JP2006500202A - 触媒粒子及びその脱硫への使用法 - Google Patents
触媒粒子及びその脱硫への使用法 Download PDFInfo
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- JP2006500202A JP2006500202A JP2004537160A JP2004537160A JP2006500202A JP 2006500202 A JP2006500202 A JP 2006500202A JP 2004537160 A JP2004537160 A JP 2004537160A JP 2004537160 A JP2004537160 A JP 2004537160A JP 2006500202 A JP2006500202 A JP 2006500202A
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- Prior art keywords
- catalyst
- nickel
- alumina
- extrudate
- catalyst particles
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000002245 particle Substances 0.000 title claims abstract description 48
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 15
- 230000023556 desulfurization Effects 0.000 title abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 92
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 67
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 239000011787 zinc oxide Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000003009 desulfurizing effect Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 21
- 239000011593 sulfur Substances 0.000 description 21
- 229910052717 sulfur Inorganic materials 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 150000003464 sulfur compounds Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002594 sorbent Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 heterocyclic sulfur compounds Chemical class 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000002453 autothermal reforming Methods 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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Abstract
Description
本発明は、酸化亜鉛及びアルミナを含む担体上に還元(reduced)原子価状態のニッケルを含有する触媒粒子及びこの触媒粒子を用いた炭化水素質原料の脱硫方法に関する。
炭化水素質流の水素に富むガスへの転化に使用される接触法、例えば水蒸気改質、自熱式改質、及び接触部分酸化は、硫黄に極めて敏感である。Co−Mo又はNi−Mo触媒を用いた従来の水素化脱硫法で得られる脱硫炭化水素質流は、一般にこれら硫黄に敏感な用途に好適なレベルには高すぎる硫黄レベルである。水素化脱硫した炭化水素質流は、チオフェン、ベンゾチオフェン、置換し縮合した環式ジベンゾチオフェン等の複素環式硫黄化合物のような除去困難な硫黄化合物を含有する。したがって、従来の水素化脱硫を受けた炭化水素質流中になお存在する少量の“困難な”硫黄化合物を除去できる触媒が必要である。
Ind.Eng.Chem.Res.40(2001)p.2367−2370には、ニッケル、酸化亜鉛及びアルミナを含む同様な二重機能触媒が記載されている。この触媒のZn:Ni比は12未満である。
ZnOを増量すると、触媒の硫化水素吸収能力が向上し、これにより触媒の再生又は交換を必要とする前に、触媒の寿命が延びるので有利である。しかし、酸化亜鉛量を増やすと、アルミナ含有量が減少し、こうして強度の低下及び/又はニッケルの分散低下をもたらす。
したがって、本発明は、酸化亜鉛及びアルミナを含む担体上に還元原子価状態のニッケルを含有すると共に、Zn:Ni原子比が12以上の触媒粒子であって、
粉末状酸化亜鉛と、粉末状のアルミナ又はアルミナ前駆体とを混合する工程、
該粉末混合物に酸及び水を、得られるドウが粉末1kg当り酸を0.8〜1.2モル当量含有するような量、添加することにより、該粉末混合物を解凝固すると共に、押出可能なドウを形成する工程、
