US20020141939A1 - Method for rapidly carrying out hydrogenation of a hydrogen storage material - Google Patents
Method for rapidly carrying out hydrogenation of a hydrogen storage material Download PDFInfo
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- US20020141939A1 US20020141939A1 US10/112,731 US11273102A US2002141939A1 US 20020141939 A1 US20020141939 A1 US 20020141939A1 US 11273102 A US11273102 A US 11273102A US 2002141939 A1 US2002141939 A1 US 2002141939A1
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- Prior art keywords
- hydrogenation
- graphite
- hydrogen
- magnesium
- activator
- 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.)
- Abandoned
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 70
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- 239000001257 hydrogen Substances 0.000 title claims abstract description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000011232 storage material Substances 0.000 title claims description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 60
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000010439 graphite Substances 0.000 claims abstract description 41
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000012190 activator Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims description 42
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910019083 Mg-Ni Inorganic materials 0.000 claims 1
- 229910019403 Mg—Ni Inorganic materials 0.000 claims 1
- 229910020828 NaAlH4 Inorganic materials 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 229910012375 magnesium hydride Inorganic materials 0.000 abstract description 24
- 150000004678 hydrides Chemical class 0.000 abstract description 19
- 239000000843 powder Substances 0.000 abstract description 10
- 230000009466 transformation Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052776 Thorium Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 229910000104 sodium hydride Inorganic materials 0.000 description 6
- 229910052688 Gadolinium Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 4
- 229910052691 Erbium Inorganic materials 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 229910052790 beryllium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 238000005551 mechanical alloying Methods 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- -1 Titanium Hydride Chemical compound 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000005844 autocatalytic reaction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- YXRURWKFBUUPRM-UHFFFAOYSA-N [NiH4] Chemical compound [NiH4] YXRURWKFBUUPRM-UHFFFAOYSA-N 0.000 description 1
- LIDSSMMRLSGOSM-UHFFFAOYSA-N [ReH6] Chemical compound [ReH6] LIDSSMMRLSGOSM-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Definitions
- the present invention relates to a method for rapidly carrying out a hydrogenation of a hydrogen storage material.
- activation The first hydrogenation that is carried out to break the oxide coating at the surface of the material is called “activation”. Such activation is usually achieved by exposing the hydrogen storage material to a high temperature, typically several hundred degrees Celsius under a high hydrogen pressure, typically from 15 to 50 bars. The lower are the temperature and the pressure required for the hydrogenation, the easier is the activation and the shorter is the hydrogenation time.
- Table 1 summarizes all the experiments disclosed in the prior art for use to produce magnesium hydride starting from a powder of metallic Mg. TABLE 1 Percentage of Hydro- hydride formed Hydrogen genation during the Method Pressure Temperature time reaction (1) Hydrogena- 15 bars 345° C. 24 h ⁇ 100% tion at high temperature and high pressure (2) Hydrogena- 5 bars 350° C. >7 h ⁇ 100% tion at high temperature and high pressure with a catalyst (MgH 2 autocatalysis) (3) Grinding 2.4 bars Room 47.5 h ⁇ 100% under hydrogen temperature atmosphere without catalyst (4) Grinding 10 bars Room 10 h ⁇ 70% under hydrogen temperature atmosphere with catalyst (Co) (5) Grinding with ⁇ 1 bar 180° C. 20 h 5% graphite followed by an hydrogenation at high temperature (5) Grinding with ⁇ 1 bar 180° C. 20 h 80% graphite in the presence of cyclohexane followed by an hydrogenation at high temperature
- the present invention is directed to a method for carrying out rapidly a hydrogenation of a hydrogen storage material, which combines three of the above methods previously used separately for hydrogenating a hydrogen storage material, namely:
- the invention as claimed hereinafter is directed to a method for rapidly carrying out the hydrogenation of a hydrogen storage material wherein the material is subjected to an intense mechanical grinding in the presence of an hydrogenation activator under a hydrogen pressure and at a temperature higher than the room temperature.
- hydrogenation activator means any solid, liquid or gaseous material which, when it is applied to the surface of the hydrogen storage material to be hydrogenated by mechanical grinding, permits to protect the surface of said hydrogen storage material against contamination and thus avoids the risks of unwanted oxidation or reaction other than hydrogenation and which, at the same time, permits infiltration of hydrogen and thus acceleration of the hydrogenation at high temperature.
