comprehensive filtration.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Membrane filtration element comprising at least one flow duct (10) having a membrane wall, a housing (11) enclosing the flow duct (10), a fluid supply (12) which is connected to one end of the flow duct (10), a retentate discharge (14) connected to the other end of the flow duct (10) and a permeate discharge (13) connected to the housing (11). The flow duct (10) extends helically in such a way around an imaginary axis that, if an axial main stream is established in the flow duct (10), a secondary flow is produced whose flow direction is substantially transverse to the direction of the main stream. In particular, the ratio c/a is less than 2.4, where a is the hydraulic radius of the flow duct (10) and c is the radius of the helix formed by the flow duct.
Description
Membrane filtration element .
The invention relates to a membrane filtration element comprising at least one flow duct having a membrane wall, a housing enclosing the flow duct, a fluid supply which is connected to one end of the flow duct, a retentate discharge connected to the other end of the flow duct and a permeate discharge connected to the housing, the flow duct extending helically around an imaginary axis.
A membrane filtration element of this type is disclosed in US-A-5 202 023. This known membrane filtration element employs a plurality of hollow fibre membranes as flow ducts. In use, one end of the hollow fibre membranes is supplied with a liquid which, as it flows through the hollow fibre membranes, partially escapes through the membrane walls and is thus separated into a permeate, to be collected in the housing, and a retentate, to be discharged at the other end of the hollow fibre membranes . In one embodiment of the known membrane filtration element the bundle hollow fibres is wrapped helically over a cylindri¬ cal core to obtain a short cylindrical configuration. The object of the invention is to provide an improved membrane filtration element which makes a higher packing density of the flow ducts possible and in which the membrane wall does not rapidly oul. Fouling of the membrane wall reduces the permeate yield. Fouling of the membrane wall occurs particularly if the flow in the flow ducts is laminar or not very turbulent, since the substances accumulating at the membrane walls are not removed effectively in that case. While highly turbulent flows in the flow ducts do result in more effective removal of these substances, the energy consumption in terms of permeate produced per membrane surface unit area is then very high, however.
According to the invention this object is achieved by a membrane filtration element of the abovementioned type wherein the shape of the helix formed by the flow duct is such that, if an axial main stream is established in the
flow duct, a secondary flow is produced whose flow direction is substantially transverse to the direction of the main stream, and that the ratio c/a is less than 2.4, where a is the hydraulic radius of the flow duct and c is the radius of the helix.
As a result of this secondary flow a flow along the membrane wall is achieved which ensures that substances accumulating at the membrane wall are removed, resulting in less rapid fouling of the membrane wall. Moreover, the fluid in the flow duct is thoroughly mixed by this secondary flow and as a result the concentration differences in the fluid of the substances dissolved or suspended in the fluid and retained by the membrane in their entirety or in part, which have been produced as a result of the permeate escaping through the membrane wall, are eliminated. This is particularly true if the diffusion velocity is low with respect to the velocity of the secondary flow, because the evening-out of the concen¬ tration differences by this convection then proceeds more rapidly than via diffusion. Particularly for a Reynolds number which, based on the internal diameter of the flow duct and the axial flow velocity, is less than 20,000, it is thus possible to obtain a relatively high permeate yield per membrane surface unit area in conjunction with low energy consumption. By making c/a relatively small, i.e. smaller than 2.4 it is possible to achieve a high packing density of the flow ducts.
The article by K. Tanishita "Tightly wound coils of microporous tubing: progress with secondary-flow blood oxygenator design" in Transactions American Society for Artificial Internal Organs, Vol. XXI, Washington, D.C., April 1975, pages 216 to 223, discloses the use of coiled tubes with inherent secondary flow in a blood oxygenator. In this article the pitch of the coiled tube is the tightest possible and the minimum value of the ratio c/a is 2.4.
Preferred embodiments of the membrane filtration element according to the invention are defined in dependent claims 2 to 9.
The invention will be explained in more detail with reference to the accompanying drawings in which:
Figure 1 is a schematic sectional view of a membrane filtration housing containing a helically extending flow duct;
Figure 2 is a side view of an embodiment of a helical flow duct;
Figure 3 is a cross-section of the flow duct of Figure 2, a secondary flow being depicted therein; Figure 4 is a side-view of three parallel helical flow ducts having a common axis;
Figure 5 is a side-view of three twisted flow ducts;
Figure 6 is a cross-section of the twisted flow ducts of Figure 5; and
Figure 7 is a side view of two parallel and both helically and spirally extending flow ducts having a common axis.
A membrane filtration element depicted in Figure 1 comprises a helically extending flow duct 10 which is accommodated in an encasing housing 11. At one end of the flow duct 10 a fluid can be supplied, here indicated by the arrow 12. The flow duct 10 has a membrane wall, and a portion of the fluid flowing through the flow duct 10 escapes through the membrane wall and thus passes into the housing 11 from which it can be discharged via a permeate discharge, here indicated by the arrow 13. That part of the fluid which is retained by the membrane wall and is also referred to as retentate exits at the other end of the flow duct 10, as indicated here by the arrow 14.
