CN1128758C - 氢气的生产方法 - Google Patents
氢气的生产方法 Download PDFInfo
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- CN1128758C CN1128758C CN99810603A CN99810603A CN1128758C CN 1128758 C CN1128758 C CN 1128758C CN 99810603 A CN99810603 A CN 99810603A CN 99810603 A CN99810603 A CN 99810603A CN 1128758 C CN1128758 C CN 1128758C
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- free copper
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 title claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 239000010949 copper Substances 0.000 claims abstract description 73
- 229910052802 copper Inorganic materials 0.000 claims abstract description 72
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 71
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims description 64
- 238000012546 transfer Methods 0.000 claims description 31
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 30
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 30
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 230000009467 reduction Effects 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- 235000011089 carbon dioxide Nutrition 0.000 claims description 13
- 239000005749 Copper compound Substances 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
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- 238000000576 coating method Methods 0.000 claims description 3
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- 230000000694 effects Effects 0.000 abstract description 5
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- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000006260 foam Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 230000007704 transition Effects 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- -1 aluminum compound Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
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- 238000009736 wetting Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 239000003701 inert diluent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0294—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing three or more CO-shift steps
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
- C01B2203/1017—Packed bed of catalytic structures, e.g. particles, packing elements characterised by the form of the structure
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1029—Catalysts in the form of a foam
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C01B2203/1076—Copper or zinc-based catalysts
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- C01B2203/1041—Composition of the catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- General Health & Medical Sciences (AREA)
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Abstract
一种使用含氧化铁的催化剂的高温转移方法，其中在与所述含氧化铁的催化剂接触之前，在280-370℃范围内的温度下使进料气与无铁含铜催化剂接触以进行一些转移反应，从而避免会使所述含氧化铁的催化剂过度还原的条件。
Description
技术领域
本发明涉及氢气，特别涉及由碳质原料生产含氢气流。此类方法是公知的，涉及烃类原料例如天然气或烃衍生物例如甲醇的蒸汽重整或用含氧气体例如基本上纯氧、空气或富氧或贫氧空气使烃或烃衍生物原料或固体碳质原料如煤部分氧化。此气体发生过程产生较高温度(通常高于700℃)的气流，它含有氢气、一氧化碳和水蒸汽，通常还含有一些二氧化碳。此气流通常含有一些甲烷及存在于反应物中的任何惰性气体如氮气。
背景技术
为增加此气流的氢气含量，已知使该气流通过适合的催化剂床经受转移反应：
低温有利于上述转移反应。但由于该反应是放热的，除非在催化剂床内采取诸如使气体冷却等步骤，如果进料含有大量一氧化碳，则通常发生温度上升，因而不能实现低出口温度和/或在低出口温度下有效的催化剂迅速失活。为此所述转移反应通常分两段进行；第一段(高温转移)采用包含氧化铁的催化剂例如氧化铁/氧化铬催化剂，某种形式的床内冷却之后，第二段(低温转移)采用含铜催化剂。
使用中，所述高温转移催化剂中的氧化铁可还原至这样的状态，其中所述催化剂趋于催化费-托反应形成烃。因此希望避免氧化铁还原至这样的状态。我们发现对于使用传统氧化铁/氧化铬催化剂和传统高温转移出口温度例如在约350-500℃范围内的高温转移而言，形成烃的危险取决于一氧化碳与二氧化碳之摩尔比和入口转移气中蒸汽的比例。形成烃的危险随一氧化碳与二氧化碳之比例增加而增加；但只要存在足够的水蒸汽，则可使此危险最小。
用于产生入口转移气的气化阶段通常在500至5000kPa(绝压)范围内、特别是1000至4000kPa(绝压)范围内的压力下操作。进行此气化阶段的温度通常在700至1200℃、特别是750至1100℃的范围内。
一氧化碳与二氧化碳之摩尔比和水蒸汽的比例与气化阶段即所述重整或部分氧化阶段所用条件有关。所述气化阶段所用出口温度升高、压力升高和/或水蒸汽与原料碳之比(即mol水蒸汽/g原料碳)降低都趋于增加所述转移阶段形成烃的危险。
一般地，为使采用氧化铁催化剂的后续高温转移阶段形成烃的危险最小，必须采用含有大量水蒸汽的气体混合物(以致水蒸汽与干气之摩尔比大于约0.5)和/或采用这样的气化条件以致所述气流中一氧化碳与二氧化碳之摩尔比限于不大于约1.9。
所述气化过程涉及蒸汽重整时，可用充分过量的水蒸汽操作以避免此问题。然而，产生如此过量的水蒸汽能效不高，考虑到经济性希望在低蒸汽/碳比下操作蒸汽重整法因而供入所述转移阶段的重整气流有较低的蒸汽/干气之摩尔比，特别地低于0.6。的确，实际的蒸汽重整法一般得到蒸汽/干气之摩尔比在0.2至0.6范围内的气体组合物。同样，在部分氧化法中，气流的一氧化碳含量一般处于导致形成烃存在问题的水平。虽然通过在转移反应之前注入水蒸汽可克服这些困难，但考虑到经济性希望注入蒸汽量最少。在转移反应中转化一摩尔一氧化碳需要一摩尔蒸汽，但为避免形成烃的危险所需蒸汽量一般远大于仅使蒸汽与一氧化碳之摩尔比为至少1.0所需要的。
US5 030 440中提出利用在高于550℃的温度下使用无铁催化剂如浸有钯的铝酸钙载体的初步转移阶段克服这些问题。
