CA2512497A1 - Methods and apparatus for the measurement of hydrogen sulphide and thiols in fluids - Google Patents
Methods and apparatus for the measurement of hydrogen sulphide and thiols in fluids Download PDFInfo
- Publication number
- CA2512497A1 CA2512497A1 CA002512497A CA2512497A CA2512497A1 CA 2512497 A1 CA2512497 A1 CA 2512497A1 CA 002512497 A CA002512497 A CA 002512497A CA 2512497 A CA2512497 A CA 2512497A CA 2512497 A1 CA2512497 A1 CA 2512497A1
- Authority
- CA
- Canada
- Prior art keywords
- electrochemical sensor
- membrane
- housing member
- housing
- fluid
- 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.)
- Granted
Links
- 239000012530 fluid Substances 0.000 title claims abstract 13
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract 8
- 150000003573 thiols Chemical class 0.000 title claims abstract 8
- 238000000034 method Methods 0.000 title claims 3
- 238000005259 measurement Methods 0.000 title 1
- 239000012528 membrane Substances 0.000 claims abstract 16
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract 2
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract 2
- 230000001419 dependent effect Effects 0.000 claims abstract 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims abstract 2
- 238000006479 redox reaction Methods 0.000 claims abstract 2
- 239000010457 zeolite Substances 0.000 claims abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 6
- 230000015572 biosynthetic process Effects 0.000 claims 5
- 239000003153 chemical reaction reagent Substances 0.000 claims 4
- 238000007789 sealing Methods 0.000 claims 4
- 229910052697 platinum Inorganic materials 0.000 claims 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims 2
- 229920002530 polyetherether ketone Polymers 0.000 claims 2
- 239000000523 sample Substances 0.000 claims 2
- 238000005070 sampling Methods 0.000 claims 2
- UMAPFAAAQBMYNJ-UHFFFAOYSA-N 1-n,2-n-dimethylbenzene-1,2-diamine Chemical compound CNC1=CC=CC=C1NC UMAPFAAAQBMYNJ-UHFFFAOYSA-N 0.000 claims 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 229910021607 Silver chloride Inorganic materials 0.000 claims 1
- 229910021612 Silver iodide Inorganic materials 0.000 claims 1
- 229910003460 diamond Inorganic materials 0.000 claims 1
- 239000010432 diamond Substances 0.000 claims 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims 1
- 229910021397 glassy carbon Inorganic materials 0.000 claims 1
- 238000005192 partition Methods 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 229940045105 silver iodide Drugs 0.000 claims 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
- G01N27/4045—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors for gases other than oxygen
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B47/00—Survey of boreholes or wells
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; viscous liquids; paints; inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Oils, i.e. hydrocarbon liquids specific substances contained in the oil or fuel
- G01N33/287—Sulfur content
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/18—Sulfur containing
- Y10T436/182—Organic or sulfhydryl containing [e.g., mercaptan, hydrogen, sulfide, etc.]
- Y10T436/184—Only hydrogen sulfide
Abstract
An electrochemical sensor for measuring the amount of hydrogen sulphide or thiols in a fluid in a wellbore comprises a temperature- and pressure-resistant housing containing a flow path for the fluids. The fluids flow over one side of a gas permeable membrane made of zeolite or a suitable ceramic material, the other side of the membrane being exposed to a chamber containing a reaction solution which together with the hydrogen sulphide or thiols create a redox reaction resulting in an electrical current dependent upon the amount of hydrogen sulphide or thiols in the fluid.
Claims (24)
1. An electrochemical sensor for measuring the amount of hydrogen sulphide or thiols in a fluid, the sensor comprising a housing having a flow path for the fluid therethrough, a substantially rigid gas permeable membrane disposed in the housing and having one side exposed to the flow path, and a chamber disposed in the housing, the chamber being exposed to the other side of the membrane and containing reagents which together with the hydrogen sulphide or thiols entering the chamber via the membrane create a redox reaction resulting in an electrical current dependent upon the amount of hydrogen sulphide or thiols in said fluid
2. The electrochemical sensor as claimed in claim 1, wherein the housing is provided with pressure balancing means for reducing the difference between the respective pressures on each side of the membrane.
3. The electrochemical sensor as claimed in claim 2, wherein the pressure balancing means comprises a movable piston having a first pressure surface in pressure communication with the flow path and a second pressure surface in pressure communication with the chamber.