- the activator may also reduce agglomeration and cold welding of particles during milling and it may facilitate powder compaction after manufacture.
- hydrocarbons such as naphthalene (C 10 H 8 ), perylene (C 20 H 12 ), pentacene (C 22 H 14 ), adamantane (C 10 H 16 ) and anthracene (C 14 H 10 ).
- hydrocarbons such as naphthalene (C 10 H 8 ), perylene (C 20 H 12 ), pentacene (C 22 H 14 ), adamantane (C 10 H 16 ) and anthracene (C 14 H 10 ).
- C60 fullerene
- vulcan organic liquids
- polymeric solids . . . .
- the method according to the invention for rapidly carrying out a hydrogenation of a hydrogen storage material consists in subjecting the material to a mechanical grinding in the presence of a hydrogenation activator under a hydrogen pressure and at a temperature higher than the room temperature.
- hydrogen storage material there is meant any element, alloy, solid solution, liquid solution or complex hydride known to be capable of absorbing hydrogen in order to store it, transport it and/or produce it. This material can belong to any one of the following non-limitative groups.
- A is at least one element selected from the group consisting of La, Ca, Y, Ce, Mm, Pr, Nd, Sm, Eu, Gd, Yb and Th
- B is at least one element selected from the group consisting of Ni, Al, Co, Cr, Cu, Fe, Mn, Si, Ti, V, Zn, Zr, Nb, Mo and Pd
- A is at least one element selected from the group consisting of Ca, Ce, Dy, Er, Gd, Ho, Hf, La, Li, Pr, Sc, Sm, Th, Ti, U, Y and Zr; and
- B is at least one element selected from the group consisting of Ni, Fe, Mn, Co, Al, Rh, Ru, Pd, Cr, Zr, Be, Ti, Mo, V, Nb, Cu and Zn.
- A is at least one element selected from the group consisting of Ti, Er, Hf, Li, Th, U and Zr;
- B is at least one element selected from the group consisting of Fe, Al, Be, Co, Cr, Mn, Mo, Nb and V.
- A is at least one element selected from the group consisting of Hf, Mg, Th, Ce, Al, Ti and Zr;
- B is a combination of Ni, Co, Fe, Al, Be, Cu, Cr, V, Zn and Pd.
- A is at least one element selected from the group consisting of Ce, Dy, Er, Gd, Ho, Lu, Nd, Sm, Tb, Th, Ti, U and Y; and
- B is at least one element selected from the group consisting of Co, Ni, Fe, Mn, Cr and Al.
- A is at least one element selected from the group consisting of Ce, Dy, Er, Gd, La, Nd, Pr, Tb, Th and Y;
- B is at least one element selected from the group consisting of Co, Ni, Fe and Mn.
- hydrogen pressure there is meant an hydrogenated atmosphere preferably maintained under a pressure higher than or equal to 1 bar.
- temperature higher than the room temperature there is meant a temperature that is preferably equal to or higher than 50° C.
- this temperature can vary within a broad range depending on the nature of the selected material. In the case of magnesium known to be difficult to hydrogenate, this temperature will preferably be of about 300° C.
- the mechanical grinding is carried out in a closed enclosure with a mechanical energy superior or equal to 0.05 kW/liter.
- This grinding can be carried out with any type of conventional grinders, such as a SPEX 8000, FRITCH or ZOZ grinder.
- the hydrogenation activator must be used in a sufficient amount to obtain the desired effect.
- a minimal amount of 1% by weight of graphite seems to be required. Excellent results are obtained with 3% by weight of graphite (see the following examples).
- the determination of the optimal amount of hydrogenation activator to be used can easily be carried out and is obvious for anyone skilled in the art, as a function of the selected material to be hydrogenated.
- the mechanical grinding can be carried out in the presence of a catalyst.
- a catalyst In this connection, one may refer to the contents of the numerous patents obtained by the Applicant in this field (see in particular international applications numbers WO 96/23906, WO 97/26214; WO 99/20422 and WO 00/18530).
- catalysts reference can be made by Pd, Ni, Pt, Ir, Rh, V, etc.
- use will be made of vanadium for the hydrogenation of Mg.
- the lower limit of the amount of hydrogenation activator to be used seems to be 1% by weight in the case of graphite.