我们发明了另一种方法，其中所述初步转移阶段在更低的温度下进行，从而在所述转移阶段之前能实现更大量的热量回收。
US4 861 745中已提出通过在含氧化铁的高温转移催化剂中包含小比例的铜降低形成烃的危险。然而在实践中发现这仅部分有效，因此在含氧化铁的催化剂中存在铜只减缓催化剂被还原至催化烃生成状态的速率。
发明内容
本发明中，在气体与含铁催化剂接触之前使气流与无铁含铜催化剂接触降低形成烃的危险。
因此，本发明提供一种使含一氧化碳和水蒸汽的气流与含氧化铁的催化剂接触的转移方法，特征在于在与所述含氧化铁的催化剂接触之前，使所述气流在280-370℃范围内的入口温度下与无铁含铜催化剂接触。
具体实施方式
通常在高温转移反应段之后进行的所谓“低温”转移反应一般使用无铁的含铜催化剂。含铜比例较高的催化剂一般不在约300℃以上的温度下使用，因为铜趋于烧结而使催化剂失去活性。然而，在本发明中，虽然不可避免地发生一些烧结和活性损失，不要求所述含铜催化剂进行转移至接近平衡，而仅进行某些程度的转移以改变一氧化碳与二氧化碳之比，从而避免后续含氧化铁的催化剂过度还原和随之发生的费-托反应问题。此外，虽然初步转移阶段的入口温度对于高温转移反应而言较低，但对于使用含高比例铜的催化剂的转移反应而言很高，此较高的入口温度补偿所述铜催化剂的活性损失。
可使用的含铜催化剂包括公知用于甲醇合成或低温转移反应的任何催化剂。典型地，所述催化剂包含还原由共沉淀的铜、锌和铝和/或铬化合物如氧化物、氢氧化物或碳酸氢盐的焙烧组合物形成的颗粒所得产品。此催化剂通常含有多于20％(重)的铜。可掺入其它组分如镁或锰化合物。但在优选的体系中，所述含铜催化剂是还原包含负载于诸如氧化铝或铝酸钙水泥等材料上的铜化合物的催化剂前体所得产品。该前体可这样生产：用可热解的铜化合物和可选的其它组分如锌、镁、铝和/或铬化合物的溶液浸渍所述载体，然后焙烧浸渍后的载体使所述铜化合物和可能的其它组分分解至氧化态。或者可用沉淀的可热解铜化合物和可能的上述其它组分的浆液涂布所述载体材料，干燥，然后焙烧使所述可热解化合物转化成氧化形式。优选地，该催化剂在还原后含有3至15％(重)的铜。在与传统的含氧化铁的高温转移催化剂相同的容器中用所述含铜催化剂作为初催化剂床时，利于使用这种通过浸渍或涂布载体制备的催化剂。该催化剂可以是所述载体颗粒的无规填充床形式的，所述载体可以是如US4 810 685中所述大孔泡沫体，或整体结构如蜂窝或如上所述大孔泡沫体，催化物质已通过例如浸清或涂布施于其中。如后面所述在某些情况下用大孔泡沫体作为载体可能是有利的。形成适用的浸渍催化剂的方法之一包括：用碳酸氨合铜配合物浸渍过渡氧化铝载体，然后加热使该配合物分解。
通常需要使用工艺气体例如来自蒸汽重整的工艺气体用于使含氧化铁的高温转移催化剂前体还原至活化态，因为惰性稀释剂中的氢气易导致所述含氧化铁的催化剂前体过度还原。然而，使用传统的粒状含铜转移催化剂或甲醇合成催化剂时，工艺气体用于所述还原阶段易导致所述含铜催化剂过热。使用在载体上有较小比例铜的催化剂，所述载体起散热片的作用使过热的危险最小化，从而可在与所述高温转移催化剂相同的容器中用所述工艺气体进行还原。或者，要求使用含较高比例铜例如高于15％(重)的催化剂时，可通过例如我们的EP 748 255中所述方法使所述催化剂预还原和钝化，其中用氧气和二氧化碳的混合物进行钝化。
可使用的高温转移催化剂包括常用于转移反应的氧化铁/氧化铬组合物，本身可能含有少量的铜。适用的高温转移催化剂的例子描述在US5 656 566中。适用的催化剂优选有60至95％(重)的氧化铁含量(用Fe2O3表示)。优选地，所述前体中铁与铬之原子比在6至20、特别是8至12的范围内。所述前体可含有其它金属如铝、锰或如前面所述尤其是铜的氧化物。特别优选的前体有10∶1至100∶1的铁/铜原子比。可通过加热时分解成氧化物的适合金属化合物与所述铁和铬化合物共沉淀引入此附加氧化物。此外，可在要求的其它氧化物或加热时分解成氧化物的化合物存在下使所述铁和铬化合物沉淀掺入此附加氧化物。或者，此氧化物或加热时分解成氧化物的化合物可在焙烧和成形为要求的颗粒之前加入沉淀的铁和铬化合物中。或者，可在焙烧和形成成形颗粒之前或之后，用加热时分解成要求的附加氧化物的化合物的溶液浸渍所述沉淀的铁和铬化合物。
如前面所述，所述初步转移阶段的入口温度应在280-370℃的范围内。优选地在280-350℃、特别是300-330℃的范围内。由于所述转移反应是放热的，所以离开所述无铁含铜的初转移催化剂的气体温度将比所述入口温度稍高一些。根据经验，混合气中的一氧化碳每转化1％(体积)(基于干气)，通常遇到的气体组合物的温升为约10℃。为使生成烃的危险最小，所述无铁含铜催化剂一般需使入口转移气中存在的5-15％一氧化碳转移。温升一般低于约50℃，通常低于30℃。供入到所述无铁含铜催化剂的气体有在0.2至0.6范围内的水蒸汽/干气之比。
