CN102802785B - 甲醇水蒸汽重整催化剂 - Google Patents
甲醇水蒸汽重整催化剂 Download PDFInfo
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- CN102802785B CN102802785B CN201080033134.3A CN201080033134A CN102802785B CN 102802785 B CN102802785 B CN 102802785B CN 201080033134 A CN201080033134 A CN 201080033134A CN 102802785 B CN102802785 B CN 102802785B
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- Prior art keywords
- catalyst
- methanol
- hydrogen
- promoter elements
- fuel cell
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000446 fuel Substances 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 35
- 229910045601 alloy Inorganic materials 0.000 claims description 33
- 239000000956 alloy Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229910001868 water Inorganic materials 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 15
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052790 beryllium Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052732 germanium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229910052701 rubidium Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 238000002407 reforming Methods 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012041 precatalyst Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims 3
- 239000000243 solution Substances 0.000 description 40
- 229910052763 palladium Inorganic materials 0.000 description 21
- 239000011701 zinc Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 229910052762 osmium Inorganic materials 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910002535 CuZn Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 2
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910002545 FeCoNi Inorganic materials 0.000 description 1
- 101001086426 Homo sapiens Olfactory receptor 1J2 Proteins 0.000 description 1
- 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 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 229910019501 NaVO3 Inorganic materials 0.000 description 1