- a mixture containing 1.002 g of Mg, 0.099 g of V and 0.031 g of perylene was ground for 2 hours at 250° C. under a pressure of hydrogen of 10 bars.
- the X-ray diffraction spectrum obtained after the grinding has shown that a complete hydrogenation was achieved.
- the hydrogenation activator may be in a form other than solid
- a test was carried out to obtain a hydrogenation of Mg with anthracene.
- a mixture containing 0,900 g of Mg and 0,100 g of anthracene was ground for 1 hour at 300° C. (a temperature at which anthracene is liquid) under a pressure of hydrogen of 4 bars.
- the X-ray diffraction spectrum obtained after grinding has shown that 40% of the material has been transformed into magnesium hydride.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Disclosed is a method for rapidly carrying out a hydrogenation of a material capable of absorbing hydrogen. It was discovered that when a powder of a material capable of absorbing hydrogen is ground under a hydrogen pressure, not at room temperature but at a higher temperature (about 300° C. in the case of magnesium) and in the presence of a hydrogenation activator such as graphite and optionally a catalyst, it is possible to transform completely the powder of this material into a hydride. Such a transformation is achieved in a period of time less than 1 hour whereas the known methods call for periods of time as much as 10 times longer. This is an unexpected result which gives rise to a considerable reduction in the cost of manufacture of an hydride, particularly MgH2.
Description
- The present invention relates to a method for rapidly carrying out a hydrogenation of a hydrogen storage material.
- It is known that the hydrogenation of a material capable of absorbing hydrogen and more specifically the first hydrogenation thereof, can be very difficult to carry out, since there is usually a natural oxide at the surface of a material, which acts as a barrier to the penetration of hydrogen. Therefore, one must break down this barrier to hydrogenate the material for a first time. Thereafter, the second and subsequent hydrogenations are carried out much more easily.
- The first hydrogenation that is carried out to break the oxide coating at the surface of the material is called “activation”. Such activation is usually achieved by exposing the hydrogen storage material to a high temperature, typically several hundred degrees Celsius under a high hydrogen pressure, typically from 15 to 50 bars. The lower are the temperature and the pressure required for the hydrogenation, the easier is the activation and the shorter is the hydrogenation time.
- One of the hydrogen storage materials that is particularly difficult to activate, is magnesium. Many researchers have tried for years to rapidly produce magnesium hydride at low cost, starting from metallic magnesium, but without great success.
- The most conventional method of hydrogenation of a magnesium powder is described as follows in the article of E. BARTMANN et al, Chem. Ber. 123 (1990) 1517, at page 1523:
- <<(Mg powder was placed into a steel autoclave fitted with a glass vessel. The autoclave was evacuated twice and pressurized with 3 bars H2. The hydrogen pressure was increased to 5 bars, and the autoclave heated to 345° C. and at that temperature the H2 pressure was then increased to 15 bars and maintained constant until completion of hydrogenation (≧24 h). >>
- The extreme conditions used in this conventional method have led researchers to experiment the use of catalysts to facilitate a first hydrogenation of magnesium.
- In U.S. Pat. No. 5,198,207 of 1993 in the name of TH. GOLDSCHMIDT AG, column 1, lines 38-45, it is described that the doping of magnesium with other metals such as aluminium, indium, iron, etc has been already used to catalyze the hydrogenation of magnesium, but without great success. As an alternative, U.S. Pat. No. 5,198,207 suggests to add to the magnesium a small amount of magnesium hydride, typically higher than 1.2% by weight, in order to catalyze the hydrogenation of magnesium at temperatures above 250° C. under a pressure ranging between 5 and 50 bars. According to what is disclosed in the patent, this technique called “autocatalysis” permits to complete the hydrogenation in a period of time longer than 7 hours (see column 3).