所述初步转移反应之后，所述混合气在含氧化铁的高温转移催化剂上经历转移反应。虽然至所述无铁含铜催化剂的入口温度可能低于常用于高温转移催化剂的温度，但在所述无铁含铜催化剂上发生的放热反应使温度升至传统合氧化铁的转移催化剂为活性的水平。如果(通常)在含氧化铁的催化剂上的高温转移反应绝热进行，则离开高温转移反应的气体的温度和一氧化碳含量将取决于入口转移气的组成和接近转移平衡的程度。但离开高温转移反应的气体的一氧化碳含量典型地在2-5％(体积)(基于干气)的范围内，出口温度在350-500℃的范围内。如需要，可使所述转移后的气体冷却，在例如200-280℃范围内的出口温度下用传统的低温转移催化剂经历低温转移。
由于所述无铁含铜的初步转移催化剂可进行显著量的转移反应，所以可减少所用含氧化铁的高温转移催化剂的体积。典型地多达10％(体积)的含氧化铁的高温转移催化剂可被所述无铁含铜催化剂替代。优选地，无铁含铜催化剂的用量为所述含氧化铁催化剂的3-5％(体积)。传统的含氧化铁的高温转移催化剂通常在2500至5000h-1范围内的湿气空速下操作，但某些现代高活性的含氧化铁的高温转移催化剂已在更高的湿气空速例如高达约7500h-1下操作。在5000h-1的总湿气空速下但用本发明无铁含铜催化剂代替5％(体积)传统的含氧化铁的高温转移催化剂操作意味着所述无铁含铜催化剂在100000h-1的湿气空速下操作。优选地，所述无铁含铜催化剂在至少20000h-1、特别是至少50000h-1的湿气空速下操作。应理解所需无铁含铜催化剂的体积主要取决于给定体积的催化剂中铜的量和该铜与工艺气体的易接近性。优选地，无铁含铜催化剂的用量使所述湿气流量在250-3000L(在NTP下)湿气/g催化剂中的铜/h的范围内。
许多工艺中，例如通过蒸汽重整和/或部分氧化生产原料气之后进行所述转移反应时，在所述转移阶段之前从工艺气体中回收热量。此热量回收通常涉及水蒸汽在埚炉中上升。这种埚炉易出故障和泄漏，结果埚炉固体例如硅酸盐和磷酸盐被工艺气体带入转移反应器。此固体沉积在转移催化剂上导致催化剂堵塞而失去活性，并使工艺气体通过转移催化剂时所遇到的压降升高。使用涂布或浸渍的大孔泡沫形式的所述无铁含铜催化剂，此埚炉固体可被泡沫捕集因而避免此压降问题。
通过以下实施例说明本发明。
实施例1
在约60℃下将含有硝酸铜和硝酸锌的水溶液加入氧化铝三水合物在碳酸钠水溶液中的浆液中，制备无铁含铜催化剂的前体。所得浆液的最终pH为7.2。使沉淀物在60℃下老化约45分钟，然后从母液中滤出，洗涤。所得滤饼在120℃下干燥过夜，粉碎，筛分通过1.4mm的筛，然后在300℃焙烧6小时。然后将焙烧后的粉末压缩，造粒成为直径5.4mm、长3.6mm的圆柱形丸粒。所述丸粒的颗粒密度为约2g/cm3，标称组成为CuO 25％w/w、ZnO 25％w/w、Al2O3 50％w/w。
使约15ml所述丸粒(共含3.2g铜)与185ml α-氧化铝碎片混合，装入内径37mm的管式反应器中。用含2％(体积)氢气的氮气使所述丸粒中的氧化铜还原成金属铜，开始时温度为225℃，经过2小时温度升至240℃，然后在2800kPa(绝压)的压力和365℃的温度下使试验气体混合物通过所述催化剂。该反应器在365℃下等温操作。所述试验气体的组成如下(％体积)：13.9 CO、6.3 CO2、53.1 H2、1.0 CH4、25.7N2，与50份(体积)水蒸汽/100份干气混合。所述气体的一氧化碳/二氧化碳之比为2.2，水蒸汽/干气之比为0.5。在延长使用期间该气体易导致含氧化铁的高温转移催化剂过度还原。为避免此危险，希望所述一氧化碳/二氧化碳之比降至低于约1.9。为使一氧化碳/二氧化碳之比低于1.9，必须使约5％或更多的一氧化碳转移而得到一氧化碳含量低于约8.8％(体积)(基于湿气)的出口气体。
在空速(升湿气/升未稀释的催化剂/小时)范围内经5天的时间进行试验，测定流出气的一氧化碳含量(基于湿气)。
为模拟催化剂通过热烧结的老化，使温度升至435℃保持5天，然后再重复在365℃下的试验5天。
为对比，以类似的方式试验可商购的掺铜氧化铁-铬高温转移催化剂。结果示于下表中。
| 湿气空速(h-1) | 无铁含铜催化剂 | 掺铜氧化铁-铬催化剂 | ||||||
| 出口气体CO(％) | CO/CO2之比 | 出口气体CO(％) | CO/CO2之比 | |||||
| 初始 | 重复试验 | 初始 | 重复试验 | 初始 | 重复试验 | 初始 | 重复试验 | |
| 60000 | 6.4 | 6.9 | 0.9 | 1.0 | 7.0 | 7.3 | 1.1 | 1.2 |
| 72000 | 6.6 | 7.2 | 1.0 | 1.1 | 7.3 | 7.4 | 1.2 | 1.2 |
