CA2644991A1 - Pumpable geopolymer formulation for oilfield application - Google Patents
Pumpable geopolymer formulation for oilfield application Download PDFInfo
- Publication number
- CA2644991A1 CA2644991A1 CA 2644991 CA2644991A CA2644991A1 CA 2644991 A1 CA2644991 A1 CA 2644991A1 CA 2644991 CA2644991 CA 2644991 CA 2644991 A CA2644991 A CA 2644991A CA 2644991 A1 CA2644991 A1 CA 2644991A1
- Authority
- CA
- Canada
- Prior art keywords
- suspension
- accelerator
- activator
- metal
- thickening
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0067—Function or property of ingredients for mortars, concrete or artificial stone the ingredients being formed in situ by chemical reactions or conversion of one or more of the compounds of the composition
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Colloid Chemistry (AREA)
- Lubricants (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides geopolymeric compositions, which have controllable thickening and setting times for a wide range of temperatures and a large range of geopolymer slurry densities. The geopolymer slurry compositions have good mixability and pumpability, whilst the set materials develop good compressive strength and permeability. The invention discloses a method for preparing geopolymer for oilfield cementing applications. The geopolymeric compositions according to the invention comprises a suspension made of an aluminosilicate source, a carrier fluid, an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, and the suspension is a pumpable composition in oilfield industry and the suspension is able to set under well downhole conditions.
Claims (52)
1. A suspension comprising:
- an aluminosilicate source, - a carrier fluid, - an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, and wherein the suspension is a pumpable composition in oilfield industry and the suspension is able to set under well downhole conditions.
- an aluminosilicate source, - a carrier fluid, - an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, and wherein the suspension is a pumpable composition in oilfield industry and the suspension is able to set under well downhole conditions.
2. The suspension of claim 1, further comprising a retarder able to control the thickening and/or the setting times of the suspension under well downhole conditions.
3. The suspension of claim 1 or 2, wherein the retarder is selected from the group constituted of boron containing compound,lignosulfate, sodium gluconate, sodium glucoheptonate, tartaric acid and phosphorus containing compound, or a mixture of them.
4. The suspension according to any one of claims 1 to 3, wherein the retarder is efficient from 20°C to 200°C.
5. The suspension according to any one of claims 1 to 4, further comprising an accelerator able to control the thickening and/or the setting times of the suspension.
6. The suspension of claim 5, wherein the accelerator is an alkali metal containing compound.
7. The suspension of claim 6, wherein the accelerator is a lithium or potassium compound.
8. The suspension according to any one of claims 5 to 7, wherein the accelerator is efficient from 20°C to 200°C.
9. The suspension according to any one of claims 1 to 8, further comprising a lightweight particle selected from the group constituted of: cenospheres, sodium-calcium-borosilicate glass, and silica-alumina microspheres.
10. The suspension according to any one of claims 1 to 9, further comprising a heavy particle selected from the group constituted of manganese tetraoxide, iron oxide (hematite), barium sulfate (barite), silica and iron/titanium oxide (ilmenite).
11. The suspension according to any one of claims 1 to 10, further comprising a gas phase.
12. The suspension of claim 11, wherein the gas phase is air or nitrogen.
13. The suspension of claim 11, further comprising a gas generating additive able to generate a gas phase within the suspension.
14. The suspension according to any one of claims 1 to 13, further comprising a water-immiscible phase.
15. The suspension of claim 14, wherein the water-immiscible phase is an oil-based phase.
16. The suspension according to any one of claims 1 to 15, wherein the density of the suspension varies between 1 gram per cubic centimeter and 2.5 grams per cubic centimeter.
17. The suspension according to any one of claims 1 to 16, further comprising an additive selected from the group constituted of: an antifoam, a defoamer, silica, a fluid loss control additive, a flow enhancing agent, a dispersant, a rheology modifier, a foaming agent, a surfactant and an anti-settling additive.
18. A suspension comprising:
- an aluminosilicate source, - a carrier fluid, - an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, and - a retarder able to retard the thickening and/or the setting times of the suspension and/or an accelerator able to accelerate the thickening and/or the setting times of the suspension, wherein the metal is an alkali metal and the oxide molar ratio M2O/SiO2 is greater than 0.20 wherein M is the metal.