該押出可能なドウを押し出して、押出物を形成する工程、
該押出物を乾燥し、焼成する工程、
該押出物をニッケル化合物の水溶液で含浸する工程、
該含浸押出物を乾燥し、焼成し、還元する工程、
により製造した該触媒粒子に関する。
いかなる理論にも束縛されるものではないが、本発明触媒粒子の製造方法によれば、完成触媒中で酸化亜鉛、及びアルミナ又はアルミナ前駆体の両方の分酸性が極めて高く、アルミナの結合特性が極めて良好で、しかも硫化水素の吸収に非常に有用な酸化亜鉛が得られるものと考えられる。
この粉末混合物に酸及び水を、粉末混合物が解凝固すると共に、押出可能なドウが形成されるような量、添加する。十分な解凝固を達成するため、ドウは、粉末1kg当り酸を0.8〜1.2モル当量、即ち、プロトンを含有する。液体、即ち、酸及び水の合計添加量は、押出可能なドウが形成されるような量でなければならない。押出可能なドウの形成に必要な液体量が特に粉末の細孔容量によることは、理解されよう。濃厚な酸を使用することが好ましい。硝酸、クエン酸及び酢酸は、好適な濃厚酸の例である。硝酸が好ましい。
焼成した押出物は、ニッケル塩の水溶液、好ましくはアルミナの等電点を超えるpHを有するニッケル塩の塩基性溶液で含浸する。更に好ましくは、焼成押出物は、ニッケル塩のアンモニア性溶液、例えば炭酸ニッケルのアンモニア溶液又は水酸化ニッケルのアンモニア性溶液で含浸する。このようなニッケルのアンモニア性溶液は、例えばアンモニアと炭酸アンモニウムとの混合物に水酸化ニッケル又は炭酸ニッケルを溶解することにより製造してよい。
引き続き、含浸した押出物は、乾燥し、焼成する。
触媒粒子のZn:Ni原子比は、12以上、好ましくは15以上、更に好ましくは20以上である。高いZn:Ni原子比の利点は、触媒の硫化水素吸収能力が大きいことである。しかし、“困難な”硫黄化合物の転化に十分なNiを保持させるため、Zn:Ni比は、最大値まで制約される。Zn:Ni原子比は、好ましくは75以下、更に好ましくは30以下である。
本発明の脱硫法に好適な原料は、ナフサ、或いはガス油又はナフサの水素化分解又は水素化脱硫で製造される中間蒸留物である。これら原料の硫黄含有量は、1000ppm以下である。本発明方法による硫黄の減少程度は、原料の種類及び原料の硫黄含有量による。例えば硫黄含有量が500〜1000ppmwの範囲にある通常の水素化脱硫ガス油の硫黄含有量は、20〜100ppmwの範囲に減少できる。硫黄含有量が10〜50ppmwの範囲にある通常の水素化分解ガス油の硫黄含有量は、1ppmw未満に減少できる。得られた脱硫炭化水素流は、水蒸気改質、自熱式改質、及び接触部分酸化のような硫黄に敏感な方法の原料として特に好適である。
実施例
本発明を以下の実施例により更に説明する。
触媒の製造
酸化亜鉛粉末(例えばDurham;Activox C80;燃焼減量3.7重量%;乾燥ZnO 4769g)4925gと、疑似ベーマイト粉末(例えばCriterion;燃焼減量27重量%;乾燥基準で530g)726gとをSimpson混合粉砕機中で混合した。この混合物に濃(65重量%)硝酸371g、水2203g及び押出助剤を添加した。得られた混合物と30分間混練して、押出可能なドウを形成した。このドウをBonnot押出機上の1.3mm3葉(trilobe)形ダイを用いて押し出した。押出物を120℃で2時間乾燥し、次いで550℃で2時間焼成した。押出物の強度を測定すると、107N/cmであった。
押出物をニッケル含浸溶液で含浸した。次いで、含浸した押出物を120℃で乾燥し、更に350℃で2時間焼成した。
焼成した触媒粒子を脱硫反応器に装入し、2バール(絶対)の圧力で粒子上に水素流(30Nl/h)を誘導することにより還元した。還元中、温度を120℃で2時間維持した後、370℃に上げ、この温度で2時間維持した。次いで温度を300℃に下げ、圧力を15バール(絶対)に上昇させ、更に硫黄含有量18ppmwの水素化分解ガス油(3Nl/kg油)を触媒粒子上に誘導した。こうして処理したガス油の硫黄含有量は、0.1ppmw未満となった。
例1と同じ製造法で、ZnOを85重量%及びアルミナを15重量%含有する触媒担体を製造した。押出物の強度を測定すると、130N/cmであった。押出物を例1に記載のニッケル溶液で含浸した。担体の重量に対し4.8重量%(金属Niとして計算して)のNi濃度が得られた。ニッケル分散は41%であった。
例1と同じ製造法で、ZnOを100重量%含み、アルミナを含まない触媒担体を製造した。押出物の強度は、20N/cm未満であった。
比較例として、押出可能なドウにニッケル前駆体を添加した触媒を製造した。ZnO粉末と疑似ベーマイト粉末との混合物に、濃硝酸、水及び硝酸ニッケル溶液及び押出助剤を加えて押出可能なドウを形成した。押出可能なドウの製造法は、水の一部分を硝酸ニッケル溶液で置換した他は例1と同じである。得られた押出物は、ZnO及びアルミナの重量に対し、ZnOを90重量%、アルミナを10重量%、及びニッケルを6.8重量%(金属ニッケルとして計算して)含有していた。押出物の強度は、30N/cmであった。
本発明触媒粒子の硫黄吸収能力を試験するため、比較的多量の硫黄化合物を含む水素化脱硫ガス油について、脱硫実験を行った。
Claims (10)
- 酸化亜鉛及びアルミナを含む担体上に還元原子価状態のニッケルを含有すると共に、Zn:Ni原子比が12以上の触媒粒子であって、
