TW200744749A - A process for the preparation of a chemical derivable from an olefin oxide, and a reactor suitable for such a process - Google Patents
A process for the preparation of a chemical derivable from an olefin oxide, and a reactor suitable for such a process Download PDFInfo
- Publication number
- TW200744749A TW200744749A TW95147800A TW95147800A TW200744749A TW 200744749 A TW200744749 A TW 200744749A TW 95147800 A TW95147800 A TW 95147800A TW 95147800 A TW95147800 A TW 95147800A TW 200744749 A TW200744749 A TW 200744749A
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- Prior art keywords
- catalyst
- reactor
- microchannel
- group
- diluent
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 199
- 230000008569 process Effects 0.000 title claims description 144
- 150000001336 alkenes Chemical class 0.000 title claims description 80
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 65
- 238000002360 preparation method Methods 0.000 title claims 2
- 239000000126 substance Substances 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims description 125
- 238000006735 epoxidation reaction Methods 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 48
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 47
- 239000001301 oxygen Substances 0.000 claims description 47
- 229910052760 oxygen Inorganic materials 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 239000003085 diluting agent Substances 0.000 claims description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- -1 terpene hydrocarbon Chemical class 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 150000000180 1,2-diols Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
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- 230000008901 benefit Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
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- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
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- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 2
- 239000011733 molybdenum Substances 0.000 claims 2
- 239000011236 particulate material Substances 0.000 claims 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 1
- 241000238413 Octopus Species 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- PTYMQUSHTAONGW-UHFFFAOYSA-N carbonic acid;hydrazine Chemical compound NN.OC(O)=O PTYMQUSHTAONGW-UHFFFAOYSA-N 0.000 claims 1