- an aluminosilicate source, - a carrier fluid, - an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, and - a retarder able to retard the thickening and/or the setting times of the suspension and/or an accelerator able to accelerate the thickening and/or the setting times of the suspension, wherein the metal is an alkali metal and the oxide molar ratio M2O/SiO2 is greater than 0.20 wherein M is the metal.
19. The suspension of claim 18, wherein the oxide molar ratio M2O/SiO2 is greater than or equal to 0.25.
20. The suspension according to any one of claims 18 to 19, wherein the retarder is a boron containing compound and wherein the suspension of said geopolymeric composition has an oxide molar ratio B2O3/H2O of less than 0.03.
21. The suspension of claim 20, wherein the oxide molar ratio B2O3/H2O is less than or equal to 0.02.
22. The suspension according to any one of claims 18 to 21, wherein the silicon to aluminum atomic ratio is between 1.8 and 2.8.
23. The suspension of claim 22, wherein the silicon to aluminum atomic ratio is substantially equal to two.
24. The suspension according to any one of claims 18 to 23, wherein the aluminosilicate source is selected from the group constituted of type C fly ash, type F fly ash, ground blast furnace slag, calcined clays, partially calcined clays (as metakaolin), aluminium-containing silica fume, natural aluminosilicate as kaolin, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite and pumice.
25. The suspension according to any one of claims 18 to 24, wherein the metal is selected from the group constituted of lithium, sodium, potassium, rubidium, and cesium.
26. The suspension according to any one of claims 18 to 25, wherein the alkali activator is an alkali metal hydroxide.
27. The suspension according to any one of claims 18 to 26, wherein the alkali activator and/or the carrier fluid is encapsulated.
28. The suspension according to any one of claims 18 to 27, wherein the metal silicate and/or the carrier fluid is encapsulated.
29. A method to control the setting time and/or the thickening time of a geopolymeric suspension for oilfield industry, comprising the step of providing said suspension within a carrier fluid by adding:
(i) a retarder and/or an accelerator;
(ii) an aluminosilicate source;
(iii) an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof.
(i) a retarder and/or an accelerator;
(ii) an aluminosilicate source;
(iii) an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof.
30. The method of claim 29, wherein the method applies for temperature ranges from 20°C to 200°C.
31. The method according to any one of claims 29 to 30, wherein the alkali activator is selected from the group constituted of: sodium hydroxide and potassium hydroxide, whether encapsulated or not.
32. The method according to any one of claims 29 to 31, wherein the retarder is selected from the group constituted of boron containing compound, lignosulfate, sodium gluconate, sodium glucoheptonate, tartaric acid and phosphorus containing compounds, or a mixture of them.
33. The method according to any one of claims 29 to 32, wherein the accelerator is an alkali metal containing compound.
34. The method of claim 33, wherein the accelerator is a lithium or potassium compound.
35. The method according to any one of claims 29 to 34, wherein the retarder and/or the accelerator is encapsulated.
36. The method according to any one of claims 29 to 35, wherein the thickening and/or the setting times are controlled by changing the nature and/or the concentration of the retarder and/or accelerator.
37. The method according to any one of claims 29 to 36, wherein the thickening and/or the setting times are controlled by changing the pH and/or the concentration of the alkali activator.
38. A method to control the density of a suspension for oilfield industry, comprising the step of providing said suspension within a carrier fluid by adding:
(i) lightweight particles and/or heavy particles;
(ii) an aluminosilicate source;
(iii) an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof.
(i) lightweight particles and/or heavy particles;
(ii) an aluminosilicate source;
(iii) an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof.
39. The method of claim 38, further comprising the step of adding a retarder able to retard the thickening and/or the setting times of the suspension and/or an accelerator able to accelerate the thickening and/or the setting times of the suspension.
40. The method of claim 38 or 39, further comprising the step of foaming the suspension of said geopolymeric composition.
41. A method to control the density of a suspension for oilfield industry, comprising the step of:
(i) providing said suspension within a carrier fluid by mixing an aluminosilicate source, and an activator taken from the list constituted by:
a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, and (ii) foaming said suspension.
(i) providing said suspension within a carrier fluid by mixing an aluminosilicate source, and an activator taken from the list constituted by:
a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, and (ii) foaming said suspension.
42. The method according to any one of claims 38 to 41, wherein the density range varies between 1 gram per cubic centimeter and 2.5 grams per cubic centimeter.