- 102100032722 Olfactory receptor 1J2 Human genes 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910008008 ZrCo Inorganic materials 0.000 description 1
- CVOKPKKDMYWRJC-UHFFFAOYSA-N [O-2].C(C)(C)[Ti+2]C(C)C Chemical compound [O-2].C(C)(C)[Ti+2]C(C)C CVOKPKKDMYWRJC-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XPPWAISRWKKERW-UHFFFAOYSA-N copper palladium Chemical compound [Cu].[Pd] XPPWAISRWKKERW-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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Abstract
本文描述可用于甲醇和水蒸汽重整为H2以用于氢燃料电池的基本上不含Cu和Zn的新型催化剂、以及它们的用途。
Description
背景技术
甲醇是用于燃料电池的优异氢气和能量源。甲醇的实用性来自其相对容易储存和运输以及使用重整反应器可以相对容易的将其转化为H2。在重整反应器中,使用金属催化的水蒸汽重整方法从甲醇制备氢气。根据反应的化学过程,在合适的条件下,甲醇和水反应以形成氢气和二氧化碳。
CH3OH+H2O→CO2+3H2(1)
重整方法的一个缺点是通过有别于氢气制备的途径形成副产物CO。重整方法的该副产物在引入给定燃料电池之前必须从产物H2中除去或“洗掉。”典型地,该洗掉过程通过水煤气转换反应而实现。或者,CO可以使用Pd或Pd合金膜来分离。尽管这样,但是Pd和Pd合金膜要求较高操作温度来产生效果;因此重整器必须在较高温度、典型地在约400℃下进行操作。然而,考虑到高温经常不利地影响催化剂寿命,这种高温要求催化剂具有优异的耐受性。
目前可得催化剂的实用性受到这些限制的影响。例如,市售铜-锌催化剂(CuO-ZnO/Al2O3)因为烧结和失活不能在250℃之上的温度下使用。而且,这些催化剂需要在重整器中使用之前进行还原。铜-锌催化剂的另外限制是它们是自燃的,从而产生处理和储存的问题。
例如,美国专利No.6,576,217以及美国专利公开No.2002/0051747,2002/0169075和2004/0006915中已经描述了多种尝试来改善CuO-ZnO催化剂配制物的性能。所述文献中提及的多种改善包括将Zr,Al, Ce或稀土元素引入铜-锌配制物。
还提出使用不同元素来替换Zn或Cu。例如,在美国专利公开No.2004/0006915中,公开含有ZnO和氧化铬但不含氧化铜的催化剂用于甲醇水蒸汽重整。对于铜-锌催化剂的其他修饰包括使用Pd替换Zn,这在JP申请No.2002263499中有所讨论;使用Ag替换Cu,这在JP申请No.2003154270中有所讨论;使用Cr替换Cu,这在JP申请No.2003160304中有所讨论;以及使用SiO2替换Zn,这在JP申请No,2008043884中有所讨论。然而,这些配制物无法解决Zn,Cu或CuZn衍生的催化剂中存在的固有限制。
近年来,非-CuZn碱-金属催化剂、氧化剂负载的FeCoNi在美国专利公开No.2007/0294942中有所描述。然而,该催化剂要求昂贵的有机金属络合物和模板分子以实现期望的晶体尺寸,因此限制其实用性。而且,如同铜-锌催化剂,该碱-金属基催化剂易于在高温下失活。
已知多种其他Zn基甲醇重整催化剂。例如,美国专利No.4,613,584描述了用于甲醇水蒸汽重整的PdZn和PtZn合金的实用性和形成。还参见Iwasa et al,,Applied Catalysis A:General,1995,125(1):145-157以及美国专利No.6,413,449。
PdZnZr基催化剂在美国专利公开No.2001/0021469中有所描述,而Pd/Pt-CuZn催化剂在美国专利公开No.2002/0039965中有所描述。尽管如此,这些催化剂还存在失活的问题。例如,已经报道氧化铝负载的PdZn催化剂在285℃下失活(参见Pfeifer et al, Applied Catalysis A:General,270(1-2),165-175,2004),并且甚至在250℃下失活(参见Kim,T.,et al,Journalof Power Sources,2006,155,(2),231-238)。PdZnZr催化剂受到在重整过程中潜在滤掉Zn的进一步困扰。滤掉的Zn可损害存在的任何分离膜以及燃料电池本身。