- All the known methods described hereinabove consist in subjecting the magnesium to a high hydrogen pressure at a high temperature to produce magnesium hydride. However, it has been discovered that it is possible to produce a magnesium hydride at room temperature by carrying out a mechanical alloying consisting in subjecting a magnesium powder to an intense mechanical grinding in presence of hydrogen under pressure. In an article entitled “Formation of metal hydrides by mechanical alloying” and published inJ. of Alloys and Compounds, 217 (1994), 181, Y. CHEN et al. have demonstrated that after 47½ hours of intensive grinding of a magnesium powder under a hydrogen pressure of 240 kPa (about 2.4 bars), a large amount of magnesium is converted to magnesium hydride. However, the time period required to complete the hydrogenation is very long. In an article entitled “Synthesis of Magnesium and Titanium Hydride via Reactive Mechanical Alloying” and published in the Journal of Alloys and Compounds, 298 (2000) 279, J. L. BOBET et al. have conducted the same type of experiments with a mechanical alloying except they added to the magnesium in the crucible of the grinder, a catalyst made of a 3d transition metal, such as cobalt. These authors have discovered that only 35% of magnesium hydride is formed after 5 hours when magnesium is ground alone in the presence of hydrogen, but this percentage is increased up to 47% within the same period of time when cobalt is added as a catalyst. However, even when cobalt is used as a catalyst, only 71% of hydride is formed after 10 hours of grinding.
- In an article entitled “Hydriding-dehydriding behaviour of magnesium composites obtained by mechanical grinding with graphite carbon” and published in theInternational Journal of Hydrogen Energy, 25 (2000) 837-843, H. IMAMURA et al. have also shown that if magnesium powder is ground with graphite in presence of cyclohexane (CH) or tetrahydrofuran (THF) with or without a catalyst (Pd), the obtained composite (Mg/C or Mg/C/Pd) CF or THF is hydrogenated more rapidly than magnesium alone when, after grinding, the mixture is exposed to a hydrogen pressure of 66.7 kPa (about 0.7 bars) at 180° C. The Mg ground with graphite alone, that is, without the presence of CH of THF, results in a composite that is not very reactive and only absorbs 5% of hydrogen in 20 hours. However, when the grinding of Mg is carried out with graphite in presence of cyclohexane, 80% of Mg is converted into hydride after 20 hours of grinding.
- Table 1 summarizes all the experiments disclosed in the prior art for use to produce magnesium hydride starting from a powder of metallic Mg.
TABLE 1 Percentage of Hydro- hydride formed Hydrogen genation during the Method Pressure Temperature time reaction (1) Hydrogena- 15 bars 345° C. 24 h ≅100% tion at high temperature and high pressure (2) Hydrogena- 5 bars 350° C. >7 h ≅100% tion at high temperature and high pressure with a catalyst (MgH2 autocatalysis) (3) Grinding 2.4 bars Room 47.5 h ≅100% under hydrogen temperature atmosphere without catalyst (4) Grinding 10 bars Room 10 h ≅70% under hydrogen temperature atmosphere with catalyst (Co) (5) Grinding with ≅1 bar 180° C. 20 h 5% graphite followed by an hydrogenation at high temperature (5) Grinding with ≅1 bar 180° C. 20 h 80% graphite in the presence of cyclohexane followed by an hydrogenation at high temperature - In view of what is summarized in Table 1, one can see that to completely convert a powder of magnesium into magnesium hydride, at least 10 hours are typically required whatever be the method that is used. In view of the strategic importance of magnesium as a hydrogen storage material, it would be very interesting, from a technical standpoint, to provide a method that would significantly reduce the time of manufacture of magnesium hydride.
- This is particularly important especially in view of the content of Applicant's international patent application WO 99/2422 published in Apr. 29, 1999, which discloses a process for the preparation of a nanocomposite for the storage of hydrogen comprising the step of subjecting to an intensive mechanical grinding a magnesium hydride or an hydride of a Mg-based compound and one or more elements or compounds that are known to absorb hydrogen and to be not miscible with magnesium during grinding. Indeed, this process requires the use of magnesium hydride as starting material.
- Of course, one may easily understand the importance of a method that would facilitate the hydrogenation of a material capable of absorbing hydrogen, and would apply not only to magnesium but to any other material currently used for hydrogen storage.
- It has now been discovered that by suitably coupling three of the methods of hydrogenation previously mentioned, one may obtain a completely unexpected synergistic effect which permits to considerably reduce the time required for the preparation of an hydride. More precisely, it has been discovered that when a powder of a material capable of absorbing hydrogen is subjecting to intense mechanical grinding under hydrogen pressure not at room temperature but at a higher temperature (of about 300° C. in the case of Mg) in the presence of an hydrogenation activator such as graphite, and optionally a catalyst, it is possible to completely transform the powder of said material into the corresponding hydride in less than one hour, whereas the above prior art methods are 10 times longer. This is of course an unexpected result, which is extraordinary and results in a considerable reduction in the cost of manufacture of a hydride, in particular MgH2.