43. A method to place a geopolymeric composition in a borehole in a formation comprising the step of:
(i) providing a suspension within a carrier fluid by mixing an aluminosilicate source, and an activator taken from the list constituted by:
a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, (ii) pumping said suspension into the borehole, and (iii) allowing said suspension to set under wellbore downhole conditions and thereby form the geopolymeric composition.
(i) providing a suspension within a carrier fluid by mixing an aluminosilicate source, and an activator taken from the list constituted by:
a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, (ii) pumping said suspension into the borehole, and (iii) allowing said suspension to set under wellbore downhole conditions and thereby form the geopolymeric composition.
44. The method of claim 43, wherein the step of providing a suspension further comprises adding a retarder able to retard the thickening and/or the setting times of the suspension.
45. The method of claim 43 or 44, wherein the step of providing a suspension further comprises adding an accelerator able to accelerate the thickening and/or the setting times of the suspension.
46. The method according to any one of claims 43 to 45, further comprising the step of activating in situ said suspension.
47. The method according to any one of claims 43 to 46, wherein the step of pumping the suspension is made with conventional tools of wellbore cementing.
48. The method according to any one of claims 43 to 48, wherein the method applies to the placement of the geopolymeric composition in an annular space between a casing and the borehole.
49. The method according to any one of claims 43 to 48, wherein the method applies to the placement of the geopolymeric composition through a hole made in a casing.
50. The method according to any one of claims 43 to 48, wherein the method applies to the placement of the geopolymeric composition to plug a zone of the borehole.
51. The method according to any one of claims 43 to 48, wherein the method applies to the placement of the geopolymeric composition to squeeze a zone of the borehole.
52. The method according to any one of claims 29 to 50, wherein the suspension is prepared before the step of pumping and is left intentionally in a liquid phase able to be stored.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/462,724 | 2006-08-07 | ||
EP20060291275 EP1887065B1 (en) | 2006-08-07 | 2006-08-07 | Geopolymer composition and application in oilfield industry |
US11/462,724 US7794537B2 (en) | 2006-08-07 | 2006-08-07 | Geopolymer composition and application in oilfield industry |
EP06291275.3 | 2006-08-07 | ||
PCT/EP2007/006815 WO2008017414A1 (en) | 2006-08-07 | 2007-08-03 | Pumpable geopolymer formulation for oilfield application |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2644991A1 true CA2644991A1 (en) | 2008-02-14 |
CA2644991C CA2644991C (en) | 2010-10-05 |
Family
ID=38608731
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2644991 Active CA2644991C (en) | 2006-08-07 | 2007-08-03 | Pumpable geopolymer formulation for oilfield application |
Country Status (6)
Country | Link |
---|---|
AU (1) | AU2007283146B2 (en) |
CA (1) | CA2644991C (en) |
MX (1) | MX2009001400A (en) |
NO (1) | NO347297B1 (en) |
RU (1) | RU2446199C2 (en) |
WO (1) | WO2008017414A1 (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2093200A1 (en) * | 2008-02-19 | 2009-08-26 | Services Petroliers Schlumberger | Pumpable geopolymer formulation for oilfield application |
CN101323778B (en) * | 2008-07-29 | 2010-12-29 | 南京工业大学 | Metakaolin-slag-based geopolymer for oil field well cementation and high-temperature retarder thereof |
GB0817501D0 (en) | 2008-09-24 | 2008-10-29 | Minova Int Ltd | Method of stabilising a blasthole |
RU2517729C2 (en) * | 2009-01-22 | 2014-05-27 | Те Католик Юниверсити Ов Америка | Geopolymer composite binders with given properties for cement and concrete |
DK2338947T3 (en) | 2009-12-17 | 2012-11-05 | Schlumberger Technology Bv | Pumpable geopolymers comprising a curing accelerator |
EP2338948B1 (en) | 2009-12-17 | 2012-08-15 | Services Pétroliers Schlumberger | Pumpable geopolymers comprising a fluid-loss agent |