Figure 2 depicts a helically extending flow duct 20 with the dimensions a, b and c, which are of particular interest; a here is the radius of the flow duct, 2τrb is the pitch of the windings and c is the radius of the helix. If the ratio between a, b and c stays within certain limits, an axial main flow through the flow duct 20 will produce a secondary flow in the flow duct.
One form of this secondary flow is depicted in Figure 3. The flow profile shown here is achieved if
where Re is the Reynolds number of the axial main flow, based on the internal diameter of the duct and the axial flow velocity prevailing in the duct.
The secondary flow has the effect of stabilizing the flow, the transition point from laminar to turbulent flow in a helical flow duct consequently being at a higher Re number than in a straight flow duct. Moreover, the thickness of the hydrodynamic boundary layer is reduced. As a result, better mixing of the boundary layer with the fluid takes place and mass transfer proceeds more rapidly. As can be seen, the secondary flow is formed here by two vortices 31 having opposite directions of rotation, which are substantially transverse to the direction of the main stream. Here the vortices 31 have the same circumference. This is achieved if in particular the following condition is met :
If the condition
is met, the one vortex will be larger than the other vortex. Four different zones can be distinguished across the cross-section shown of the flow duct: two zones A where the two vortices 31 flow along the membrane wall 32; a zone B which is situated between the points where the respective vortices 31 detach from the membrane wall 32;
a zone C which is situated between the points where the respective vortices 31 attach to the membrane wall 32; and a zone D which is situated in the central section of the flow duct .
As a result of permeate escaping through the membrane wall 32, concentration differences, seen across the cross-section of the flow duct, are produced in the remaining fluid, the concentration increasing from C to A to B and then decreasing from B to D to C. As a result of mixing by the vortices 31, these concentration differences are advantageously largely eliminated again. Thus it is easier for permeate to escape, the permeate yield being increased as a result . Figure 4 depicts three parallel helical flow ducts
40, 41 and 42 having a common axis. This configuration enables a high packing density of flow ducts per unit volume of the housing to be achieved.
A high packing density can be achieved if the value of the ratio c/a is smaller than 2.4. Such a small value is possible by making the pitch of the helix greater than the diameter of the flow duct (space between the windings) . Preferably, 0,1 ≤ c/a ≤ 1.5 and more preferably 1 ≤ c/a ≤ 1.5. Figures 5 and 6 depict an embodiment thereof, which can be fabricated by three flow ducts 50, 51, 52 being twined or twisted round one another. Of course, the number of flow ducts may be varied. The flow ducts support each other which improves the stability. In Figure 7, flow ducts 70 and 71 extend both helically and spirally. As can be seen, the helix diameter decreases from the top downwards. Thus it is possible for a plurality of such flow ducts to be nested inside one another in a simple manner. To obtain the above-described secondary flow together with an axial main stream it is also possible to use a flow duct having an oval cross-sectional shape. In that case too a flow duct is obtained in which a helical shape extending around an imaginary axis can be discerned.
In case of a flow duct with an oval cross-section in the formulas shown above the parameter a is the hydraulic radius which is defined as 2A/1, where A is the cross- sectional area of the flow duct and 1 is the circumference of the flow duct. For a round cross-section the hydraulic radius is of course equal to the radius. Moreover, the secondary flow can be generated by a flow duct which has an oval shape and is twisted solely around its centre line. In this case the ratio c/a is zero. The membrane filtration element according to the invention can thus be used, thanks to the helically wound flow duct, to obtain a high permeate yield in conjunction with low energy consumption and a high packing density. Advantageously, a plurality of membrane filtration elements are connected in series. Supplying the retentate from the one element in turn as a fluid to the next element makes it possible to achieve more comprehensive filtration.
Claims
1. Membrane filtration element comprising at least one flow duct having a membrane wall, a housing enclosing the flow duct, a fluid supply which is connected to one end of the flow duct, a retentate discharge connected to the other end of the flow duct and a permeate discharge connected to the housing, the flow duct extending helically around an imaginary axis, characterized in that the shape of the helix formed by the flow duct is such that, if an axial main stream is established in the flow duct, a secondary flow is produced whose flow direction is substantially transverse to the direction of the main stream, and that the ratio c/a is less than 2.4, where a is the hydraulic radius of the flow duct and c is the radius of the helix.
2. Membrane filtration element according to claim 1, wherein the ratio c/a meets the condition 0,1 ≤ c/a ≤ 1.5.
3. Membrane filtration element according to claim 2, wherein the ratio c/a meets the condition 1 ≤ c/a ≤ 1.5.
4. Membrane filtration element according to anyone of claims 1 to 3 , wherein the following condition is met :
where a is the hydraulic radius of the flow duct, 27rb the pitch and c the radius of the helix, and Re is the Reynolds number of the flow in the flow duct.