| 86000 | 6.8 | 7.3 | 1.0 | 1.2 | - | 7.7 | - | 1.3 |
| 98000 | 7.0 | 7.7 | 1.1 | 1.3 | 7.6 | 7.8 | 1.3 | 1.4 |
| 110000 | - | 7.9 | - | 1.4 | 7.9 | 8.0 | 1.4 | 1.5 |
从以上结果可见，所述无铁含铜初步转移催化剂是有效的，甚至在高湿气空速下也使一氧化碳的转化足以使一氧化碳/二氧化碳之比降至低于1.9，从而可用所述无铁含铜初步转移催化剂代替在5000h-1的湿气空速下操作的部分(低于5％体积)传统含氧化铁的高温转移催化剂，在气体遇到所述含氧化铁的催化剂之前实现足够的一氧化碳转化。
实施例2
该实施例中，用大孔氧化铝泡沫作为载体制备无铁含铜催化剂的前体。所述载体为直径16mm、高16mm的圆柱形丸粒，孔隙度为35-40％，密度为约1.3g/cm3，通过US4 810 685中所述方法制备。将所述丸粒浸入含约40％(重)共沉淀的铜、锌和铝化合物的浆液中，近似原子比为3.4Cu∶1.7Zn∶1Al。将浸渍后的载体干燥，在380-420℃下焙烧使所述铜、锌和铝化合物分解成相应的氧化物。所得含铜泡沫丸粒含有1.42％(重)的铜。
将45ml所述含铜泡沫丸粒(共含0.59g铜)粉碎，与155ml α-氧化铝碎片混合，装入内径37mm的管式反应器中。在2800kPa(绝压)的压力下通入如实施例1中所用但含50份(体积)水蒸汽/50份干气的试验气体，使所述丸粒中的氧化铜还原成金属铜。在250℃下开始还原，使温度逐渐升至440℃，并在此温度保持4小时。然后使试验气体中水蒸汽量降至50份(体积)水蒸汽/100份干气。
使温度降至365℃，在5天的时间内改变空速(升湿气/升未稀释的催化剂/小时)。在不同的空速下测定流出气的一氧化碳含量(基于湿气)。为模拟催化剂通过热烧结的老化，使温度升至400℃保持5天，然后再重复在365℃下的试验5天。为模拟埚炉泄漏，使反应器冷却至室温，水沉积在催化剂上。然后在20000h-1的空速下在365℃下试验此老化的润湿的催化剂5天。结果示于下表中。
| 湿气空速(h-1) | 出口气体CO(％) | CO/CO2之比 | ||||
| 初始 | 重复试验 | 润湿后 | 初始 | 重复试验 | 润湿后 | |
| 20000 | 3.7 | 5.5 | 6.3 | 0.4 | 0.7 | 0.9 |
| 24000 | 4.1 | 5.9 | - | 0.4 | 0.8 | - |
| 28000 | 4.3 | 6.2 | - | 0.5 | 0.9 | - |
| 32500 | 4.5 | 6.4 | - | 0.5 | 0.9 | - |
| 37000 | 4.7 | 6.7 | - | 0.5 | 1.0 | |
实施例3
重复实施例2，但使用含60％(重)所述共沉淀的铜、锌和铝化合物的浆液。所得含铜泡沫丸粒含有1.94％(重)的铜。45ml的泡沫丸粒其含0.85g铜。结果示于下表中。
| 湿气空速(h-1) | 出口气体CO(％) | CO/CO2之比 | ||||
| 初始 | 重复试验 | 润湿后 | 初始 | 重复试验 | 润湿后 | |
| 20000 | 3.6 | 5.2 | 6.3 | 0.4 | 0.6 | 0.9 |
| 24000 | 3.8 | 5.6 | - | 0.4 | 0.7 | - |
| 28000 | 4.2 | 5.8 | - | 0.5 | 0.8 | - |
| 32500 | 4.7 | 6.0 | - | 0.5 | 0.8 | - |
| 37000 | 4.4 | 6.3 | - | 0.5 | 0.9 | |
实施例4
重复实施例2，但不使用所述铜、锌和铝化合物的浆液，而将所述泡沫丸粒浸入含铜、锌和铝的硝酸盐和尿素的水溶液中，在泡沫丸粒存在下使所述铜、锌和铝化合物均匀沉淀。所述溶液是将212.85g尿素加入含302g Cu(NO3)2·3H2O、145.77g Zn(NO3)2·6H2O和48.77gAl(NO3)3·9H2O的水溶液中制备。
从所述丸粒中排出过量的溶液，然后在450℃下焙烧。所述丸粒含有4.38％(重)的铜。将25ml所述含铜泡沫丸粒(共含0.92g铜)粉碎，与175ml α-氧化铝碎片混合，装入内径37mm的管式反应器中。在2800kPa(绝压)的压力下通入如实施例1中所用但含50份(体积)水蒸汽/50份干气的试验气体，使所述丸粒中的氧化铜还原成金属铜。在250℃下开始还原，使温度逐渐升至440℃，并在此温度保持4小时。然后使试验气体中水蒸汽量降至50份(体积)水蒸汽/100份干气。
使温度降至365℃，在5天的时间内改变空速(升湿气/升未稀释的催化剂/小时)。在不同的空速下测定流出气的一氧化碳含量(基于湿气)。结果示于下表中。