- 150000001925 cycloalkenes Chemical class 0.000 claims 1
- 150000002923 oximes Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 description 38
- 239000012530 fluid Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 20
- 238000011144 upstream manufacturing Methods 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
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- 238000009826 distribution Methods 0.000 description 11
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- 238000010791 quenching Methods 0.000 description 11
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- 230000000171 quenching effect Effects 0.000 description 9
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 7
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- 150000004820 halides Chemical class 0.000 description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 229960003750 ethyl chloride Drugs 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910000484 niobium oxide Inorganic materials 0.000 description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 206010036790 Productive cough Diseases 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
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- 150000002009 diols Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
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- QCDJOJKIHZQJGX-UHFFFAOYSA-N 1-nitropropan-2-one Chemical compound CC(=O)C[N+]([O-])=O QCDJOJKIHZQJGX-UHFFFAOYSA-N 0.000 description 1
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Description
200744749 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種在反應器中裝置環氧化催化劑之方 法。本發明亦係關於一種用於烯烴環氧化之方法。本發明 亦係關於_種用於製備可衍生自烯烴氧化物之化學品之方 法。詳言之,該化學品可為丨,^二醇、i,2_二醇醚、丨’^碳 酸醋或燒醇胺。本發明亦係關於一種適用於該方法之反應 器。 ~
【先前技術】 壞氧乙燒及其他烯烴氧化物為重要之工業化學品,其用 作製這諸如乙二醇、丙二醇、乙二醇醚、碳酸乙二酯、乙 醇胺及清潔劑之化學品的原料。一種用於製造烯烴氧化物 之方法為藉由烯烴環氧化,亦即以氧氣催化部分氧化烯烴 而付到烯烴氧化物。如此所製造之烯烴氧化物可與水、 酉子、一氧化碳或胺反應,以產生丨,2-二醇、i,2_:醇醚、 ^•、碳酸s旨或烧醇胺。該^二醇、丨义二醇醚、丨,2_碳酸 酉曰或烷醇胺之產生通常係與烯烴氧化物之製造分開進行, 在任何h況下該兩種製程_般在獨立反應器中進行。 在烯烴%氧化過程中,使含有烯烴及氧氣之饋料通過保 :在特疋反應條件下之反應區中所含之催化劑床。市售環 =化反應器通常為殼管式熱交換器形式,纟中複數個大體 =長、相對狹小之管子為成形催化劑顆粒所填充以形 成填料床,且其中該殼含右 又3有冷卻劑。無關於所用環氧化催 化知彳之類型,在商章摔作φ 肉茶拣作中内部管徑常常在20至4〇 mm範 H7072.doc 200744749 圍内,且每個反應器之管子數目可在數千範圍内變化,例 如高達12,000個。 