EP2338949B1 (en) | 2009-12-17 | 2012-08-15 | Services Pétroliers Schlumberger | Pumpable geopolymers comprising a mixing aid and dispersing agent |
CA2797342C (en) | 2010-04-26 | 2018-11-06 | Construction Research & Technology Gmbh | Alkali-activated aluminosilicate binder containing glass beads |
EP2385029B1 (en) | 2010-05-03 | 2016-10-26 | Services Pétroliers Schlumberger | Compositions and method for well cementing |
US9834719B2 (en) | 2010-11-30 | 2017-12-05 | Schlumberger Technology Corporation | Methods for servicing subterranean wells |
US9950952B2 (en) | 2010-11-30 | 2018-04-24 | Schlumberger Technology Corporation | Methods for servicing subterranean wells |
CN102604613B (en) * | 2012-03-12 | 2013-08-21 | 中成新星油田工程技术服务股份有限公司 | Oil-based ultrafine cement paste and production method thereof |
US8557036B1 (en) * | 2012-11-09 | 2013-10-15 | Halliburton Energy Services, Inc. | Settable compositions comprising wollastonite and pumice and methods of use |
EP3080226A4 (en) * | 2013-12-12 | 2017-06-14 | Halliburton Energy Services, Inc. | Settable compositions comprising cement kiln dust and methods of use |
CN104312558B (en) * | 2014-11-13 | 2017-03-08 | 中国海洋石油总公司 | Metakaolin waterborne suspension and its preparation method and application and reinforcing oil well cement mortar |
US9863231B2 (en) | 2014-12-01 | 2018-01-09 | Saudi Arabian Oil Company | Fracturing fluid for subterranean formations |
JP7296135B2 (en) * | 2017-12-15 | 2023-06-22 | ザ カトリック ユニバーシティ オブ アメリカ | Controlling curing time of geopolymer compositions containing high CA reactive aluminosilicate materials |
US11453815B2 (en) | 2018-02-07 | 2022-09-27 | Petroliam Nasional Berhad | Pumpable geopolymer cement |
CA3160249A1 (en) * | 2019-12-06 | 2021-06-10 | Mahmoud KHALIFEH | Method of mineralization of co2 in inorganic polymers (geopolymers) |
CN111646719A (en) * | 2020-06-04 | 2020-09-11 | 浙江建设职业技术学院 | Geopolymer material for leaking stoppage and water prevention and preparation method thereof |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0026687B1 (en) * | 1979-09-04 | 1986-08-13 | Joseph Davidovits | Synthetic inorganic polymer of the silicoaluminate family and process for the preparation thereof; moulded articles containing this polymer, and process for their preparation |
SU1583589A1 (en) * | 1987-10-27 | 1990-08-07 | Днепропетровский инженерно-строительный институт | Plugging composition |
EP0518980B1 (en) * | 1990-03-07 | 1994-12-14 | Joseph Davidovits | Process for obtaining a geopolymeric alumino silicate and products thus obtained |
RU2149981C1 (en) * | 1998-11-24 | 2000-05-27 | Открытое акционерное общество "ПермНИПИнефть" | Grouting mortar |
RU2178060C2 (en) * | 1999-11-30 | 2002-01-10 | Федеральное государственное унитарное предприятие "Научно-производственный центр по сверхглубокому бурению и комплексному изучению недр Земли" (ФГУП НПЦ "Недра") | Method of well casing |
US7048053B2 (en) * | 2002-12-10 | 2006-05-23 | Halliburton Energy Services, Inc. | Zeolite compositions having enhanced compressive strength |
NZ527772A (en) * | 2003-08-22 | 2005-10-28 | Ind Res Ltd | Alkali activated fly ash based geopolymer cements and methods for their production |
CA2540429C (en) * | 2003-11-04 | 2007-01-30 | Global Synfrac Inc. | Proppants and their manufacture |
-
2007
- 2007-08-03 AU AU2007283146A patent/AU2007283146B2/en active Active
- 2007-08-03 CA CA 2644991 patent/CA2644991C/en active Active
- 2007-08-03 RU RU2009108324/03A patent/RU2446199C2/en active
- 2007-08-03 WO PCT/EP2007/006815 patent/WO2008017414A1/en active Application Filing
- 2007-08-03 MX MX2009001400A patent/MX2009001400A/en active IP Right Grant
- 2007-08-03 NO NO20090602A patent/NO347297B1/en unknown
Also Published As
Publication number | Publication date |
---|---|
RU2446199C2 (en) | 2012-03-27 |
NO347297B1 (en) | 2023-09-04 |
MX2009001400A (en) | 2009-03-13 |
NO20090602L (en) | 2009-05-07 |
AU2007283146B2 (en) | 2013-03-28 |
WO2008017414A1 (en) | 2008-02-14 |
AU2007283146A1 (en) | 2008-02-14 |
RU2009108324A (en) | 2010-09-20 |
CA2644991C (en) | 2010-10-05 |
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