适用于甲醇水蒸汽重整的其他已知合金包括ZrCu,ZrAu,HfCu,ZrCo和Yni。尽管它们具有实用性,但是这些催化剂难以制备并且要求熔融金属盐前体。例如参见美国专利No.5,635,439。
Pd-Ga,Pd-In,Pt-Ga和Pt-In催化剂(Iwasa,Catalyst Letter 54,1998,119-123)以及Pt-Ce/Fe/La-负载在氧化铝上(美国专利公开No.2007/0183968)同样显示对于甲醇水蒸汽重整具有活性。这些催化剂非常需要熔融金属前体或包括Pt的预还原、然后依次承载其他金属的多个步骤过程。因此,尽管现有技术描述了多种催化剂用于甲醇水蒸汽重整,但是多种已知催化剂中的每种具有至少一种特性:使催化剂更不易于大规模商业使用。
鉴于此,本公开的目的是提供新型催化剂配制物和制备这些催化剂的方法,其解决目前可得甲醇水蒸汽重整催化剂的多种或全部不足。特别地,本公开的目的是提供用于甲醇重整的空气稳定的催化剂,其在至少约350℃下连续操作并且不需要熔融或预还原。
发明概述
在实施方案中,催化剂可以包含:Pt或Pd;合金形成用元素,其选自Sc,Hf,V, Nb,Ta,Ru,Os,Co,Rh,Ir,Ni,B,Al,Ga,In,Ti,C,Si,Ge,Sn和Pb;以及至少一种助催化剂(promoter)元素,其选自Li,Na,K,Rb,Cs,Be,Mg,Ca,Sr, Ba,Fe,La,Y, Zr及其组合。催化剂基本上不含Cu和Zn。催化剂还包含合适的载体或负载体,选自氧化铝,氧化硅,CeO2,碳及其混合物。
在实施方案中,催化剂可以在至少约200℃的温度下操作。在另一实施方案中,催化剂可以在约350至约425℃的温度下操作。本文所述的催化剂不显示铜-锌或钯-锌催化剂的任何上述缺点。另外,本文所述的催化剂的制备不包括熔融金属或金属前体,和不包括涉及一种元素的预还原、接着依次承载的多个步骤。公开的催化剂可以应用于传统氧化物负载体,陶瓷,或金属基材(包括箔、热交换板等)以制备用于氢燃料电池应用的高效和密实甲醇重整器。
所述催化剂可以快速和容易地制备,并且可以应用于多种结构化金属和非金属表面。或者,所述催化剂可以用作粉末、颗粒形式、小球、或任何其他适于靶向应用的物理形式。
本公开描述了不含Cu和Zn的催化剂。该催化剂可以包含:选自Pt或Pd的第一金属;合金形成用元素其选自Sc,Hf,Hf,V, Nb,Ta,Ru,Os,Co,Rh,Ir,Ni,B,Al,Ga,In,Ti,C,Si,Ge,Sn和Pb;以及至少一种助催化剂元素,其选自Li,Na,K,Rb,Cs,Be,Mg,Ca,Sr,Ba,Fe,La,Y,Zr及其组合。
在一个实施方案中,第一金属是Pt。在子实施方案中,合金形成用元素是V。在进一步子实施方案中,至少一种助催化剂是Zr。在另外子实施方案中,合金形成用元素是Ti。在进一步子实施方案中,至少一种助催化剂元素是Zr。
在另外实施方案中,第一金属是Pd。在一个子实施方案中,合金形成用元素是Ga。在进一步子实施方案中,至少一种助催化剂元素是Zr。在进一步子实施方案中,催化剂包含第二助催化剂元素。在某些实施方案中,第二助催化剂元素是Y。在其他实施方案中,第二助催化剂元素是Ba。
在进一步子实施方案中,催化剂包含第三助催化剂元素。在某些实施方案中,第三助催化剂元素是Ba。在其他实施方案中,第三助催化剂元素是Fe。
本发明的催化剂可以进一步包含负载体。在某些实施方案中,负载体是CeO2。
本公开还包括制备本文所述催化剂的方法。在某些实施方案中,该方法包括:形成所述第一金属的络合物或盐、所述合金形成用元素的络合物或盐、和所述至少一种助催化剂的络合物或盐的第一水溶液。该方法还可包括:形成包含碳酸钠和任选的脲的第二水溶液。该方法还可包括:将负载体加入所述第二水溶液,从而形成浆料。该方法还可包括:混合所述第一水溶液和所述浆料,从而形成第二浆料。
该方法还可包括:研磨所述第二浆料;干燥所述浆料以形成预催化剂;以及煅烧所述预催化剂以形成本文所述的催化剂。
本公开还包括将甲醇和水蒸汽重整为氢气的方法。在一个实施方案中,该方法包括:加热甲醇水溶液以形成甲醇水蒸气。该方法还可包括:将所述蒸气供入甲醇重整设备,所述甲醇重整设备含有加热至至少约200℃的甲醇水重整催化剂。该方法还可包括:使所述甲醇水蒸气接触所述加热的催化剂。