- Thus, the present invention is directed to a method for carrying out rapidly a hydrogenation of a hydrogen storage material, which combines three of the above methods previously used separately for hydrogenating a hydrogen storage material, namely:
- 1) the conventional method wherein the hydrogenation is carried out at high temperature and high pressure;
- 2) the method wherein the hydrogenation is carried out by grinding under a hydrogen atmosphere with or without additives; and
- 3) the method wherein the material is ground with a hydrogenation activator such as graphite and thereafter hydrogenated at high temperature.
- More precisely, the invention as claimed hereinafter is directed to a method for rapidly carrying out the hydrogenation of a hydrogen storage material wherein the material is subjected to an intense mechanical grinding in the presence of an hydrogenation activator under a hydrogen pressure and at a temperature higher than the room temperature.
- In the present description and the appended claims, the expression “hydrogenation activator” means any solid, liquid or gaseous material which, when it is applied to the surface of the hydrogen storage material to be hydrogenated by mechanical grinding, permits to protect the surface of said hydrogen storage material against contamination and thus avoids the risks of unwanted oxidation or reaction other than hydrogenation and which, at the same time, permits infiltration of hydrogen and thus acceleration of the hydrogenation at high temperature. The activator may also reduce agglomeration and cold welding of particles during milling and it may facilitate powder compaction after manufacture. As an example of a particularly efficient hydrogenation activator, reference can be made to graphite. As other examples of hydrogenation activators, reference can be made to hydrocarbons such as naphthalene (C10H8), perylene (C20H12), pentacene (C22H14), adamantane (C10H16) and anthracene (C14H10). Reference can also be made to fullerene (C60); vulcan; organic liquids; polymeric solids . . . .
- A non-restrictive, more detailed description of the invention will now be given.
- As indicated hereinabove, the method according to the invention for rapidly carrying out a hydrogenation of a hydrogen storage material, consists in subjecting the material to a mechanical grinding in the presence of a hydrogenation activator under a hydrogen pressure and at a temperature higher than the room temperature.
- By “hydrogen storage material”, there is meant any element, alloy, solid solution, liquid solution or complex hydride known to be capable of absorbing hydrogen in order to store it, transport it and/or produce it. This material can belong to any one of the following non-limitative groups.
- 1) Elements selected from the group consisting of Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Pd, Cs, Ba, La, Hf, Ta, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th and U.
- 2) Alloys of the AB5 type, in which:
- A is at least one element selected from the group consisting of La, Ca, Y, Ce, Mm, Pr, Nd, Sm, Eu, Gd, Yb and Th
- B is at least one element selected from the group consisting of Ni, Al, Co, Cr, Cu, Fe, Mn, Si, Ti, V, Zn, Zr, Nb, Mo and Pd
- 3) Alloys of the AB2 type in which:
- A is at least one element selected from the group consisting of Ca, Ce, Dy, Er, Gd, Ho, Hf, La, Li, Pr, Sc, Sm, Th, Ti, U, Y and Zr; and
- B is at least one element selected from the group consisting of Ni, Fe, Mn, Co, Al, Rh, Ru, Pd, Cr, Zr, Be, Ti, Mo, V, Nb, Cu and Zn.
- 4) Alloys of the AB type in which:
- A is at least one element selected from the group consisting of Ti, Er, Hf, Li, Th, U and Zr; and
- B is at least one element selected from the group consisting of Fe, Al, Be, Co, Cr, Mn, Mo, Nb and V.
- 5) Alloys of the A2B type in which:
- A is at least one element selected from the group consisting of Hf, Mg, Th, Ce, Al, Ti and Zr; and
- B is a combination of Ni, Co, Fe, Al, Be, Cu, Cr, V, Zn and Pd.
- 6) Alloys of the AB3 type in which:
- A is at least one element selected from the group consisting of Ce, Dy, Er, Gd, Ho, Lu, Nd, Sm, Tb, Th, Ti, U and Y; and
- B is at least one element selected from the group consisting of Co, Ni, Fe, Mn, Cr and Al.