5. Membrane filtration element according to claim 4, wherein the following condition is met:
6. Membrane filtration element according to anyone of claims 1 to 5, wherein the cross-section of the flow duct is of oval shape.
7. Membrane filtration element according to claim 6, wherein the flow duct is twisted around its centre line to obtain the helical shape, the ratio c/a being zero.
8. Membrane filtration element according to anyone of claims 1 to 6, wherein the radius of the helix decreases from the one end towards the other end of the flow duct .
9. Membrane filtration element according to anyone of claims 1 to 6, wherein two or more flow ducts are used, which are twined or twisted around one another.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1002397A NL1002397C2 (en) | 1996-02-20 | 1996-02-20 | Membrane filtration element. |
NL1002397 | 1996-02-20 | ||
PCT/NL1997/000074 WO1997030779A1 (en) | 1996-02-20 | 1997-02-19 | Membrane filtration element |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0881941A1 true EP0881941A1 (en) | 1998-12-09 |
Family
ID=19762351
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97904651A Ceased EP0881941A1 (en) | 1996-02-20 | 1997-02-19 | Membrane filtration element |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0881941A1 (en) |
AU (1) | AU1736297A (en) |
CA (1) | CA2246675A1 (en) |
NL (1) | NL1002397C2 (en) |
WO (1) | WO1997030779A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5626758A (en) | 1995-08-08 | 1997-05-06 | Rensselaer Polytechnic Institute | Coiled membrane filtration system |
CA2242332C (en) * | 1996-11-07 | 2005-12-27 | Bucher-Guyer Ag | Membrane module for a membrane separation system, its use and process for producing the same |
WO1999022851A1 (en) * | 1997-11-04 | 1999-05-14 | Millipore Corporation | Membrane filtration device |
FR2801809B1 (en) * | 1999-12-03 | 2002-02-22 | Degremont | METHOD FOR MEMBRANE FILTRATION OF LIQUIDS AND DEVICE FOR CARRYING OUT SAID METHOD |
US6461513B1 (en) * | 2000-05-19 | 2002-10-08 | Filtration Solutions, Inc. | Secondary-flow enhanced filtration system |
DE102010031509A1 (en) * | 2010-07-19 | 2012-01-19 | Hemacon Gmbh | Apparatus and method for filtering a fluid |
JP6365542B2 (en) * | 2013-08-08 | 2018-08-01 | 東洋紡株式会社 | Hollow fiber membrane element and membrane module for forward osmosis |
EP3061519B1 (en) * | 2013-10-21 | 2021-04-21 | Toyobo Co., Ltd. | Hollow-fiber membrane element and membrane module for forward osmosis |
FR3060410B1 (en) * | 2016-12-21 | 2019-05-24 | Technologies Avancees Et Membranes Industrielles | TANGENTIAL FLOW SEPARATION ELEMENT INTEGRATING FLEXIBLE CHANNELS |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4241787A (en) * | 1979-07-06 | 1980-12-30 | Price Ernest H | Downhole separator for wells |
US4311589A (en) * | 1979-11-06 | 1982-01-19 | Biomedics, Inc. | Toroidal flow blood reactor |
US4354933A (en) * | 1981-02-23 | 1982-10-19 | Lester James P | Implantable artificial kidney |
GB2223690B (en) * | 1988-10-17 | 1991-05-01 | Roger Stanley White | Filtration systems |
US5202023A (en) * | 1991-12-20 | 1993-04-13 | The Dow Chemical Company | Flexible hollow fiber fluid separation module |
GB9208313D0 (en) * | 1992-04-15 | 1992-06-03 | Pawliszyn Janusz B | Continuous separation of organic compounds from water with hollow fibre membranes and supercritical fluids |
US5204002A (en) * | 1992-06-24 | 1993-04-20 | Rensselaer Polytechnic Institute | Curved channel membrane filtration |
GB9305788D0 (en) * | 1993-03-19 | 1993-05-05 | Bellhouse Brian John | Filter |
US5626758A (en) * | 1995-08-08 | 1997-05-06 | Rensselaer Polytechnic Institute | Coiled membrane filtration system |
-
1996
- 1996-02-20 NL NL1002397A patent/NL1002397C2/en not_active IP Right Cessation
-
1997
- 1997-02-19 WO PCT/NL1997/000074 patent/WO1997030779A1/en not_active Application Discontinuation
- 1997-02-19 AU AU17362/97A patent/AU1736297A/en not_active Abandoned
- 1997-02-19 CA CA002246675A patent/CA2246675A1/en not_active Abandoned
- 1997-02-19 EP EP97904651A patent/EP0881941A1/en not_active Ceased
Non-Patent Citations (1)
Title |
---|
See references of WO9730779A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU1736297A (en) | 1997-09-10 |
CA2246675A1 (en) | 1997-08-28 |
NL1002397C2 (en) | 1997-08-25 |
WO1997030779A1 (en) | 1997-08-28 |
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