在将甲醇和水蒸汽重整为氢气的方法的某些实施方案中,所述催化剂基本上不含Cu和Zn的催化剂,并且包含:选自Pt或Pd的第一金属;合金形成用元素,其选自Sc,Hf,V, Nb,Ta,Ru,Os,Co,Rh,Ir,Ni,B,Al,Ga,In,Ti,C,Si,Ge,Sn和Pb;以及至少一种助催化剂元素,其选自Li,Na,K,Rb,Cs,Be,Mg,Ca,S r,Ba,Fe,La,Y,Zr及其组合。
附图简述
为了描述本文所述的催化剂的实用性,在附图中的多个表和图中示出某些实施方案。然而,本发明不限于附图中所示的实施方案的精确布置方式和手段。
图1示出使用PtV-Zr/CeO2的情况下的运行时间性能。
图2示出使用PtTi-Zr/CeO2的情况下的运行时间性能。
图3示出使用PdGa-ZrY/CeO2的情况下的运行时间性能。
图4示出使用PdGa-BaZrY/CeO2的情况下的运行时间性能。
图5示出使用PdGa-FeBaZr/CeO2的情况下的运行时间性能。
图6示出使用PdZn-ZrY/CeO2的情况下的运行时间性能。
发明详述
定义和缩写
依照该详述,适用下列缩写和定义。必须注意,除非另有清楚地标明,否则单数形式的″a″,″an″和″the″包括复数标记。因此,例如,涉及″催化剂″时包括多种这样的催化剂,并且涉及″所述催化剂″时包括一种或多种催化剂和本领域技术人员已知的等同形式等。
除非另有定义,所有本文中使用的技术和科学术语一般具有如本领域普通技术人员所理解的相同的意思。下面提供术语。
如本文使用的,术语″合金″是指两种或多种元素以它们的还原或部分还原形式的结合结构,在元素展示的情况中不限制为任何特定配合形式。
涉及元素周期表的元素是已知的它们的一个或两个字母标记。
催化剂包含通常为催化剂的约0.2至约20重量%的Pt或Pd。在某些实施方案中,Pt或Pd占催化剂的约0.5至约10重量%。
催化剂还包含合金形成用元素与Pt或Pd。合金形成用元素选自Sc,Hf,V, Nb,Ta,Ru,Os,Co,Rh,Ir, Ni,B,Al,Ga,In,Ti,C,Si,Ge,Sn或Pb。示例性合金形成用元素的例子包括V, Ni,Ti,Ga,In和Co。合金元素与Pt或Pd的摩尔比为至少约1至约5。在某些实施方案中,摩尔比为至少约1至约3。本文所述的催化剂基本上不含Cu和Zn。
催化剂还包含至少一种助催化剂元素。助催化剂元素选自Li,Na,K,Rb,Cs,Be,Mg,Ca,Sr, Ba,Fe,La,Y, Zr及其组合。助催化剂元素可以存在为总催化剂的0至约10重量%。在某些实施方案中,助催化剂可以存在为约0.1至约3重量%。用作助催化剂的示例性元素的例子包括Mg,Ba,Fe,La,Y, Zr及其混合物。
催化剂还可包含合适的载体或负载体。合适的载体和负载体的例子包括氧化铝,氧化硅,CeO2,陶瓷和碳。也可以使用这些负载体的混合物。在某些实施方案中,负载体的表面积为至少约5m2/g。示例性负载体是CeO2。
负载体可以在使用或不使用碱性预处理的情况下进行制备。当使用时,碱性预处理包括使用至少脲和碳酸钠的水溶液处理负载体例如CeO2。不希望受到任何特定理论的束缚,据信碱性预处理降低CeO2负载体的酸性,进而导致催化剂具有明显更高的甲醇重整活性。
当在固体负载体上制备、接着进行干燥和煅烧工序以制备氧化的催化剂时,催化剂可以加热至至少约200℃的温度以产生接触甲醇和水的氢气。在某些实施方案中,将催化剂加热至约350至约425℃。在某些实施方案中,将催化剂加热至约400℃,以有效地产生氢气,并且蒸气化的甲醇水溶液通过热催化剂。
不希望受到特定理论的束缚,据信在甲醇和水蒸汽存在的条件下,在煅烧过程中形成的Pd或Pt的氧化物还原至它们的零氧化态,在该点Pd或Pt金属原位和合金形成用元素形成合金。如前面所识别的,这些元素包括Sc,Hf,V, Nb,Ta,Ru,Os,Co,Rh,Ir,Ni,B,Al,Ga,In,Ti,C,Si,Ge,Sn和Pb。这些元素(也可以在煅烧过程中具有形成的氧化物)同样可以在催化过程中还原。助催化剂元素选自Li,Na,K,Rb,Cs,Be,Mg,Ca,Sr, Ba,Fe,La,Y和Zr,其还可以在本文所述的条件下部分还原。
本文所述的催化剂可以以较短制备顺序来制备。根据通常的制备方法,形成水溶性Pt或Pd的盐或络合物的第一水溶液。然后通常加入形成合金用元素的水溶性盐或络合物,接着加入特定配制物所需要的一种或多种助催化剂元素的一种或多种水溶性盐或络合物。
然后,可以制备第二水溶液。该溶液任选地含有脲,并且任选地含有助催化剂元素的水溶性盐或络合物。在一个实施方案中,例如,钠可以是助催化剂元素,其可以以Na2CO3的形式加入。加入第二溶液的助催化剂元素的盐或络合物可以和加入第一溶液的助催化剂元素的盐或络合物相同或不同。随后,将已知量的固体负载体加入第二水溶液,从而形成稠密浆料。