烯烴環氧化通常係以相對低之烯烴轉化率及氧氣轉化率 而進行。通常應用未轉化烯烴及氧氣之再循環以增強該方 法之經濟性。通常該饋料另外包含大量所謂壓载氣體以有 助於***極限以外之操作。壓载氣體包括飽和烴,詳言之 為曱烷及乙烷。因此,再循環通常涉及對大量包括未轉化 烯烴、未轉化氧氣及壓載氣體之製程物料流之處理。如在 稀烴環氧化工廠中通常應用之再循環物料流處理亦相當複 雜,因為其涉及到烯烴氧化物回收、二氧化碳移除、:移 除及再增壓。使用麼載氣體不僅有助於處理成本,其亦降 低環氧化反應速率。 #環氧化催化劑通常在成形載體材料上含有催化活性物 質,通常為第11族金屬(詳言之為銀)及促進劑組份。成形 載體材料通常經仔細選擇以滿以例如)強度及对磨性、表 、儿隙率之要求。成形載體材料通常係藉由燒結所選 …、機材料直至達到其具有所要性質之程度而製得。 $在%乳化期間,催化劑經受效能衰減,此本身代表催化 ^之活f生及形成所要婦烴氧化物之選擇性的損失。回應於 :性之損失’環氧化反應溫度可加以升高以使得烯烴氧化 =生產率得以保持。市售反應器之操作一般就反應溫度 存在限制,且當已達到適當溫度限制時必須中斷婦 乳化物之製造,以將現有環氧化催化劑裝料換成新鮮裝 117072.doc 200744749 用時, 右改良ί衣氧化方法及改良環氧化反應器將變得可 其將具有極大價值。 【發明内容】 。。本’X月提供如此之改良環氧化方法及改良環氧化反應 益。本發明之實施例利用包含複數個微通道(下文中為1 程微通道")之反應器。該等製程微通道可經調適以便在^ 等微通道内可進行環氧化反應域情況進行其他過程,且/ 使得其與適於含有熱交換流體之通道(下文中為,,孰交換通 道”)處於熱交換關係。包含製程微通道之反應器在本文中 係藉由使用術語"微通道反應器"來提及。如本文中所用之 術語’’第11族”係指元素週期表中之第u族。 、在貫轭例中,本發明提供一種在一微通道反應器之一 或多個製程微通道中裝置環氧化催化劑之方法,法包 含:將該催化劑於基本上無水之稀釋劑中之分散體系引入 該或該等製程微通道中,及移除至少_部分該稀釋劑。 在另一實施例中,本發明提供一種用於烯烴環氧化之方 法,其包含: -在一微通道反應器之一或多個製程微通道中裝置環氧化 催化劑,此藉由以下步驟來進行: 將忒催化劑於基本上無水之稀釋劑中之分散體系引入該或 該等製程微通道中;及 移除至少一部分該稀釋劑,以及 -在裝置於該或該等製程微通道中之該環氧化催化劑存在 的情況下使包含該烯烴及氧氣之饋料發生反應。 117072.doc 200744749 在另:實施例中’本發明提供一種用於製❿二醇、 1,2-二醇醚、;ι,2·碳酸酯或烷醇胺之方法,該方法包含: -在-微通道反應器之—或多個製程微通道中裝置環氧化 催化劑,此藉由以下步驟來進行:將該催化劑於基本上無 • 纟之稀釋劑中之分散體系引人該或該等製程微通道中;及 . 移除至少一部分該稀釋劑, _在裝置於該或該等製程微通道中之該環氧化催化劑存在 • %情;兄下使包含烯煙及氧氣之饋料發生反應以得到稀煙氧 化物,以及 ;使用水、醇、二氧化碳或胺使該烯烴氧化物轉化以形成 該1,2-二醇、該丨义二醇醚、該丨,2_碳酸醋或該烷醇胺。 在另一實施例中,本發明提供一種適用於烯烴環氧化之 反應器,該反應器為一包含一或多個其中已裝置呈催化劑 填充床形式之環氧化催化劑之製程微通道的微通道反應 器,且其中該環氧化催化劑包含第11族金屬,其中該第^ • 族金屬之量處於10至500 kg/m3反應器體積之範圍内,反應 為體積係由該等微通道為該環氧化催化劑所佔據部分之橫 截面積及總長度所界定的總體積。 〃 ,【實施方式】 使用根據本發明其中已裝置催化劑之微通道反應器導致 下列優勢中之一或多者: _環氧化催化劑不涉及使用成形載體,此可消除對於一形 成成形載體之步驟的需要。 _在製程微通道内驟冷烯烴氧化物可實現當可處於***極 117072.doc 200744749 、内之條件將被應用於—習知殼管式熱交換器反應器時 在該等條件下之操作。該等條件可藉由在製程微通道内使 乳氣富集―組份與㈣料組份接觸而達成,該氧 氣富集饋料組份及該烯烴富集饋料組份一般在***極限以 夕卜在製程微通道内之驟冷亦減少諸如路及錢之副產物 的形成。 "在製程微通道内之環蓋士 虱化了有利地在烯烴、氧氣及烯烴
氧化物之較高總濃度條件下谁并甘n 、 你什卜進仃,其可導致較高環氧化率 及/或較低環氧化反應溫度。 、 又 丨+低娘乳化反應溫度可導致
改良選擇性及改良催化劑I八03 X y π〒。採用烯烴、氧氣及烯烴氧 化物之較南總濃度條件亦可靖 π 了 4除使用壓載氣體之需要,其 提供更有效之處理及再循環成本之降低。 -在製程微通道中進行之援氧 > 、 匕可以氧氣或浠烴氧化物之 繼率水平錢作。尤其當該製程係以高浠烴轉化率水 丁時,以早^作來操作該環氧化製程係有利的,其