4. The electrochemical sensor as claimed in claim 3, wherein the first pressure surface of the movable partition, piston or bellow is directly exposed to the fluid, and the second pressure surface of the movable piston is directly exposed to the reagents.
5. The electrochemical sensor as claimed in any preceding claims, wherein the membrane is trapped between respective sealing means which extend around the periphery of the membrane on each side thereof.
6. The electrochemical sensor as claimed in any preceding claims, wherein the housing includes a first housing member which is generally cup-shaped and is provided with a centrally disposed aperture in its base, and a second housing member which is substantially cylindrical and screws coaxially into the cup-shaped housing member so as to trap the membrane between the end of the second housing member within the first housing member and the base of the cup shape of the first housing member, said other side of the membrane completely covering said aperture, and the flow path extending transversely through both housing members and communicating with said one side of the membrane via a coaxially disposed conduit in the second housing member.
7. The electrochemical sensor as claimed in claim 6, the housing includes a third housing member having a generally cylindrical recess for coaxially receiving the first and second housing members so as to define therewith a cylindrical space between the base of the cup shape of the first housing member and the base of the recess, said cylindrical space forming at least part of the chamber.
8. The electrochemical sensor as claimed in claim 6 or claim 7, wherein the sealing means on said other side of the membrane comprises a substantially coaxially disposed O-ring trapped between said other side of the membrane and the base of the cup shape of the first housing member, while the sealing means on the one side of the membrane comprises sealing engagement between said one side of the membrane and a planar surface formed on the end of the second housing member within the first housing member.
9. The electrochemical sensor as claimed in any one of claims 6 to 8, wherein a further coaxially disposed O-ring is trapped between the base of the cup shape of the first housing member and the base of the recess.
10. The electrochemical sensor as claimed in any preceding claim, wherein the chamber includes a working electrode, a counter electrode and a reference electrode.
11. The electrochemical sensor as claimed in claim 10, wherein the electrodes are spaced apart in the chamber and arranged such that said current flows between the working and counter electrodes.
12. An electrochemical sensor as claimed in claim 11, wherein the working electrode is made from boron-doped diamond.
13. An electrochemical sensor as claimed in claim 11, wherein the working electrode is made from glassy carbon.
14. An electrochemical sensor as claimed in claim 11, wherein the working electrode is made from platinum.
15. The electrochemical sensor as claimed in any one of claims 10 to 14, wherein the counter electrode may be made of platinum.
16. The electrochemical sensor as claimed in any one of claims 10 to 15, wherein the reference electrode is made of silver coated with silver chloride or silver iodide, or platinum.
17. The electrochemical sensor as claimed in any one of claims 10 to 16, wherein the electrodes are mounted on or in an insulating base made from polyetheretherketone.
18. The electrochemical sensor as made in any preceding claim, wherein the housing members are made from polyetheretherketone.
19. The electrochemical sensor as claimed in any preceding claim, wherein the reagents include dimethylphenylenediamine or its structural analogues.
20. The electrochemical sensor as claimed in any one of preceding claims, wherein the reagents include an aqueous ferrocyanide or ferrocene solution.
21. The electrochemical sensor as claimed in any preceding claims, wherein the membrane is made from zeolite or a suitable ceramic material.
22. The electrochemical sensor as claimed in any preceding claims, equipping a wellbore tool and wherein the fluid is a formation fluid.
23. The electrochemical sensor as claimed in claim 22, wherein the wellbore tool is provided with a sampling probe, said sampling probe being located at a distance comprised between 8 and 30 cm from said electrochemical sensor.