| 湿气空速(h-1) | 出口气体CO(％) | CO/CO2之比 |
| 36000 | 7.6 | 1.3 |
| 43500 | 7.8 | 1.4 |
| 51000 | 8.0 | 1.5 |
| 58500 | 8.1 | 1.5 |
| 66000 | 8.2 | 1.5 |
实施例5
重复实施例4的步骤，但仅将87.65g(代替212.85g)尿素加入所述500ml铜、锌和铝的硝酸盐溶液中，焙烧后，将所述浸渍过的丸粒再浸入所述溶液中，排干，焙烧。将此再浸渍、排干和焙烧步骤再重复一遍。所得丸粒含有9.01％(重)的铜。
如实施例4中所述试验该丸粒。结果示于下表中。
| 湿气空速(h-1) | 出口气体CO(％) | CO/CO2之比 |
| 36000 | 5.7 | 0.7 |
| 43500 | 5.9 | 0.8 |
| 51000 | 6.3 | 0.9 |
| 58500 | 6.6 | 0.9 |
| 66000 | 6.8 | 1.0 |
Claims (7)
1.一种使含一氧化碳和水蒸汽的气流与含氧化铁的催化剂接触的转移方法，其特征在于，在与所述含氧化铁的催化剂接触之前，使所述气流在280-370℃范围内的入口温度下以及至少20000h-1的湿气空速下与无铁含铜催化剂接触，所述无铁含铜催化剂是还原用铜化合物浸渍或涂布的载体得到的产品，以使所述无铁含铜催化剂含有3-15％重的铜。
2.权利要求1的方法，其中所述入口温度在280-330℃的范围内。
3.权利要求1的方法，其中所述无铁含铜催化剂在至少50000h-1的湿气空速下操作。
4.权利要求1的方法，其中无铁含铜催化剂的量是这样的以使在标准温度压力条件下所述湿气流量在250-3000升湿气/克所述催化剂中的铜/小时的范围内。
5.权利要求1的方法，其中供入到所述无铁含铜催化剂的气体除一氧化碳和水蒸汽之外还含有氢气和二氧化碳，并且一氧化碳/二氧化碳之摩尔比高于1.9。
6.权利要求1的方法，其中供入到所述无铁含铜催化剂的气体有在0.2至0.6范围内的水蒸汽/干气之比。
7.权利要求1的方法，其中所述无铁含铜催化剂使供入到所述无铁含铜催化剂的气体中的5-15％的一氧化碳转化。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9820608.9A GB9820608D0 (en) | 1998-09-23 | 1998-09-23 | Hydrogen |
| GB9820608.9 | 1998-09-23 |
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| CN1316974A CN1316974A (zh) | 2001-10-10 |
| CN1128758C true CN1128758C (zh) | 2003-11-26 |
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| CN99810603A Expired - Fee Related CN1128758C (zh) | 1998-09-23 | 1999-09-06 | 氢气的生产方法 |
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| US (1) | US6500403B2 (zh) |
| EP (1) | EP1115650B1 (zh) |
| JP (1) | JP4462763B2 (zh) |
| KR (1) | KR100580417B1 (zh) |
| CN (1) | CN1128758C (zh) |
| AT (1) | ATE240259T1 (zh) |
| AU (1) | AU749434C (zh) |
| BR (1) | BR9913974A (zh) |
| CA (1) | CA2342877C (zh) |
| CZ (1) | CZ297415B6 (zh) |
| DE (1) | DE69907934T2 (zh) |
| ES (1) | ES2201765T3 (zh) |
| GB (1) | GB9820608D0 (zh) |
| ID (1) | ID27916A (zh) |
| MY (1) | MY126426A (zh) |
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| JP2002079100A (ja) * | 2000-09-08 | 2002-03-19 | Hiroshima Industrial Technology Organization | メタノール水蒸気改質用球状微粒子触媒前駆体並びにメタノール水蒸気改質用球状微粒子触媒及びその製造方法 |