思謂不應用再循環物料流。 ^ ^ 为夕卜在此情況下可將空氣代 替自空氣分離之氧氣而饋入势 表私试通道中係有利的,其可 消除對於空氣分離單元之需要。 -在製程微通道内進行嫌柄严与 订婦垣每氧化可實現在該等相同製程 试通道内使所形成之烯烴氧 ^ 乳化物轉化為1,2-二醇、1,2-二 醇_、1,2-碳酸酯或燒醇胳 醉胺此可消除對用於該進一步轉 化之額外反應器之需要。甘★ 一 ★ #亦可消除對於烯烴氧化物回收 早元及/或一氧化妷移除單元 ♦ _ ^ ^ ^ ^ 之而要’且其可減少對於熱 父換设備之舄要。因此,並^^ ” 了降低在製造廠中習知例如用 117072.doc -10- 200744749 於產物回收之額外處理的複雜性。在製程微通道内烯烴氧 化物之轉化亦減少了諸如酸及叛酸之副產物的形成。 適用於本發明之微通道反應器及其操作已在…⑺厂 2004/099113、WO-A-01/12312、WO-01/54812、US-A-6440895、US-A-6284217、US-A-6451864、US-A-6491880、US-A-6666909、US-6811829、US-A-6851171、 US-A-6494614、US-A-6228434 及 US-A-6192596 中描述, 该等案以引用之方式併入本文中。如在該等參照案中所述 之製造微通道反應器、裝載催化劑及操作之方法通常可適 用於本發明之實施。 參看圖1,微通道反應器100可包含一製程頂蓋1〇2、複 數個製程微通道104及一製程腳座1 〇8。該製程頂蓋1 〇2為 /’il體k供一流入製程微通道1 〇4中之過道。該製程腳座1 〇8 為流體提供一自製程微通道1 〇4流出之過道。 一微通道反應器中所含之製程微通道數可極大。例如, 該數目可多達105個,或甚至多達106個或多達2xl〇6個。通 常,製程微通道數可為至少10個或至少1〇〇個,或甚至至 少1000個。 該等製程微通道通常平行排列,例如其可形成一平面微 通道陣列。該等製程微通道可具有至少一多達i 5 mm之高 度或寬度之内部尺寸,例如〜05至10 mm,尤其為〇1至5 mm,更尤其為0.5至2 mm。高度或寬度之另一内部尺寸可 為(例如)〇·1至100 cm,尤其為0.2至75 cm,更尤其為〇 3至 50 cm。該等製程微通道之長度可為(例如)1至5〇〇,尤 117072.doc 200744749 其為2至300 cm,更尤其為3至mo cm或5至100 cm。 微通道反應器100另外包含與製程微通道104進行熱交換 接觸之熱交換通道(未在圖1中展示)。該等熱交換通道亦可 為微通道。該微通道反應器經調適以便使熱交換流體可自 熱交換頂蓋110經由熱交換通道流至熱交換腳座112。該等 熱父換通道可經對準以提供相對於製程微通道丨04中之流 動而S在並流、逆流或(較佳)交叉流方向上之流動。該交 叉流方向係如箭頭114及11 6所示。 該等熱交換通道可具有至少一多達15 mm之高度或寬度 之内部尺寸,例如0.05至1〇 mm,尤其為〇1至5 mm,更尤 其為0.5至2 mm。高度或寬度之另一内部尺寸可為(例 如)〇·1至100 cm,尤其為0·2至75 cm,更尤其為〇.3至5〇
Cm 5亥等熱交換通道之長度可為(例如)1至500 cm,尤其 為2至30〇(:111,更尤其為3至2〇〇0111或5至1〇〇(:111。 製耘锨通道1 04與最近相鄰熱交換通道之間的間距可處 於〇.〇5mm至5 mm、尤其〇·2至2mm之範圍内。 在本發明之一些實施例中,提供第一熱交換通道及第二 熱父換通道,或第一熱交換通道、 熱父換通道,或甚至多達第五熱交 、第二熱交換通道及第三
製程頂蓋102、製程腳座1〇8、 a rnj及熱交換腳座112,藉 熱父換頂蓋11 〇接收熱交換 t換腳座112中。 、熱交換頂蓋11 〇、熱交換 117072.doc -12- 200744749 腳座112、製程微通道1Q4及熱交換通道可獨立地由任何提 供足夠強度、尺寸穩定性及熱轉移特徵之結構材料製成, 以允許根據本發明之方法之操作。合適之結構材料包括 (例如)鋼(例如不銹鋼及炭鋼)、蒙乃爾合金(m〇ne〇、鈦、
銅、玻璃及聚合物組合物。熱交換流體之種類對於本發明 並不重要’且該熱交換流體可選自多種種類。合適之熱交 換流體包括蒸汽、丨、空氣及油。在包括複數個熱交換= 道組之本發明實施例中,該等熱交換通道組可以不同熱交 換流體或以具有不同溫度之熱交換流體進行操作。’、又 包含一或多個 元。現參看圖 根據本發明之微通道反應器可包含複數個 製知微通道及一或多個熱交換通道之重複單 2’其展示一典型重複單元及其操作。 製程微通道210具有一上游端22〇及一下游端23〇,且可 包含一第-區240,該區可含有催化劑(未晝出),例如環氧 化催化劑。第-區240可與第—熱交換通道25()進行熱交換 接觸,允許製程微通道21〇之第—區24〇與第一熱交換通道 250之間的熱交換。該重複單元可包含第—饋料通道_ , 其經由一或多個第一孔280終止於第一區24〇中。通常—或 多個第一孔280可設置於相對於另—第一孔28〇之下游。在 操作期間,包含烯烴及氧氣之饋料可經由上游端22〇中一 開口及/或經由第一饋料通道26〇及一或多個第—孔28〇進 入製程微通道210之第一區240中。 化劑 不含 製程微通道21〇可包含一可適於或可不適於含有催 之第二區340。如本文中所述,第二區34〇可含有或可 117072.doc -13 - 200744749 有催化劑。第二區340係設置於第-區240之下游。第二區 340可與第二熱交換通道⑽進行熱交換接觸,允許製程微 通道210之第二區34〇與第二熱交換通道㈣之間的熱交 換、在“施例中,第二區340適於藉由與第二熱交換 通道350中之熱交換流體之熱交換來驟冷在第一區240中獲 得且自第一區240接收之烯煙氧化物。在存在複數個(例如 兩個或三個或四個)第二熱交換通道350之情況下,可以一 或多個階段達成驟冷。