24. A method of measuring the amount of hydrogen sulphide or thiols in formation fluid from an earth formation surrounding a wellbore, the method comprising positioning a downhole tool equipped with an electrochemical sensor in accordance with any preceding claim in the wellbore adjacent to the formation, exposing the sensor to the formation fluid, and measuring the current produced by the sensor.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0300812.5 | 2003-01-15 | ||
| GB0300812A GB2397651B (en) | 2003-01-15 | 2003-01-15 | Methods and apparatus for the measurement of hydrogen sulphide and thiols in fluids |
| PCT/GB2003/002345 WO2004063743A1 (en) | 2003-01-15 | 2003-05-28 | Methods and apparatus for the measurement of hydrogen sulphide and thiols in fluids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2512497A1 true CA2512497A1 (en) | 2004-07-29 |
| CA2512497C CA2512497C (en) | 2012-11-27 |
Family
ID=9951127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2512497A Expired - Fee Related CA2512497C (en) | 2003-01-15 | 2003-05-28 | Methods and apparatus for the measurement of hydrogen sulphide and thiols in fluids |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US7758734B2 (en) |
| EP (1) | EP1583962B1 (en) |
| AT (1) | ATE504831T1 (en) |
| AU (1) | AU2003234049A1 (en) |
| CA (1) | CA2512497C (en) |
| DE (1) | DE60336682D1 (en) |
| EA (1) | EA009570B1 (en) |
| GB (1) | GB2397651B (en) |
| MX (1) | MXPA05007540A (en) |
| NO (1) | NO338035B1 (en) |
| WO (1) | WO2004063743A1 (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2397651B (en) | 2003-01-15 | 2005-08-24 | Schlumberger Holdings | Methods and apparatus for the measurement of hydrogen sulphide and thiols in fluids |
| GB2404738B (en) | 2003-08-04 | 2005-09-28 | Schlumberger Holdings | System and method for sensing using diamond based microelectrodes |
| US8758593B2 (en) | 2004-01-08 | 2014-06-24 | Schlumberger Technology Corporation | Electrochemical sensor |
| US7664607B2 (en) | 2005-10-04 | 2010-02-16 | Teledyne Technologies Incorporated | Pre-calibrated gas sensor |
| WO2007089550A2 (en) * | 2006-01-26 | 2007-08-09 | Nanoselect, Inc. | Cnt-based sensors: devices, processes and uses thereof |
| US20090278556A1 (en) * | 2006-01-26 | 2009-11-12 | Nanoselect, Inc. | Carbon Nanostructure Electrode Based Sensors: Devices, Processes and Uses Thereof |
| US20080135237A1 (en) * | 2006-06-01 | 2008-06-12 | Schlumberger Technology Corporation | Monitoring injected nonhydrocarbon and nonaqueous fluids through downhole fluid analysis |
| GB2444276B (en) | 2006-12-02 | 2009-06-03 | Schlumberger Holdings | System and method for qualitative and quantitative analysis of gaseous components of multiphase hydrocarbon mixtures |
| ATE491078T1 (en) | 2007-08-23 | 2010-12-15 | Prad Res & Dev Nv | APPARATUS AND METHOD FOR ANALYZING LIGHT CHEMICAL COMPOUNDS |
| US7520160B1 (en) | 2007-10-04 | 2009-04-21 | Schlumberger Technology Corporation | Electrochemical sensor |
| GB2476237B (en) * | 2009-12-15 | 2012-01-11 | Schlumberger Holdings | Calibration of electrochemical sensor |
| DE102010016103B4 (en) * | 2010-03-23 | 2012-01-26 | Andreas Hettich Gmbh & Co. Kg | Measuring device with resonator |
| US8596354B2 (en) | 2010-04-02 | 2013-12-03 | Schlumberger Technology Corporation | Detection of tracers used in hydrocarbon wells |
| AU2010353761B2 (en) | 2010-05-21 | 2015-07-09 | Halliburton Energy Services, Inc. | Downhole spectroscopic detection of carbon dioxide and hydrogen sulfide |
| GB201009136D0 (en) * | 2010-06-01 | 2010-07-14 | Isis Innovation | Electrochemical method |
| GB2493718A (en) | 2011-08-15 | 2013-02-20 | Schlumberger Holdings | Electrochemical sensor with surfactants |