然后第一水溶液加入稠密浆料。将所述组合物良好地搅拌,然后进行湿法研磨,典型地在球磨机中进行,以提供期望尺寸的固体颗粒。在某些实施方案中,颗粒的直径可以为至少约3至约20μm。在其他实施方案中,在研磨后颗粒的直径可以为至少约5至约10μm。然后催化剂可以涂覆在单块陶瓷、或金属结构件、或金属箔、或热交换器上以进行干燥。或者,催化剂可以直接干燥。
在任一情况下,将研磨的浆料在至少约100℃的温度下进行干燥。在某些实施方案中,将浆料在至少约120℃下干燥至少约1小时。在某些实施方案中,研磨的浆料可以干燥至少2小时。干燥时间和温度可以随着制备的催化剂的变化而变化。确定在煅烧催化剂之前是否催化剂是足够干燥的是本领域技术人员的技术水平。在干燥后,催化剂在约100至约700℃下在空气中煅烧。在一个实施方案中,催化剂可以在约500℃下煅烧。在另一实施方案中,催化剂可以在约550℃下煅烧。在一个实施方案中,煅烧过程通常需要至少约3小时。在一些实施方案中,煅烧可以要求更多时间,例如至少约4小时。
实施例
现在参照下列实施例来进一步详述本文公开的催化剂。这些实施例提供仅仅为了描述的目的,并且本文公开的催化剂绝不应该理解为限制为这些实施例,相反应该理解为涵盖任何和所有变体形式,这些变体形式作为本文提供教导的结果是明显的。同样提供催化剂比较例。不同于本文公开的催化剂,比较例在它们配制物中包含锌。
在下面提供的各例子中,″水″是指去离子水。除非另有说明,所有反应在大气压下进行。
实施例1:PtV-Zr/CeO2
通过下列方式制备含有Pt和V的第一溶液:将15.244g的六羟基(IV)铂酸(H2Pt(OH)6)溶液(16.40重量%Pt)、1.795g NaVO3和1.484g Zr(OH)4加入35g的水中搅拌。
通过将7.5g脲和0.461g Na2CO3加入30.0g水中制备第二溶液。然后将第二溶液在球磨机瓶中混合50.0g的CeO2(HSA20,来自Rhodia),从而导致形成稠密浆料。然后使第一溶液接触稠密浆料。将所得混合物球磨直到约90%的固体颗粒的直径小于约10μm。随后,将浆料在约120℃下干燥约2h并且在约550℃下在空气中煅烧4h。
在图1中可见,在甲醇/水的供料速度为0.25-1.0mL/min的情况下,在300℃下使用该催化剂获得超过95%的甲醇转化率。在约400℃下增加供料速度为2.5mL/min导致甲醇转化率降低和CO选择率稍微增加。
实施例2:PtTi-Zr/CeO2
通过下列方式制备含有Pt和Ti的第一溶液:将15.244g的六羟基(IV)铂酸(H2Pt(OH)6)溶液(16.40重量%Pt)、7.611g二异丙氧化钛二(乙酰基丙酮酸)(C6H28OeTi,异丙醇中的75%溶液)和1,484g Zr(OH)4加入35g的水中搅拌。
通过将7.5g脲和0.461g Na2CO3加入30.0g水中制备第二溶液。然后将第二溶液在球磨机瓶中混合50.0g的CeO2(HSA20,来自Rhodia),从而导致形成稠密浆料。然后使第一溶液接触稠密浆料。将所得混合物球磨直到约90%的固体颗粒的直径小于10μm。随后,将浆料在约120℃下干燥约2h并且在约550℃下在空气中煅烧约4h。
上述催化剂的性能表现稍微劣于实施例1中的情况。实施例2的催化剂具有更低的甲醇转化率和更高的CO选择率。然而,该催化剂有效地产生H2。
实施例3:PdGa-ZrY/CeO2
通过下列方式制备含有Pd和Ga的第一溶液:将11.844g的Pd(NO3)2溶液(20.77重量%Pd),27.506g硝酸镓水合物、1.484g Zr(OH)4和8.952gY(NO3)3·6H2O加入42.0g的水中搅拌。
通过将7.5g脲和0.461g Na2CO3加入30.0g水中制备第二溶液。然后将第二溶液在球磨机瓶中混合50.0g的CeO2(HSA20,来自Rhodia),从而导致形成稠密浆料。然后使第一溶液接触稠密浆料。将所得混合物球磨直到约90%的固体颗粒的直径小于约10μm。随后,将浆料在约120℃下干燥约2h并且在约550℃下在空气中煅烧约4h。
在使用甲醇/水的供料速度为约0.25mL/min的情况下,在约300℃下使用该实施例的催化剂观察到甲醇的完全转化。当甲醇/水的供料速度降低至约2.0mL/min并且温度升至约400℃时,甲醇转化率降低至80%。
实施例4:PdGa-BaZrY/CeO2
通过下列方式制备含有Pd和Ga的第一溶液:将11.844g的Pd(NO3)2溶液(20.77重量%Pd),27.506g硝酸镓水合物、1.484g Zr(OH)4、0.477gBa(NO3)和8.952g Y(NO3)3·6H2O加入42.0g的水中搅拌。