該複數個第二熱交換通道350可適 於含有具有不同溫度之熱交換流體,詳言之以便在第二區 340之下游方向上,盥冬 ^ ^ 與3有具有較低溫度之熱交換流體的 弟二熱交換通道350發生熱交 _ ㈣…乂 ' -亥重複早το可包含第二 3二二i,其經由一或多個第二孔380終止於第二區 饋料可自製程微通道210中之上游及 340中。、甬α_Λ、360及一或多個第二孔380進入第二區 孔之或多個第二孔380可設置於相對於另一第二 1 、;。在其中第二區34°適於可供歸烴氧化物至 一以二醇驗」,碳酸醋或垸醇胺之轉化 ρ例中’在操作期間經由第二饋料通道36〇及一 第一孔380進入之饋料可包含 、 一 化劑亦可經由帛'减碳或胺。催 或多個帛13_ 右而要,則可能存在具有一或多個 第二饋料通道獨立組(未畫出畫出)之 立饋入。 貝及催化劑之獨 第一及第二饋料通道或则與第—及第二孔_或⑽ 117072.doc .14· 200744749 組合,藉以一或多個第一或第二孔28〇或38〇分別設置於另 一第一或第二孔280或380之下游,以允許對反應物之補 充。反應物之補充為本發明之一些實施例中的特徵。 製程微通道210可包含一中間區44〇,其設置於第一區 240之下游及第二區34〇之上游。中間區料〇可與第三熱交 換通道450進行熱交換接觸,允許製程微通道21〇之中間區 440與第三熱交換通道450之間的熱交換。在一些實施例 中,例如在其中第二區340適於可供烯烴氧化物至丨,2_二 醇、1,2-二醇醚、碳酸酯或烷醇胺之轉化使用的實施 例中,中間區440適於藉由與第三熱交換通道45〇中之熱交 換流體之熱交換來驟冷在第一區24〇中獲得且自第一區 接收之烯烴氧化物。在存在複數個(例如兩個或三個或四 個)第三熱交換通道450之情況下,可以若干階段達成驟 冷。該複數個第三熱交換通道450可適於含有具有不同溫 度之熱交換流體,詳言之以便在中間區44〇之下游方向 上,與含有具有較低溫度之熱交換流體的第三熱交換通道 450發生熱交換。 饋料通道可為微通道。其可具有至少一多達15 mm之高 度或寬度之内部尺寸,例如〇·〇5至1〇 mm,尤其為〇」至5 mm,更尤其為〇.5至2 mm。高度或寬度之另一内部尺寸可 為(例如)0.1至1〇〇 cm,尤其為〇2至75 cm,更尤其為〇3至 5〇 cm。該等饋料通道之長度可為(例如)1至25〇 cm,尤其 為2至150 cm,更尤其為3至1〇〇 cm或5至50 cm。 製程微通道區之長度可彼此獨立地根據(例如)所需熱交 117072.doc -15 - 200744749 換谷里或该區中可含有之催化劑量而進行選擇。該等區之 長度較佳為至少1 cm ’或至少2 cm,或至少5 cm。該等區 之長度車父佳為至多25〇 cm,或至多150 cm,或至多100 cm,或至多50 cm。該等區之其他尺寸係由製程微通道21〇 - 之相應尺寸所支配。 ,本發明之微通道反應器可使用已知技術來製造,例如習 知機械加工、雷射切割、成型、衝壓及蝕刻以及其組合。 φ 本發明之微通道反應器可藉由形成其中特徵經移除以允許 流通之薄片而製造。藉由使用已知技術,例如擴散黏結、 雷射焊接、冷焊、擴散釺焊及其組合,可將該等薄片之堆 疊進行組裝以形成一積體裝置。本發明之微通道反應器包 含適當之頂蓋、腳座、閥門、管線及其他特徵以控制反應 物之輸入、產物之輸出及熱交換流體之流動。該等者未在 圖式中顯示,但其可由熟習此項技術者容易地提供。亦存 在其他熱交換設備(未圖示),其用於饋料之溫度控制,尤 • 其用於在饋料或饋料組份進入製程微通道前將其加熱,或 用於產物之溫度控制’尤其用於在產物已離開製程微通道 後將其驟冷。如此之其他熱交換設備可與微通道反應器整 • 纟在-心但其更通常地將為獨立設備。料者未在圖式 • 巾顯示,但其可由熟習此項技術者容易地提供。可例如藉 由使用%氧化製程之反應熱用於加熱饋料組份或用於其他 加熱目的來應用熱整合。 通常,在環氧化反應條件下環氧化催化劑為固體催化 劑。該等催化劑可在製程微通道 <、<扣疋區中形成填料床, H7072.doc -16· 200744749 且/或其可在製程微通道之指$區的至少一部&壁上形成 塗層。熟習此項技術者將理解該塗層將設置於製程微通道 之内壁上。另外,該等催化劑中之一或多者可為可置^ 程微通道之指定區中之***物上的塗層形式。 • 可用於本發明之環氧化催化劑通常為包含一或多種第u • 族金屬之催化劑。第11族金屬可選自由銀及金組成之群。 該第1,1族金屬較佳包含銀。詳言《,根據銀金屬之重量相 φ 對於第11族金屬總重量(按金屬計)而計算,第11族金屬包 含至少90%w之量之銀,纟更尤其為至少95%w,例如至少 99〇/〇w或至少99.5%w。通常,環氧化催化劑另外包含一 2 多種促進劑組份。更通常,環氧化催化劑包含第丨丨族金 屬、一或多種促進劑組份及額外之一或多種包含一或多種 其他元素之組份。在一些實施例中,環氧化催化劑可包含 載體材料,在該材料上可沈積第丨丨族金屬、任意促進劑1 份及任意包含一或多種其他元素之組份。合適促進劑組份 • 及包含一或多種其他元素之合適組份及合適載體材料可如 下文中所描述。 在一些實施例中,其上可沈積第丨丨族金屬或陽離子第^ . 族金屬組份之製程微通道之壁係至少經部分粗糙化或波紋 - 化。粗糙化或波紋化可提供凹槽及凸起,以便使經粗糙化 或波紋化之壁表面被有效地增大,例如相對於該粗糙化或 波紋化壁表面由其外部尺寸所界定之表面積而言,可有效 地增大0.5至10倍,或丨至5倍。