| US9546959B2 (en) | 2011-09-16 | 2017-01-17 | Schlumberger Technology Corporation | Method and system for measurement of reservoir fluid properties |
| GB2497795B (en) | 2011-12-21 | 2020-04-08 | Schlumberger Holdings | Derivatization of carbon |
| GB2497791B (en) | 2011-12-21 | 2021-01-20 | Schlumberger Holdings | Derivatization of carbon |
| GB2497788B (en) | 2011-12-21 | 2020-12-30 | Schlumberger Holdings | Derivatization of carbon |
| GB2497972B (en) * | 2011-12-23 | 2016-03-16 | Schlumberger Holdings | Electrochemical sensors |
| US9212546B2 (en) * | 2012-04-11 | 2015-12-15 | Baker Hughes Incorporated | Apparatuses and methods for obtaining at-bit measurements for an earth-boring drilling tool |
| US9394782B2 (en) * | 2012-04-11 | 2016-07-19 | Baker Hughes Incorporated | Apparatuses and methods for at-bit resistivity measurements for an earth-boring drilling tool |
| US9605487B2 (en) | 2012-04-11 | 2017-03-28 | Baker Hughes Incorporated | Methods for forming instrumented cutting elements of an earth-boring drilling tool |
| GB2507042B (en) | 2012-10-16 | 2018-07-11 | Schlumberger Holdings | Electrochemical hydrogen sensor |
| AU2014240947B2 (en) * | 2013-03-28 | 2018-04-12 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Hydrogen sulfide detecting apparatus |
| CN103291290B (en) * | 2013-06-03 | 2016-04-06 | 西南石油大学 | A kind of mud gas downhole detection method |
| US10605068B2 (en) * | 2013-12-17 | 2020-03-31 | Schlumberger Technology Corporation | Downhole electrochemical fluid sensor and method of using same |
| WO2016144774A1 (en) | 2015-03-06 | 2016-09-15 | Shell Oil Company | Methods of measuring hydrogen sulfide concentrations in reservoir fluids |
| WO2017039789A1 (en) * | 2015-08-31 | 2017-03-09 | Exxonmobil Upstream Research Company Corp-Urc-E2. 4A.296 | Smart electrochemical sensor for pipeline corrosion measurement |
| US9562430B1 (en) | 2015-10-05 | 2017-02-07 | Baker Hughes Incorporated | Chemiresistive sensors for downhole tools |
| US10025000B2 (en) | 2016-01-21 | 2018-07-17 | Baker Hughes Incorporated | Optical sensors for downhole tools and related systems and methods |
| US10120097B2 (en) | 2016-04-05 | 2018-11-06 | Baker Hughes Incorporated | Methods and apparatus for measuring hydrogen sulfide in downhole fluids |
| US11180989B2 (en) | 2018-07-03 | 2021-11-23 | Baker Hughes Holdings Llc | Apparatuses and methods for forming an instrumented cutting for an earth-boring drilling tool |
| US10584581B2 (en) | 2018-07-03 | 2020-03-10 | Baker Hughes, A Ge Company, Llc | Apparatuses and method for attaching an instrumented cutting element to an earth-boring drilling tool |
| US20210215633A1 (en) * | 2020-01-13 | 2021-07-15 | Beckman Coulter, Inc. | Solid state ion selective electrodes |
| CN114717533B (en) * | 2022-02-25 | 2023-03-10 | 中国地质大学（北京） | Method for preparing sensor electrode protection film by utilizing bionic structure and application |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE275924C (en) | ||||
| US3780575A (en) * | 1972-12-08 | 1973-12-25 | Schlumberger Technology Corp | Formation-testing tool for obtaining multiple measurements and fluid samples |
| US3988233A (en) * | 1973-01-05 | 1976-10-26 | Bbc Brown Boveri & Company Limited | Apparatus for measuring dissolved gases in a fluid medium |
| US3915831A (en) * | 1973-04-09 | 1975-10-28 | Orion Research | Hydrogen sulfide sensing cell |
| US3859851A (en) * | 1973-12-12 | 1975-01-14 | Schlumberger Technology Corp | Methods and apparatus for testing earth formations |
| US4490234A (en) * | 1982-02-22 | 1984-12-25 | Beckman Instruments, Inc. | Method for measuring ionic concentration utilizing an ion-sensing electrode |
| JPS6028826A (en) * | 1983-07-26 | 1985-02-14 | Hiroshi Suzuki | Compound film having surface layer of thin film of cage zeolite and preparation thereof |
