RU2005133637A - Способ эпоксидирования олефинов и катализатор для применения в способе - Google Patents
Способ эпоксидирования олефинов и катализатор для применения в способе Download PDFInfo
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- RU2005133637A RU2005133637A RU2005133637/04A RU2005133637A RU2005133637A RU 2005133637 A RU2005133637 A RU 2005133637A RU 2005133637/04 A RU2005133637/04 A RU 2005133637/04A RU 2005133637 A RU2005133637 A RU 2005133637A RU 2005133637 A RU2005133637 A RU 2005133637A
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- rhenium
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- 239000003054 catalyst Substances 0.000 title claims 34
- 238000000034 method Methods 0.000 title claims 17
- 150000001336 alkenes Chemical class 0.000 title claims 7
- 238000006735 epoxidation reaction Methods 0.000 title 1
- 229910052702 rhenium Inorganic materials 0.000 claims 18
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 5
- 229910052709 silver Inorganic materials 0.000 claims 5
- 239000004332 silver Substances 0.000 claims 5
- 150000001875 compounds Chemical class 0.000 claims 4
- 230000000694 effects Effects 0.000 claims 4
- 150000000180 1,2-diols Chemical class 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 3
- 150000004820 halides Chemical class 0.000 claims 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 229910052796 boron Inorganic materials 0.000 claims 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 2
- 239000011733 molybdenum Substances 0.000 claims 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 2
- 239000011574 phosphorus Substances 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- 239000010937 tungsten Substances 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- -1 ether 1, 2-diol Chemical class 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/08—Epoxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Claims (22)
1. Способ эпоксидирования олефина, который включает взаимодействие сырья, содержащего олефин, кислород и органический галогенид в присутствии катализатора, содержащего серебро и рений, нанесенные на носитель, где катализатор содержит рений в количестве, самое большее 1,5 ммоль/кг массы катализатора и, самое большее 0,0015 ммоль/м2 площади поверхности носителя и в котором температуру реакции повышают, чтобы, по меньшей мере, частично снизить эффект потери активности катализатора, а органический галогенид присутствует в относительном количестве Q, которое поддерживают на постоянном уровне, где относительным количеством Q является отношение эффективного молярного количества частиц активного галогена, присутствующих в сырье, к эффективному молярному количеству углеводорода, присутствующего в сырье.
2. Способ по п.1, в котором носителем является носитель из α-оксида алюминия, имеющий площадь поверхности в диапазоне от 0,3 до 5 м2/г, в частности, от 0,5 до 3 м2/г массы носителя, и содержание серебра в катализаторе находится в диапазоне от 50 до 400 г/кг массы катализатора.
3. Способ по п.1 или 2, где содержание рения в катализаторе находится в диапазоне от 0,1 до 1,2 ммоль/кг массы катализатора.
4. Способ по п.3, где содержание рения катализатора находится в диапазоне от 0,2 до 0,9 ммоль/кг массы катализатора.
5. Способ по п.1, где содержание рения в катализаторе находится в диапазоне от 0,00005 до 0,0013 ммоль/м2 площади поверхности носителя.
6. Способ по п.5, где содержание рения в катализаторе находится в диапазоне от 0,0001 до 0,0012 ммоль/м2 площади поверхности носителя.
7. Способ по п.1, где катализатор дополнительно содержит металл группы IA или его соединение в количестве от 0,01 до 500 ммоль/кг, в частности, от 0,05 до 100 ммоль/кг, вычисленном из расчета на элемент по отношению ко всему катализатору, сопромотор рения, выбранный из вольфрама, молибдена, хрома, серы, фосфора, бора и их соединений, в количестве от 0,1 до 30 ммоль/кг, вычисленном из расчета общего количества элементов относительно массы катализатора.
8. Способ по п.1, где олефином является этилен и органическим галогенидом является хлоруглеводород.
9. Способ по п.1, где относительное количество Q находится в диапазоне от 2·10-6 до 60·10-6.
10. Способ по п.9, где относительное количество Q находится в диапазоне от 3·10-6 до 50·10-6.
11. Способ по п.1, где для любого повышения температуры на 10°С для того, чтобы, по меньшей мере, частично снизить эффект потери активности катализатора, относительное количество Q поддерживают в пределах, самое большее 20% отклонения от величины Q в начале указанного повышения температуры.
12. Способ по п.11, где относительное количество Q поддерживают в пределах, самое большее 15% отклонения от величины Q в начале указанного повышения температуры.
13. Способ по п.12, где относительное количество Q поддерживают в пределах, самое большее 10% отклонения от величины Q в начале указанного повышения температуры.
14. Способ получения 1,2-диола, простого эфира 1,2-диола или алканоламина, включающий получение оксида олефина способом эпоксидирования олефина по любому из пп.1-13 и превращение оксида олефина в 1,2-диол, простой эфир 1,2-диола или алканоламин.
15. Катализатор, содержащий серебро, рений и сопромотор рения, выбранный из вольфрама, молибдена, хрома, серы, фосфора, бора и их соединений, осажденные на носитель, где катализатор содержит рений в количестве, самое большее 0,9 ммоль/кг массы носителя и, самое большее 0,0015 ммоль/м2 площади поверхности носителя и где катализатор дополнительно содержит сопромотор рения в количестве, по меньшей мере, 0,1 ммоль/кг из расчета общего количества элементов относительно массы катализатора.