| JP2002079101A (ja) * | 2000-09-08 | 2002-03-19 | Hiroshima Industrial Technology Organization | メタノール水蒸気改質用触媒前駆体並びにメタノール水蒸気改質用触媒及びその製造方法 |
| GB0121680D0 (en) * | 2001-09-08 | 2001-10-31 | Ici Plc | Catalysts |
| GB0217801D0 (en) * | 2002-08-01 | 2002-09-11 | Ici Plc | Hydrogen |
| CA2520988A1 (en) * | 2003-04-01 | 2004-10-14 | Haldor Topsoe A/S | Process for the preparation of a hydrogen-rich stream |
| US7169376B2 (en) * | 2004-06-10 | 2007-01-30 | Chevron U.S.A. Inc. | Method for making hydrogen using a gold containing water-gas shift catalyst |
| US7510696B2 (en) * | 2005-02-07 | 2009-03-31 | Air Products And Chemicals, Inc. | Method and apparatus for the production of hydrogen-rich gas |
| US20080128655A1 (en) * | 2006-12-05 | 2008-06-05 | Diwakar Garg | Process and apparatus for production of hydrogen using the water gas shift reaction |
| US20080131361A1 (en) * | 2006-12-05 | 2008-06-05 | Diwakar Garg | Process and apparatus for the production of hydrogen gas |
| RU2445160C1 (ru) * | 2011-04-05 | 2012-03-20 | Государственное образовательное учреждение высшего профессионального образования "Ивановский государственный химико-технологический университет" | Способ приготовления катализатора среднетемпературной конверсии оксида углерода водяным паром |
| GB201119957D0 (en) * | 2011-11-18 | 2012-01-04 | Johnson Matthey Plc | Process |
| GB201119960D0 (en) * | 2011-11-18 | 2012-01-04 | Johnson Matthey Plc | Process |
| DE102014004391A1 (de) | 2014-03-26 | 2015-10-15 | Clariant International Ltd. | Verfahren zur Herstellung von Katalysatoren mit erhöhter Festigkeit und verringertem Volumenschwund |
| RU2603641C1 (ru) * | 2015-12-28 | 2016-11-27 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" (ИГХТУ) | Способ приготовления катализатора среднетемпературной конверсии оксида углерода водяным паром |
| BR102020020748A2 (pt) | 2020-10-08 | 2022-04-19 | Petróleo Brasileiro S.A. - Petrobras | Métodos de preparo de catalisadores de deslocamento do gás d'água a alta tempertaura, catalisadores e processo para redução de monóxido de carbono |