| US4994671A (en) * | 1987-12-23 | 1991-02-19 | Schlumberger Technology Corporation | Apparatus and method for analyzing the composition of formation fluids |
| DD275924A1 (en) * | 1988-10-03 | 1990-02-07 | Junkalor Dessau | AMPEROMETRIC MEASURING CELL FOR THE DETERMINATION OF SULFUR HYDROGEN IN GASES AND LIQUIDS |
| DE4319573A1 (en) * | 1993-06-14 | 1994-12-15 | Mannesmann Ag | Electrochemical gas detector |
| US5480808A (en) * | 1994-01-31 | 1996-01-02 | The Unversity Of Dayton | Voltammetric method for measuring peroxide concentration in hydrocarbon fuels |
| GB2292805B (en) * | 1994-08-26 | 1998-09-09 | Mil Ram Techn Inc | Method and apparatus for the detection of toxic gases |
| US5499528A (en) * | 1994-09-26 | 1996-03-19 | W. L. Gore & Associates, Inc. | Apparatus for measuring hot gas content |
| US5667558A (en) * | 1995-07-13 | 1997-09-16 | Adapco, Inc. | Apparatus and associated method for reducing an undesired constituent of gas associated with wastewater |
| GB2359631B (en) | 2000-02-26 | 2002-03-06 | Schlumberger Holdings | Hydrogen sulphide detection method and apparatus |
| US6629444B2 (en) * | 2001-08-08 | 2003-10-07 | Industrial Scientific Corporation | Method and apparatus for diagnosing gas sensors |
| DE10144862B4 (en) * | 2001-09-12 | 2006-06-29 | Drägerwerk AG | Electrochemical gas sensor with diamond electrode |
| GB2391314B (en) | 2002-07-25 | 2005-08-10 | Schlumberger Holdings | Methods and apparatus for the measurement of hydrogen sulphide and thiols in fluids |
| GB2397651B (en) * | 2003-01-15 | 2005-08-24 | Schlumberger Holdings | Methods and apparatus for the measurement of hydrogen sulphide and thiols in fluids |
| GB2404738B (en) * | 2003-08-04 | 2005-09-28 | Schlumberger Holdings | System and method for sensing using diamond based microelectrodes |
| US7520160B1 (en) * | 2007-10-04 | 2009-04-21 | Schlumberger Technology Corporation | Electrochemical sensor |
-
2003
- 2003-01-15 GB GB0300812A patent/GB2397651B/en not_active Expired - Fee Related
- 2003-05-28 DE DE60336682T patent/DE60336682D1/en not_active Expired - Lifetime
- 2003-05-28 EP EP03727719A patent/EP1583962B1/en not_active Expired - Lifetime
- 2003-05-28 MX MXPA05007540A patent/MXPA05007540A/en active IP Right Grant
- 2003-05-28 EA EA200501127A patent/EA009570B1/en not_active IP Right Cessation
- 2003-05-28 WO PCT/GB2003/002345 patent/WO2004063743A1/en not_active Application Discontinuation
- 2003-05-28 CA CA2512497A patent/CA2512497C/en not_active Expired - Fee Related
- 2003-05-28 US US10/541,568 patent/US7758734B2/en active Active
- 2003-05-28 AT AT03727719T patent/ATE504831T1/en not_active IP Right Cessation
- 2003-05-28 AU AU2003234049A patent/AU2003234049A1/en not_active Abandoned
-
2005
- 2005-07-06 NO NO20053314A patent/NO338035B1/en not_active IP Right Cessation
-
2010
- 2010-06-09 US US12/797,148 patent/US8268146B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| NO338035B1 (en) | 2016-07-25 |
| WO2004063743A1 (en) | 2004-07-29 |
| US20100243480A1 (en) | 2010-09-30 |
| GB2397651B (en) | 2005-08-24 |
| GB0300812D0 (en) | 2003-02-12 |
| EA200501127A1 (en) | 2006-02-24 |
| US7758734B2 (en) | 2010-07-20 |
| DE60336682D1 (en) | 2011-05-19 |
| EP1583962B1 (en) | 2011-04-06 |
| AU2003234049A1 (en) | 2004-08-10 |
| AU2003234049A8 (en) | 2004-08-10 |
| ATE504831T1 (en) | 2011-04-15 |
| GB2397651A (en) | 2004-07-28 |
| US20060243603A1 (en) | 2006-11-02 |
| EA009570B1 (en) | 2008-02-28 |
| NO20053314D0 (en) | 2005-07-06 |
| MXPA05007540A (en) | 2005-09-21 |
| NO20053314L (en) | 2005-10-14 |
| EP1583962A1 (en) | 2005-10-12 |
| US8268146B2 (en) | 2012-09-18 |
| CA2512497C (en) | 2012-11-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20190528 |