此可增加沈積於壁上之環 氧化催化劑之黏著力,且將導致更多環氧化催化劑表面幫 117072.doc -17- 200744749 助催化該環氧化反應。粗糙化及波紋化可藉由此項技術中 已知之方法,例如藉由餘刻或施加研磨力而達成。 在一貫施例中,本發明提供一種在一微通道反應器之一 或多個製程微通道中裝置環氧化催化劑之方法,該方法包 含:將分散於基本上無水之稀釋劑中之該催化劑分散體系 引入該或該等製程微通道中,及移除該稀釋劑。 該基本上無水之稀釋劑可為液體,或其可呈氣體形式。 如本文中所用,對於液體稀釋齊j,”基本上無水,,意謂該稀 釋劑之水含量相對於該稀釋劑重量而言為至多,尤 其至多10%w,更尤其至多5%w,例如至多2%w,或甚至 至多l%w,或至多〇.5%w。詳言之,對於氣體稀釋劑,"基 本上無水,,意謂存在於製程微通道中時該稀釋劑處於露點 溫度以上。相較於應用含水稀釋劑之情況,該稀釋劑中大 體上或完全無液態水使得催化劑能夠在裝置期間更佳地維 持其在形態、組成及性質中之一或多個方面之完整性。合 適之基本上無水之液體稀釋劑包括有機稀釋劑,例如煙、 鹵化煙、醇、g同、驗及酷人、金 . 及知合適之醇包括(例如)甲醇及乙 Z。可存在於該液體稀釋财之催化劑的量相對於該催化 劑與該液體稀釋劑之總重量而言可處於15G%W、尤其2 至30%w之範圍内。 合二之基本上無水之氣相稀釋劑包括(例如)空氣、氮 的旦=化碳。可存在於該氣體稀釋劑中之催化劑 的里备妝該催化劑重量相々 ^ ^ ^矾相稀釋劑體積而計算可 處㈣至·g/I、尤其22至扇的之範圍内。 H7072.doc 200744749 存在於分散體系中之環氧化催化劑可藉由粉碎習知之成 形催化劑且繼而視情況加以篩分而獲得。存在於分散體系 中之該催化劑之粒徑通常為如此以便使‘處於〇ι至_ μπι、尤其0·5至50 _之範圍内。如本文中所用稱為”心"之 平均粒徑係如藉由Horiba LA900粒徑分析儀量測,且表示 存在大於及小於該所述平均粒徑之顆粒的相等球當量體積 時之顆粒直徑。該量測方法包括藉由超音處理來分散顆 粒,由此使次級顆粒分解為初級顆粒。持續該超音處理直 至值無進一步可察覺之變化,當使用H〇riba la9〇〇粒徑 分析儀時此通常需要5分鐘超音處理。較佳地,該環氧化 催化劑包含具有如此之尺寸以便使其穿過一具有大小為製 程微通道最小尺寸之至多50%、尤其至多3〇%之開口的篩 之顆粒。 習知之成形環氧化催化劑通常包含經分散於成形載體材 料上的第11族金屬、一或多種促進劑組份及視情況之一或 多種包含其他元素之組份。就第u族金屬、促進劑組份及 包含其他7L素之組份之量而言,合適載體材料、合適促進 劑組份、合適之包含其他元素之組份及合適催化劑組合物 可如下文中所描述。 另外,且較佳地,存在於分散體系中之催化劑係如本文 中所述來製備。 可將該催化劑分散體系引入,以便在一或多個製程微通 道之4曰疋區中开> 成催化劑填充床’或另外以便使該等區之 至少一部分壁為催化劑所覆蓋。在前者情況下,在引入該 117072.doc -19- 200744749 催化劑分散體系之前,可先將一支撐設備(例如篩或級配 ‘粒材料)置於該或該等製程微通道之指定區的下游部分 中,以支撐該催化劑且防止其進一步向下游移動。在後者 十月況下,可在組裝製程微通道之前或之後將催化劑沈積於 製程微通道壁上,或催化劑可存在於經置於製程微通道之 指定區中的***物上。 存在於製程微通道之第一區中之第u族金屬總量對於本 發明並不重要,且可在廣泛範圍内進行選擇。通常,第u 族金屬之總量可在10至500 kg/m3反應器體積之範圍内,更 通常在50至400 kg/m3之範圍内,尤其在100至3〇〇 kg/m3之 範圍内,其中反應器體積係由製程微通道為環氧化催化劑 (以填料床及/或以壁上之環氧化催化劑存在)所佔據部分之 橫截面積及總長度所界定的總體積。為避免疑義,如此所 疋義之反應器體積不包括不包含環氧化催化劑之製程微通 道的部分。在其中饋料包含總量為至少5〇莫耳%之烯烴及 氧氣的本發明之實施例中,第u族金屬之總量可在5至25〇 kg/m反應器體積之範圍内,更通常在2〇至2〇〇 之範 圍内,尤其在50至150 kg/m3之範圍内,其中反應器體積如 上文中定義。 一種製備微粒環氧化催化劑之方法包含沈積第u族金屬 及一或多種促進劑組份於具有一孔徑分佈以便使具有〇2 至1 〇 μπι範圍内之直徑之孔隙為總孔隙體積之至少7〇%的 微粒載體材料上。 可用於本發明之載體材料可為天然或人工無機材料,且 H7072.doc -20- 200744749 :可包括耐火材料、碳切、黏ι沸石、炭及驗土金屬 奴酸鹽’例如碳酸鈣。較佳為耐火材料,諸如氧化 化錢、氧化結及二氧切。最佳材料為α_氧化銘。通常, 載體材料包含相對於載體重量而言為至少―、 至少嶋w、《其至少95%Wk氧化|g,往往包含高達 ^9%W^-氧化銘。α·氧化銘之其他組份可包含(例如)二 氧化石夕㉟孟屬組份(例如納及/或鉀組份)及/或驗土金屬 組份(例如鈣及/或鎂組份)。 載體材料之表面積相對於載體重量而言可適當地為至少 〇、·1 m /g ’較佳為至少〇·3 m2/g,更佳為至少〇·5 ^2/g,且 尤其為至> 0.6 m2/g ;且該表面積相對於載體重量而言可 適當2地為至多1〇 m2/g,較佳為至多5 mVg,且尤其為至多 3 m /g。如本文中所用之,,表面積,,係理解為係關於如藉由