粉末状酸化亜鉛と、粉末状のアルミナ又はアルミナ前駆体とを混合する工程、
該粉末混合物に酸及び水を、得られるドウが粉末1kg当り酸を0.8〜1.2モル当量含有するような量、添加することにより、該粉末混合物を解凝固すると共に、押出可能なドウを形成する工程、
該押出可能なドウを押し出して、押出物を形成する工程、
該押出物を乾燥し、焼成する工程、
該押出物をニッケル化合物の水溶液で含浸する工程、
該含浸押出物を乾燥し、焼成し、還元する工程、
により製造した該触媒粒子。 - 前記酸が、硝酸、クエン酸又は酢酸、好ましくは硝酸である請求項1に記載の触媒粒子。
- 前記ニッケル化合物の水溶液が、ニッケル塩のアンモニア性溶液である請求項1又は2に記載の触媒粒子。
- 前記担体が、酸化亜鉛及びアルミナからなる請求項1〜3のいずれか1項に記載の触媒粒子。
- 前記Zn:Ni原子比が、15以上、好ましくは20以上であり、かつZn:Ni原子比が、75以下、好ましくは30以下である請求項1〜4のいずれか1項に記載の触媒粒子。
- 前記担体が、アルミナを20重量%以下、好ましくは5〜15重量%含有する請求項1〜5のいずれか1項に記載の触媒粒子。
- 80N/cm以上、好ましくは100N/cm以上の強度を有する請求項1〜6のいずれか1項に記載の触媒粒子。
- 前記ニッケルの濃度が、担体の全重量に対し0.5〜5重量%、好ましくは1〜4重量%、更に好ましくは1〜3重量%の範囲である請求項1〜7のいずれか1項に記載の触媒粒子。
- 20%以上、好ましくは30%以上のニッケル分散を有する請求項1〜8のいずれか1項に記載の触媒粒子。
- 炭化水素質原料を水素の存在下に、150〜500℃の範囲の温度、1〜50バール(絶対)の範囲の圧力、及び0.1〜50kg原料/触媒1リットル/時間、好ましくは0.1〜10kg原料/触媒1リットル/時間の範囲の液体速度で、請求項1〜8のいずれか1項に記載の触媒粒子と接触させる炭化水素質原料の脱硫方法。
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US8216324B2 (en) * | 2008-03-28 | 2012-07-10 | IFP Energies Nouvelles | Process for the production of hydrogen with a thermally-integrated desulfurization unit |
KR101274314B1 (ko) * | 2008-09-24 | 2013-06-13 | 신닛테츠스미킨 카부시키카이샤 | 타르 함유 가스의 개질용 촉매의 제조 방법, 타르 개질 방법 및 타르 함유 가스의 개질용 촉매의 재생 방법 |
DE102009022242A1 (de) | 2009-05-22 | 2010-11-25 | Süd-Chemie AG | Verfahren zur adsorptiven Entschwefelung flüssiger Kohlenwasserstoffe unter Verwendung von Wasserstoffdonatoren |
FR2962727B1 (fr) * | 2009-09-11 | 2012-08-10 | IFP Energies Nouvelles | Procede de preparation d'esters alcooliques et de glycerine a partir de triglycerides et d'alcools au moyen d'un catalyseur heterogene en presence d'eau en teneur controlee |
GB0916161D0 (en) | 2009-09-15 | 2009-10-28 | Johnson Matthey Plc | Desulphurisation process |
WO2013065007A1 (en) | 2011-11-03 | 2013-05-10 | Indian Oil Corporation Ltd. | Nano structured adsorbent for removal of sulphur from diesel and gasoline like fuels and process for preparing the same |
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EP1554037A1 (en) | 2005-07-20 |
ATE359119T1 (de) | 2007-05-15 |
US20080083658A1 (en) | 2008-04-10 |
US7897037B2 (en) | 2011-03-01 |
WO2004026465A1 (en) | 2004-04-01 |
US20110108463A1 (en) | 2011-05-12 |
US8246812B2 (en) | 2012-08-21 |
EP1554037B1 (en) | 2007-04-11 |
DE60313201T2 (de) | 2008-01-31 |
DE60313201D1 (de) | 2007-05-24 |
AU2003299027A1 (en) | 2004-04-08 |
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