通过将7.5g脲和0.461g Na2CO3加入30.0g水中制备第二溶液。然后将第二溶液在球磨机瓶中混合50.0g的CeO2(HSA20,来自Rhodia),从而导致形成稠密浆料。然后使第一溶液接触稠密浆料。将所得混合物球磨直到约90%的固体颗粒的直径小于约10μm。随后,将浆料在约120℃下干燥约2h并且在约550℃下在空气中煅烧约4h。
将作为助催化剂的Ba加入实施例3的催化剂会改善催化剂活性和稳定性。在约400℃下使用甲醇/水供料速度为约2-2.5mL/min,获得超过约95%的甲醇转化率。
实施例5:PdGa-FeBaZr/CeO7.
通过下列方式制备含有Pd和Ga的第一溶液:将11.844g的Pd(NO3)2溶液(20.77重量%Pd),27.506g硝酸镓水合物、0.477g Ba(NO3)和1.809gFe(NO3)3·9H2O加入42.0g的水中搅拌。
通过将7.5g脲和0.461g Na2CO3加入30.0g水中制备第二溶液。然后将第二溶液在球磨机瓶中混合50.0g的CeO2(HSA20,来自Rhodia),从而导致形成稠密浆料。然后使第一溶液接触稠密浆料。将所得混合物球磨直到约90%的固体颗粒的直径小于10μm。随后,将浆料在约120℃下干燥约2h并且在约550℃下在空气中煅烧4h。
将作为助催化剂的Fe加入实施例4中所述的配制物导致活性稍微降低,但是CO2选择率从约65%改善至约70%。
比较例1:PdZn-ZrY/CeO2
通过下列方式制备含有Pd,Zn,Y和Zr的溶液:将4.734g的Pd(NO3)2溶液(20.77重量%Pd)、15.508g Zn(NO3)2·6H2O、0.581g Zr(OH)4和4.269gY(NO3)3·6H2O加入7.0g的水中搅拌。然后使该溶液接触20g的CeO2负载体(HSA5,来自Rhodia)。将所得浆料球磨直到约90%的固体颗粒的直径小于约10μm。随后,将浆料在约120℃下干燥约2h并且在约550℃下在空气中煅烧4h。在例子中所述的PdZn催化剂的性能示于图6。
比较例2:PdZn-ZrYLa/CeO2
通过下列方式制备含有Pd,Zn,Y, La和Zr的第一溶液:将11.844g的Pd(NO3)2溶液(20.77重量%Pd),38.659g Zn(NO3)2·6H2O、1.484g Zr(OH)4、9.024gY(NO3)3·6H2O和0,668g LaCl3·7H2O加入45.0g的水中搅拌。
通过将7.5g脲和0.461g Na2CO3加入30.0g水中制备第二溶液。然后将50.0g的CeO2(HSA20,来自Rhodia)在球磨机瓶中加入第二溶液,从而导致形成稠密浆料。然后将第一溶液加入CeO2的稠密浆料。将所得混合物球磨直到约90%的固体颗粒小于10μm。随后,将浆料在约120℃下干燥约2h并且在约550℃下在空气中煅烧约4h。
催化剂性能
在管状填充床型反应器中进行用于甲醇的水蒸汽-重整的催化剂性能的测量,该反应器包括钝化(Silicosteel
)不锈钢管,其内径为5/8-英寸。将该反应器的床填充3g催化剂,该催化剂已经被破碎和筛选至平均直径为约125-250μm。然后将反应器在N2流下加热至400℃。
在反应器达到该温度后,通过HPLC泵以2mL/min(10Psig)将甲醇在去离子水中的约63重量%溶液供入在240℃下操作的蒸汽机。然后使蒸发的甲醇-水混合物通过加热的反应器。蒸汽机优化以保持稳定的流速,并且气相中的水-甲醇摩尔比的波动最小化。
离开反应器的气体的组成使用装有四个通道和四个TCD检测器的Agilent 3000A Micro gas chromatography system(GC)来监控和分析。整个系统是自动的,并且使用计算机来控制以进行操作和数据采集。分析下列气相物质:H2,CO2,CO,H2O,CH4和CH3OH。按照下列方式计算甲醇的转化率和选择率:
在上面提供的等式中,CO%,CO2%,CH4%和CH3OH%表示CO,CO2,CH4和CH3OH在反应器流出物中的的摩尔分数百分比,这分别通过GC来分析。基于重整反应(等式1)的化学计量,至H2的选择率等于至CO2的选择率。
使用上述方法,对于实施例1至5的催化剂,获得表1中详述的选择率结果。
表1.在400℃(*)下催化剂性能的概述
*3g催化剂,以2mL/min供入的63重量%水性甲醇溶液;10Psig,以约15-20h运行
时间操作的性能;
*以约15-20h运行时间操作的数据
如表1中所示,对于甲醇水蒸汽重整,本文所述的催化剂的″不含Zn″的实施方案提供比PdZn催化剂更好或相当的性能。这样,本文所述的催化剂可以用于引入氢气分离膜的燃料电池中。
尽管已经参照上面的实施例来详细描述了上面的催化剂、组合物和方法,但是应该理解,多种改变可以在不偏离它们精神的情况下进行,并且这将使本领域技术人员容易知道的。