- 7) Alloys of the A2B7 type in which:
- A is at least one element selected from the group consisting of Ce, Dy, Er, Gd, La, Nd, Pr, Tb, Th and Y; and
- B is at least one element selected from the group consisting of Co, Ni, Fe and Mn.
- 8) Solid solutions where the solvent is an element selected from the group consisting of Pd, Ti, Zr, Nb and V.
- 9) Complex hydride of transition metals selected among those comprising at least one of the following complex structures: [ReH9]2−, [ReH6]5−, [FeH6]4−, [RuH6]4−, [Ru2H6]12−, [RuH4]n, [CoH5]4−, [CoH4]5−, [NiH4]4−, [PdH3]3− et [ZnH4]2−.
- 10) Complex hydride selected from the family of hydrides of the general formula A(BH4)n in which A is a metal (typically of group IA or IIA) with a valence n and B is a metal of group IIIB (typically B, Al or Ga).
- 11) Alloys of the BCC type as described in U.S. Pat. No. 5,968,291.
- By “hydrogen pressure”, there is meant an hydrogenated atmosphere preferably maintained under a pressure higher than or equal to 1 bar.
- By “temperature higher than the room temperature”, there is meant a temperature that is preferably equal to or higher than 50° C. Of course, this temperature can vary within a broad range depending on the nature of the selected material. In the case of magnesium known to be difficult to hydrogenate, this temperature will preferably be of about 300° C.
- Preferably, the mechanical grinding is carried out in a closed enclosure with a mechanical energy superior or equal to 0.05 kW/liter. This grinding can be carried out with any type of conventional grinders, such as a SPEX 8000, FRITCH or ZOZ grinder.
- In practice, the hydrogenation activator must be used in a sufficient amount to obtain the desired effect. In the particular case of magnesium, a minimal amount of 1% by weight of graphite seems to be required. Excellent results are obtained with 3% by weight of graphite (see the following examples). The determination of the optimal amount of hydrogenation activator to be used can easily be carried out and is obvious for anyone skilled in the art, as a function of the selected material to be hydrogenated.
- According to a preferred embodiment of the invention, the mechanical grinding can be carried out in the presence of a catalyst. In this connection, one may refer to the contents of the numerous patents obtained by the Applicant in this field (see in particular international applications numbers WO 96/23906, WO 97/26214; WO 99/20422 and WO 00/18530). As examples of catalysts, reference can be made by Pd, Ni, Pt, Ir, Rh, V, etc. Preferably, use will be made of vanadium for the hydrogenation of Mg.
- As is shown in Table 1 hereinabove, one of the shortest times that has ever been obtained for the hydrogenation of magnesium as a hydrogen storage material is of about 7 hours (see the U.S. patent of TH. GOLDSMITH). Moreover, all the articles mentioned hereinabove that describe the step of grinding magnesium prior to subjecting it to hydrogenation at a high temperature, mention an hydrogenation time of 20 hours. In accordance with the present invention, it has been discovered that when the hydrogenation of magnesium at high temperature is carried out simultaneously with a grinding thereof with graphite under a hydrogen pressure as low as 4 bars, this hydrogenation time, formerly of 20 hours, is significantly reduced to less than 1 hour. Such was a priori not obvious and demonstrates the existence of a synergistic effect.
- Using the method according to the invention, three tests were carried out in order to obtain a first hydrogenation of magnesium using 5% at. of V as a catalyst. These three tests were respectively carried out with 3%, 1% and 0.3% by weight of graphite, as an hydrogenation activator. All the grindings were carried out for 1 hour at 300° C. under 4 bars of hydrogen.
- With 3% by weight of graphite, the transformation of Mg into MgH2 was almost complete.
- With 1% by weight of graphite, the transformation of Mg into MgH2 was achieved but the amount was much lower.
- With 0.3% by weight of graphite, the powder of magnesium agglomerated in little balls and there was no formation of hydride.
- Thus, in the case of magnesium, the lower limit of the amount of hydrogenation activator to be used seems to be 1% by weight in the case of graphite.
- In order to verify the importance of using graphite in the method according to the invention, a comparative test was carried out with the same material as in example 1 (Mg+V at. %) under the same conditions (1 hour at 300° C. under 4 bars of hydrogen), but without graphite.