16. Катализатор по п.15, в котором носителем является носитель из α-оксида алюминия, имеющий площадь поверхности в диапазоне от 0,5 до 3 м2/г массы носителя, и в котором содержание серебра находится в диапазоне от 50 до 400 г/кг по отношению к массе катализатора.
17. Катализатор по п.15 или 16, в котором содержание рения находится в диапазоне от 0,1 до 0,9 ммоль/кг по отношению к массе катализатора.
18. Катализатор по п.17, в котором содержание рения находится в диапазоне от 0,2 до 0,9 ммоль/кг массы катализатора.
19. Катализатор по п.15, в котором содержание рения находится в диапазоне от 0,00005 до 0,013 ммоль/м2 площади поверхности носителя.
20. Катализатор по п.19, в котором содержание рения находится в диапазоне от 0,0001 до 0,012 ммоль/м2 площади поверхности носителя.
21. Катализатор по п.15, где катализатор дополнительно содержит металл группы IA или его соединение в количестве от 0,01 до 500 ммоль/кг, в частности, от 0,05 до 100 ммоль/кг, из расчета на элемент по отношению к всему катализатору, сопромотор рения в количестве от 0,1 до 30 ммоль/кг, из расчета на общее количество элементов по отношению к массе катализатора.
22. Способ получения катализатора по любому из пп.15-21, который включает осаждение серебра и достаточных количеств рения, сопромотора рения и дополнительных компонентов, если они указываются, на носитель.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US45950203P | 2003-04-01 | 2003-04-01 | |
US60/459,502 | 2003-04-01 |
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RU2005133637A true RU2005133637A (ru) | 2006-04-20 |
RU2328491C2 RU2328491C2 (ru) | 2008-07-10 |
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RU2005133637/04A RU2328491C2 (ru) | 2003-04-01 | 2004-03-30 | Способ эпоксидирования олефинов и катализатор для применения в способе |
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US (1) | US7932407B2 (ru) |
EP (1) | EP1613428B1 (ru) |
JP (1) | JP2006522138A (ru) |
KR (1) | KR20060002920A (ru) |
CN (1) | CN100361984C (ru) |
AT (1) | ATE376879T1 (ru) |
CA (1) | CA2520776C (ru) |
DE (1) | DE602004009776T2 (ru) |
IN (1) | IN2005DN04374A (ru) |
MX (1) | MXPA05010375A (ru) |
RU (1) | RU2328491C2 (ru) |
TW (1) | TW200507933A (ru) |
WO (1) | WO2004089537A2 (ru) |
Families Citing this family (35)
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RU2008145498A (ru) * | 2006-04-18 | 2010-05-27 | Дау Глобал Текнолоджиз Инк. (Us) | Катализатор оксида алкилена и его применение |
US7977274B2 (en) * | 2006-09-29 | 2011-07-12 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Catalyst with bimodal pore size distribution and the use thereof |
AR066468A1 (es) * | 2007-05-09 | 2009-08-19 | Shell Int Research | Un catalizador de epoxidacion, un proceso para preparar el mismo, y un proceso para producir un oxido de olefina , un 1,2- diol, un 1,2 - diol eter, un 1,2- carbonato, o una alcanolamina |
WO2008141032A1 (en) * | 2007-05-09 | 2008-11-20 | Shell Oil Company | An epoxidation catalyst, a process for preparing the catalyst, and a process for the production of an olefin oxide, a 1,2-diol, a 1,2-diol ether, a 1,2-carbonate, or an alkanolamine |
EP2162446B8 (en) | 2007-05-11 | 2016-06-01 | SD Lizenzverwertungsgesellschaft mbH & Co. KG | Start-up of high selectivity catalysts in olefin oxide plants |
US7803957B2 (en) * | 2007-09-11 | 2010-09-28 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Ethylene oxide production using fixed moderator concentration |
WO2009137431A2 (en) * | 2008-05-07 | 2009-11-12 | Shell Oil Company | A process for the production of an olefin oxide, a 1,2-diol, a 1,2-diol ether, a 1,2-carbonate, or an alkanolamine |
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- 2004-03-30 CN CNB2004800088572A patent/CN100361984C/zh not_active Expired - Fee Related
- 2004-03-30 KR KR1020057018758A patent/KR20060002920A/ko not_active Application Discontinuation
- 2004-03-30 DE DE602004009776T patent/DE602004009776T2/de not_active Expired - Lifetime
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- 2004-03-30 MX MXPA05010375A patent/MXPA05010375A/es unknown
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IN2005DN04374A (ru) | 2010-01-15 |
ATE376879T1 (de) | 2007-11-15 |
CA2520776C (en) | 2012-05-08 |
CN100361984C (zh) | 2008-01-16 |
EP1613428B1 (en) | 2007-10-31 |
US7932407B2 (en) | 2011-04-26 |
CA2520776A1 (en) | 2004-10-21 |
RU2328491C2 (ru) | 2008-07-10 |
KR20060002920A (ko) | 2006-01-09 |
DE602004009776T2 (de) | 2008-08-28 |
JP2006522138A (ja) | 2006-09-28 |
WO2004089537A3 (en) | 2004-11-25 |
EP1613428A2 (en) | 2006-01-11 |
WO2004089537A2 (en) | 2004-10-21 |
US20040198993A1 (en) | 2004-10-07 |
DE602004009776D1 (de) | 2007-12-13 |
CN1809419A (zh) | 2006-07-26 |
TW200507933A (en) | 2005-03-01 |
MXPA05010375A (es) | 2005-11-17 |
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