出于所有目的,上面所涉及的所有引用专利和公开全部通过引用的方式并入本文。
Claims (14)
1.一种用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,所述催化剂包含:
催化剂的0.5至10重量%的Pd;
合金形成用元素,该合金形成用元素在催化剂面临甲醇和水蒸汽时能够与Pd形成合金,其中该合金形成用元素选自Sc,Nb,Ta,B,Al,Ga,In,Ti,Ge,Sn和Pb,其中所述合金形成用元素与Pd的摩尔比为1至5;
至少一种助催化剂元素,其选自Li,Na,K,Rb,Cs,Be,Mg,Ca,Sr,Ba,Fe,La,Y,Zr及其组合,其中所述至少一种助催化剂元素以催化剂的0至10重量%存在;以及
负载体,其中该负载体是CeO2,并具有大于5m2/g的表面积;
并且所述催化剂不含Cu和Zn。
2.权利要求1所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,其中所述合金形成用元素是Ti。
3.权利要求2所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,其中所述至少一种助催化剂元素是Zr。
4.权利要求1所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,其中所述合金形成用元素是Ga。
5.权利要求4所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,其中所述至少一种助催化剂元素是Zr。
6.权利要求5所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,所述催化剂还包含第二助催化剂元素。
7.权利要求6所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,其中所述第二助催化剂元素是Y。
8.权利要求7所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,所述催化剂还包含第三助催化剂元素。
9.权利要求8所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,其中所述第三助催化剂元素是Ba。
10.权利要求6所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,其中所述第二助催化剂元素是Ba。
11.权利要求10所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,所述催化剂还包含第三助催化剂元素。
12.权利要求11所述的用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂,其中所述第三助催化剂元素是Fe。
13.一种制备用于甲醇和水蒸汽重整为氢以用于氢燃料电池的催化剂的方法,该催化剂包含:
催化剂的0.5至10重量%的Pd;
合金形成用元素,该合金形成用元素在催化剂面临甲醇和水蒸汽时能够与Pd形成合金,其中该合金形成用元素选自Sc,Nb,Ta,B,Al,Ga,In,Ti,Ge,Sn和Pb,其中所述合金形成用元素与Pd的摩尔比为1至5;
至少一种助催化剂元素,其选自Li,Na,K,Rb,Cs,Be,Mg,Ca,Sr,Ba,Fe,La,Y,Zr及其组合,其中所述至少一种助催化剂元素以催化剂的0至10重量%存在;以及
负载体,其中该负载体是CeO2,并具有大于5m2/g的表面积;
并且所述催化剂不含Cu和Zn;
该方法包括:
a.形成Pd的络合物或盐、所述合金形成用元素的络合物或盐、和所述至少一种助催化剂的络合物或盐的第一水溶液;
b.形成包含碳酸钠和任选的脲的第二水溶液;
c.将所述负载体加入所述第二水溶液,从而形成浆料;
d.混合所述第一水溶液和所述浆料,从而形成第二浆料;
e.研磨所述浆料;
f.干燥所述浆料以形成预催化剂;以及
g.煅烧所述预催化剂以形成所述催化剂。
14.一种将甲醇和水蒸汽重整为氢气的方法,所述方法包括:
a.加热甲醇水溶液以形成甲醇水蒸气;
b.将所述蒸气供入甲醇重整设备,所述甲醇重整设备含有加热至350℃至425℃的甲醇水重整催化剂;以及
c.使所述蒸气接触所述加热的催化剂;
其中所述催化剂不含Cu和Zn,并且包含:
催化剂的0.5至10重量%的Pd;
合金形成用元素,该合金形成用元素在催化剂面临甲醇和水蒸汽时能够与Pd形成合金,其中该合金形成用元素选自Sc,Nb,Ta,B,Al,Ga,In,Ti,Ge,Sn和Pb,其中所述合金形成用元素与Pd的摩尔比为1至5;