- During this test, only a very small amount of hydride was produced. In fact, the powder agglomerated and formed little balls of magnesium like in the case of example 1 with 0.3% of graphite.
- Therefore, the use of a minimum of at least 1% by weight of graphite seems to be essential to obtain good results with magnesium.
- In order to verify the importance of carrying out the grinding at a temperature higher than the room temperature, another comparative test was carried out with the same material as in example 1 (Mg+V 5% at) in the presence of 3% by weight of graphite. The grinding was carried out under a pressure of 4 bars of hydrogen, but at room temperature rather than at 300° C.
- Even after 2 hours, no transformation of magnesium into hydride was detected. This confirms that it is necessary to grind the material under hot conditions.
- By using the method according to the invention, three tests were carried out to obtain a first hydrogenation of magnesium with 5% at. of vanadium as a catalyst.
- These tests were carried out with 3% by weight of graphite at 300° C. under 4 bars of hydrogen, for periods of time of 30 min., 1 hour and 2 hours, respectively.
- The determination of the amount of hydride formed during the grinding was made by X-ray diffraction. After ½ hour, more than 50% of the magnesium was transformed into Mg hydride β-MgH2. After 1 hour, more than 95% of the magnesium was transformed into β-MgH2. We also detected that in either one of the cases, traces of metastable Mg hydride γ-MgH2. After 2 hours, the obtained result was similar to the one obtained after 1 hour. However, there was a larger amount of metastable MgH2 (γ-MgH2) due to the intensive mechanical grinding of the γ-MgH2 phase.
- The amounts of hydrides thus obtained are reported in Table 2 below.
TABLE 2 Percentage of Hydro- hydride formed Hydrogen genation during the Pressure Temperature time grinding Grinding under 4 bars 300° C. 30 min ≅64% hydrogen at high temperature with graphite and a catalyst Grinding under 4 bars 30° C. 1 h ≅100% hydrogen at high temperature with graphite and a catalyst Grinding under 4 bars 300° C. 2 h ≅100% hydrogen at high temperature with graphite and a catalyst - By using the method according to the invention, a test was carried out to obtain a first hydrogenation of pure Mg without a catalyst. This test was carried out with 3% by weight by graphite at a temperature of 300° C. under a hydrogen pressure of 4 bars.
- After 2 hours of grinding, the hydrogenation was not complete. There was still some metallic magnesium that was not hydrogenated. However, in the presence of vanadium, all the magnesium was hydrogenated after 1 hour.
- Thus, the use of a catalyst seems to help hydrogenation. However, even without vanadium, the reaction of hydrogenation at high temperature under hydrogen atmosphere in the presence of graphite under mechanical action is much more rapid than the reaction that was ever tested so far in the prior art.
- To prove the applicability of the method according to the invention on other types of materials, tests were carried out to obtain a first hydrogenation of a mixture of sodium hydride and aluminium.
- By carrying out the grinding of a NaH+Al system with 3% by weight of graphite at 140° C. for 9 hours under 12 bars of hydrogen, β-Na3AlH6 was formed. Thus, the method according to the invention also applies to systems other than magnesium.
- By carrying out the grinding of a 3 NaH+Al system with 3% by weight of graphite during 14 hours under 12 bars of hydrogen at 140° C., the transformation of the starting system into β-Na3AlH6was not complete. In fact, the reaction turned out to be slower than for the system NaH+Al.
- By carrying out the same type of grinding as previously described (that is, with a 3 NaH+Al system during 14 hours under 12 bars of hydrogen at 140° C.) but with 6% by weight of graphite as compared to 3%, the transformation turned out to be almost complete. This is exceptional inasmuch as it is known that this first hydrogenation of a mixture of NaH and Al is known to be extremely difficult to carry out (see for example A. Zaleska et al.,J. of Alloys and Compounds, 298(2000) 125.)
- The above results confirm that the presence of graphite is essential but the percentage of graphite to be used can be optimised as a function of the nature of the material or system to be hydrogenated. As previously described, this optimization is easy and obvious for any one skilled in the art.
- To prove that there are materials other than graphite that have a beneficial effect similar to graphite for favorising the hydrogenation reaction and thus can be used as hydrogenation activators, a test was carried out in order to obtain a first hydrogenation of Mg+V5% at. with perylene.