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| US4021366A (en) * | 1975-06-30 | 1977-05-03 | Texaco Inc. | Production of hydrogen-rich gas |
| DK147937C (da) * | 1980-11-18 | 1985-07-01 | Haldor Topsoe As | Fremgangsmaade til fremstilling af hydrogenholdige gasser, specielt ammoniaksyntesegas, ud fra carbonhydrider |
| EP0361648B1 (en) * | 1988-07-22 | 1993-04-07 | Imperial Chemical Industries Plc | Hydrogen production including a shift reaction process |
| US4861745A (en) * | 1988-08-03 | 1989-08-29 | United Catalyst Inc. | High temperature shift catalyst and process for its manufacture |
-
1998
- 1998-09-23 GB GBGB9820608.9A patent/GB9820608D0/en not_active Ceased
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- 1999-09-06 EP EP99943150A patent/EP1115650B1/en not_active Expired - Lifetime
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- 1999-09-06 AT AT99943150T patent/ATE240259T1/de not_active IP Right Cessation
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- 1999-09-06 BR BR9913974-0A patent/BR9913974A/pt not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| US6500403B2 (en) | 2002-12-31 |
| EP1115650B1 (en) | 2003-05-14 |
| CA2342877A1 (en) | 2000-03-30 |
| DE69907934T2 (de) | 2004-05-19 |
| MY126426A (en) | 2006-09-29 |
| ATE240259T1 (de) | 2003-05-15 |
| GB9820608D0 (en) | 1998-11-11 |
| KR100580417B1 (ko) | 2006-05-16 |
| WO2000017096A1 (en) | 2000-03-30 |
| US20010024632A1 (en) | 2001-09-27 |
| AU5642099A (en) | 2000-04-10 |
| CZ297415B6 (cs) | 2006-12-13 |
| AU749434C (en) | 2004-01-29 |
| CZ2001943A3 (en) | 2001-06-13 |
| DE69907934D1 (de) | 2003-06-18 |
| ES2201765T3 (es) | 2004-03-16 |
| BR9913974A (pt) | 2001-06-12 |
| EP1115650A1 (en) | 2001-07-18 |
| CA2342877C (en) | 2009-05-19 |
| KR20010079903A (ko) | 2001-08-22 |
| ZA200101692B (en) | 2002-05-28 |
| JP2002526357A (ja) | 2002-08-20 |
| ID27916A (id) | 2001-05-03 |
| AU749434B2 (en) | 2002-06-27 |
| JP4462763B2 (ja) | 2010-05-12 |
| CN1316974A (zh) | 2001-10-10 |
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