至少一种助催化剂元素,其选自Li,Na,K,Rb,Cs,Be,Mg,Ca,Sr,Ba,Fe,La,Y,Zr及其组合,其中所述至少一种助催化剂元素以催化剂的0至10重量%存在;以及
负载体,其中该负载体是CeO2,并具有大于5m2/g的表面积。
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EP (1) | EP2435182A4 (zh) |
JP (1) | JP5678041B2 (zh) |
KR (1) | KR101764440B1 (zh) |
CN (1) | CN102802785B (zh) |
AU (1) | AU2010254196B2 (zh) |
CA (1) | CA2763124C (zh) |
RU (1) | RU2011152487A (zh) |
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CN102872867B (zh) * | 2012-10-19 | 2014-05-07 | 厦门大学 | 一种用于甲醇水蒸气重整制氢的催化剂及其制备方法 |
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CN105618131B (zh) * | 2016-01-25 | 2019-02-01 | 华南农业大学 | 一种复合双载体催化剂及其制备方法与应用 |
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CA2996961A1 (fr) * | 2018-03-01 | 2019-09-01 | Hydro-Quebec | Inhibiteur pour metaux alcalins et alcalino-terreux |
CN108855065B (zh) * | 2018-05-24 | 2021-07-06 | 厦门大学 | 一种将Pd/ZnAl2O4催化剂用于甲醇蒸汽重整制氢的方法 |
US20200030776A1 (en) | 2018-07-27 | 2020-01-30 | Johnson Matthey Public Limited Company | Twc catalysts containing high dopant support |
CN112588279B (zh) * | 2020-12-15 | 2022-08-02 | 华东理工大学 | 一种用于甲醇蒸汽重整制氢的催化剂的制备方法及其产品和应用 |
EP4166230A1 (en) * | 2021-10-12 | 2023-04-19 | Johnson Matthey Public Limited Company | Catalyst article for exhaust system of natural gas engine |
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US9174199B2 (en) | 2015-11-03 |
AU2010254196B2 (en) | 2016-04-07 |
US20160023193A1 (en) | 2016-01-28 |
JP5678041B2 (ja) | 2015-02-25 |
EP2435182A2 (en) | 2012-04-04 |
KR20120024841A (ko) | 2012-03-14 |
ZA201109481B (en) | 2014-10-29 |
US20100303713A1 (en) | 2010-12-02 |
CA2763124C (en) | 2018-05-01 |
KR101764440B1 (ko) | 2017-08-02 |
WO2010138483A2 (en) | 2010-12-02 |
JP2012528007A (ja) | 2012-11-12 |
CA2763124A1 (en) | 2010-12-02 |
RU2011152487A (ru) | 2013-07-10 |
WO2010138483A3 (en) | 2011-03-24 |
EP2435182A4 (en) | 2013-04-17 |
CN102802785A (zh) | 2012-11-28 |
AU2010254196A1 (en) | 2011-12-22 |
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