- A mixture containing 1.002 g of Mg, 0.099 g of V and 0.031 g of perylene was ground for 2 hours at 250° C. under a pressure of hydrogen of 10 bars. The X-ray diffraction spectrum obtained after the grinding has shown that a complete hydrogenation was achieved.
- This clearly demonstrates that the present invention can be broadened to encompass other hydrogenation activators, such as naphtalene, fullerene, vulcan, pentacene and/or adamantane.
- To prove that the hydrogenation activator may be in a form other than solid, a test was carried out to obtain a hydrogenation of Mg with anthracene. A mixture containing 0,900 g of Mg and 0,100 g of anthracene was ground for 1 hour at 300° C. (a temperature at which anthracene is liquid) under a pressure of hydrogen of 4 bars. The X-ray diffraction spectrum obtained after grinding has shown that 40% of the material has been transformed into magnesium hydride.
- This demonstrates that the present invention can be broadened to encompass hydrogenation activators which are not in a solid form, for instance liquid hydrocarbons such as anthracene at elevated temperatures.
Claims (18)
1. A method for rapidly carry out a hydrogenation of a hydrogen storage material, comprising the step of subjecting said material to a mechanical grinding in the presence of a hydrogenation activator and under hydrogen pressure and a temperature higher than the room temperature.
2. The method according to claim 1 , wherein the hydrogen pressure is equal to or higher than 1 bar.
3. The method according to claim 2 , wherein the temperature is equal to or higher than 50° C.
4. The method according to claim 3 , wherein the mechanical grinding is carried out within an enclosure with a mechanical energy equal to or higher than 0.05 kW/liter.
5. The method according to claim 4 , wherein the hydrogenation activator is graphite.
6. The method according to claim 5 , wherein the graphite is used in an amount equal to or higher than 1% by weight.
7. The method according to claim 6 , wherein the graphite is used in an amount equal to or higher than 3% by weight.
8. The method according to claim 4 , wherein the hydrogenation activator is a hydrocarbon.
9. The method according to claim 4 , wherein the hydrogenation activator is selected from the group consisting of naphthalene, perylene, pentacene, adamantane, fullerene and vulcan.
10. The method according to claim 4 , wherein the material is magnesium.
11. The method according to claim 10 , wherein in that the hydrogen pressure is equal to about 4 bars and the temperature is equal to about 300° C.
12. The method according to claim 11 , wherein the hydrogenation activator is graphite and is used in an amount equal to or higher than 1% by weight.
13. The method according to claim 12 , wherein the mechanical grinding is carried out in the presence of vanadium as a catalyst.
14. The method according to claim 4 , wherein the mechanical grinding is carried out in the presence of a catalyst.
15. The method according to claim 14 , wherein the catalyst consists of vanadium and is present in an amount equal to or higher than 1% at.
16. The method according to claim 4 , wherein said material contains sodium and aluminum.
17. A material for the storage, transportation and/or production of hydrogen said material containing a hydrogenation activator and having been subjected to a hydrogenation carried out by the method according to claim 4 , with the proviso that when the activator is graphite, cyclohexane, tetrahydrofuran or anthracene, then the material is not selected from the group consisting of Mg, Mg—Ni, Mg—Ru, Mg—Pt, Mg—Pd, NaAlH4 and Na3AlH6.
18. The material according to claim 16 , wherein the hydrogenation activator is a solid, liquid or gaseous hydrocarbon.
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- 2001-10-02 CA CA002427605A patent/CA2427605A1/en not_active Abandoned
- 2001-10-02 EP EP01975908A patent/EP1332107A2/en not_active Withdrawn
- 2001-10-02 CN CNA018198325A patent/CN1478055A/en active Pending
- 2001-10-02 WO PCT/CA2001/001403 patent/WO2002038494A2/en active Application Filing
- 2001-10-02 JP JP2002541038A patent/JP2004512254A/en active Pending
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Also Published As
Publication number | Publication date |
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CN1478055A (en) | 2004-02-25 |
US6680042B1 (en) | 2004-01-20 |
WO2002038494A2 (en) | 2002-05-16 |
CA2427605A1 (en) | 2002-05-16 |
WO2002038494A3 (en) | 2002-09-06 |
WO2002038494A8 (en) | 2003-06-12 |
JP2004512254A (en) | 2004-04-22 |
EP1332107A2 (en) | 2003-08-06 |
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