Journal of the American Chemical Society 60 (1938)第 30、 3 16頁中所述之B.E.T.(Brunauer,Emmett and Teller)方法測 疋之表面積。高表面積載體材料,尤其當其為視情況另外 包含二氧化矽、鹼金屬及/或鹼土金屬組份之心氧化鋁時, &供改良效能及操作穩定性。 該载體材料之吸水率通常在〇2至〇8 g/g2範圍内,較佳 在〇·3至〇·7 g/g之範圍内。較高吸水率可有利於更有效地沈 積第Π族金屬、促進劑沈積及包含一或多種元素之組份。 如本文中所用之吸水率係根據astm C20量測,且將吸水 率表示為相對於載體重量而言可吸收至載體孔隙中之水的 重量。 117072.doc -21 - 200744749 微粒載體材料可具有一孔徑分佈以便使具有〇 2至丨〇 μηι 範圍内之直徑之孔隙為總孔隙體積之至少70%。如此相對 狹窄之孔徑分佈可有助於催化劑之活性、選擇性及耐久性 中之一或多者。耐久性可與維持催化劑活性及/或維持選 擇性有關。如本文中所用之孔徑分佈及孔隙體積係如使用
Micromeretics Autopore 9200型(130°接觸角,汞具有 0.473 N/m之表面張力,且對汞壓縮進行校正)藉由達3〇xl〇8 pa 之壓力的壓汞法(merCUry intrusi〇n)來量測。 較佳地,該孔徑分佈係使具有〇·2至1〇 μιη範圍内之直徑 之孔隙為總孔隙體積之75%以上,尤其80%以上,更佳 85。/。以上,最佳90%以上。通常,孔徑分佈係使具有〇.2至 10 μιη範圍内之直徑之孔隙為總孔隙體積之99.9%以下,更 通常為99%以下。 較佳地,該孔徑分佈係使具有0.3至10 μιη範圍内之直徑 之孔隙為包含在具有0.2至10 μπι範圍内之直徑之孔隙中的 孔隙體積的75%以上,尤其為80%以上,更佳85%以上, 最佳90%以上,尤其高達1〇〇%。 通常,該孔徑分佈係使具有小於0.2 μιη之直徑之孔隙為 總孔隙體積之10%以下,尤其為5%以下。通常,具有小於 〇·2 μπι之直徑之孔隙為總孔隙體積之0.1%以上,更通常為 0 · 5 %以上。 通常,該孔徑分佈係使具有大於1 0 μπι之直徑之孔隙為 總孔隙體積之20%以下,尤其為10%以下,更尤其為5%以 下。通常,具有大於10 μπι之直徑之孔隙為總孔隙體積之 117072.doc -22- 200744749 ο·ι%以上,尤其為〇 5%以上。 包含-或多種經分散於載體材料上之第u族金屬 化催化劑在該第U族金屬含量相對於該摧化劑重量而:為 =10_時展現明顯之催化活性。該催化劑較佳包:量 為50至500g/kg、更佳聰400 g/kg之第_金屬。 促進餘份可包含—或多種選自鍊in =物之元素。該促進劑組份較佳包含作為其元素之^ 該促進劑組份通常可以按照元素(亦即銖、鶴、翻及/或 ,。)總I相對於第η族金屬重量而計算為至少〇〇5毫莫 =、更通常至少〇.5毫莫耳/kg及較佳至少i毫莫耳心之 ::在於%氧化催化劑卜該促進劑組份可以 =相對於第㈣金屬重量而計算為至多㈣毫莫耳 土至多毫莫耳/kg、更佳至多25毫莫耳~之量存在。該 促進劑組份可得以沈積之形式對本發明並不重要。例如, 錢進劑組份可適當地作為氧化物或作為氧陰離子(例 D,作為銖酸鹽、高銖酸鹽或鎢酸鹽),以鹽或酸 提供。 八 妒當環氧化催化劑包含含銖促進劑組份時,銖通常可以按 '、、、凡素罝相對於第11族金屬重量而計算為至少0.5毫莫 g更通吊至少2.5毫莫耳/kg及較佳至少5毫莫耳/kg、 尤其至少7.5毫莫耳/kg之量存在。基於相同算法,銖通常 係^至多25毫莫耳/kg、較佳至多15毫莫耳心、更佳至多 10«莫耳/kg、尤其至多75毫莫耳/kg之量存在。 H7072.doc -23 - 200744749 另外,當環氧化催化劑包含含錄促 劑可較佳包含銖共促進劑, 、,、伤時,該催化 份。該銖共促進劑可適當地選於载體上之其他組 找^ 選自包含選自鎢、欽、相 &、磷、硼及其混合物之元 ° 鉬 , ”的、、且份。該銖共促進劑較佳 係選自包含鎢、鉻、鉑、硫及其 八進⑽佳 進劑尤其較佳包含料為元素。 ,且77。邊銖共促 該銖共促㈣通常可以按照元素(亦㈣、鉻、顏、 二Si之總量)相對於第U族金屬重量而計算為至 =莫耳kg、更通常至少。.5毫莫耳~及較佳至少25 ^/kgt量存在。基於相同算法,該銖共促進劑可 以至多200宅莫耳/kg、較佳至多 古处 少宅旲耳/kg、更佳至多25 笔莫耳/kg之總量存在。命蚀止作、公 什隹忒銖共促進劑可得以沈積之形式 對本發明並不重要。例如,其可適當地作為氧化物或作為 乳陰離子(例如’作為硫酸鹽、硼酸鹽或㈣鹽),以鹽或 酸之形式提供。 環氧化催化劑較佳包含第u族金屬、促進劑組份及包含 其他元素之組份。適當之其他元素可選自氮、氣、驗金 屬、驗土金屬、鈦、給、錯、鈒、銘、处、组、銳、録及 鍺及其混合物之群。驗金屬較佳係選自鐘、鉀、撕及絶。 鹼金屬最佳為鐘、鉀及/或铯。驗土金屬較佳係選自辦及 鋇。通常,該其他元素係以按照元素相對於第丨丨族金屬重 量而計算為0.05至2500毫莫耳/kg、更通常0.25至5〇〇毫莫 耳/kg之總ϊ存在於該環氧化催化劑中。該等其他元素可 以任何形式提供。例如,鹼金屬鹽或鹼土金屬鹽為合適。 H7072.doc -24- 200744749 如本文中所用,在太 #在於%氧化催化劑中之鹼金屬的量被 w為係在其可使用去離子 、― 千火於100 C下自該環氧化催化劑 中付以卒取之範圍内的量。 °亥卒取方法包含藉由在I00°c 下於母份為20 ml之丰雜工, — 切子水中加熱5分鐘將1G公克催化劑 樣品卒取三次,及藉由# 更用已知方法(例如原子吸收光譜) 在經組合萃取物中測定相關金屬。 、:本文中所用,存在於環氧化催化劑中之鹼土金屬的量 被㈣為係在其可使用去離子水中之1G%W硝酸於⑽。c下自 該環氧化催化劑中得以萃取之範圍内的量。該萃取方法包 含藉由與每份為1001111之10。“石肖酸一…30分鐘 (1如’亦即UH.3 kPa)來對1〇公克催化劑樣品進行萃取, 及稭由使用已知方法(例如原子吸收光譜)在經組合萃取物 中測定相關金屬。參考US_A_58()1259,該案以引用之方式 併入本文中。 、用於於载體材料上沈積第U族金屬、該或該等促進劑組 伤及4或4等包含其他凡素之組份的方法在此項技術中為 已知,且該等方法可應用於本發明之實施中。可參考1;8_ Α-5380697 、 EP-A-266015 及 US-B- US-A_5739075 、 v 8998 ’ δ亥等案以引用之方式併入本文中。該等方法適 當地包括以包含陽離子第u族金屬_胺錯合物及還原劑之 液體混合物浸潰微粒載體材料。 在些貫施例中,本發明提供用於烤烴環氧化之方法, 其包含使包含烯烴及氧氣之饋料在一微通道反應器之一或 多個製程微通道中所含有的如上文所述之環氧化催化劑存 117072.doc -25- 200744749 在的情況下發生反應^ 用於本發明之烯煙可為芳族㈣,例如苯乙烯;或共輛 或非共軛之二烯煙’例#1,9_癸二稀或以丁二烯。可使 用烯烴混合物。通常’該歸烴為單稀烴,例如2•丁烤或異 烯4烯烴較佳為單α烯烴,例如L 丁烯或丙烯。最佳 之烯烴為乙烯。 用於本發明之環氧化製程之饋料包含烯烴及氧氣。如本
中斤用對於一製程之饋料應理解為代表饋入其中發生 料製程之製程微通道區中的反應物及其他組份之總和。 一些饋料組份可經由製程微通道210之上游端22G中的一開 口饋至環氧化製程中。一些饋料組份可經由第一饋料通道 260及—或多個第一孔28〇饋入。例如,烯烴富集饋料組份 可經由製程微通道之上游端中的開口饋人,而氧氣富集饋 料㈣可經由第-饋料通道及該或該等第—孔饋入。或 者,氧氣富集饋料組份可經由製程微通道之上游端中的開 口饋入’而稀煙富㈣料組份可經由第_饋料通道及該或 該等第一孔饋入。特定饋料組份可經由製程微通道之上游 端中的開口且經由第一饋料通道及該或該等第一孔饋入。 例如,烯烴可部分經由製程微通道之上游端中的開口饋 入,且部分經由第一饋料通道及該或該等第一孔饋入。又 例如,氧氣可部分經由製程微通道之上游端中的開口饋 入,且部分經由第一饋料通道及該或該等第一孔饋入。 有機鹵化物可作為反應改質劑存在於饋料中,以便相對 於烯烴氧化物之所要形成而言提高選擇性,抑制烯烴或烯 117072.doc -26- 200744749 烴氧化物至二氧化碳及水之非所要的氧化過程。該有機鹵 化物可作為液體或蒸汽饋入。該有機鹵化物可經由製程^ 通道2 10之上游端220中的一開口或經由第一饋料通道2⑽ 及一或多個第一孔2 8 〇與其他饋料組份分別饋入或一同饋 入。經由複數個第一孔饋入有機鹵化物之一態樣為,沿著 環氧化催化劑之長度有機_化物之含量可增加,由此可根 據EP-A-352850之教示來控制環氧化催化劑之活性及/或選 擇性,該案以引用之方式併入本文中。例如,當使用^ 環氧化催化劑時,該環氧化催化劑之活性可沿著該環氧化 催化劑之長度而增強。此可允許相較於饋入氧氣及烯烴之 區域而言在氧氣或稀烴空乏之區域中對環氧化催化劑:利 用更佳。 有機函化物尤其為有機演化物,且更尤其為有機氣化 物。較佳之有機齒化物為氣烴或溴煙。其更佳係選自由氯 甲烷、氯乙烷、二氯化乙烯、二溴化乙烯、氯乙烯或其混 合物之群。氯乙烷及二氣化乙烯為最佳。 除有機鹵化物外,可採用有機或無機氮化合物作為反應 改質劑’但此通常為次佳。應認為在環氧化製程之操作條 件下,含氮反應改質劑為硝酸鹽或亞石肖酸鹽之前驅體(例 如參考EP-A-3642及US_A_48229〇〇,該等案以引用之方式 併入本文中)。可採用有機氮化合物及無機氮化合物。合 適有機氮化合物為硝基化合物、亞硝基化合物、胺、硝酸 鹽及亞硝酸鹽’例如確基甲烧、I硝基丙燒或24基丙 烧。合適無機氮化合物為(例如)氮氧化物、肼、胲或气。 117072.doc •27- 200744749 合適之氮氧化物具有通式N〇x,其中χ處於1至2之範圍内 且包括(例如)NO、N2〇3及N204。 有機函化物及有機或無機氮化合物在以較低總濃度⑼ 如相對於總饋料而言為至多0·01莫耳%)使用時,作為反應 改質劑通常係有效的。該有_化物較佳·相對於總饋' 料而言為至多50χ10-4莫耳%、尤其至多20xl0·4莫耳。乂、更 尤其至多⑸心莫耳%且相對於總饋料而言為較佳至少 0·2χ10-4莫耳%、尤其至少〇.5χΐ〇_4莫耳%、更尤其至少 1Χ10·4莫耳%之濃度存在。 除烯烴、氧氣及有機鹵化物外,饋料可另外包含一或多 種其他組份,例如飽和烴(作為壓載氣體)、惰性氣體及二 氧化碳。該或該等其他組份可經由製程微通道21G之上游 端220中的—開口或經由第-饋料通道260及—或多個第L 孔280與其他饋料組份分別饋入或一同饋入。 饋料中之烯烴濃度可在一廣泛範圍内選擇。通常,饋料 中之:烴濃度相對於總饋料而言將為至多8〇莫耳%。基於 相同算法’其較佳將處於G·5至7G莫耳%、尤其u6〇莫耳 %之範圍内。 、 饋料:之减濃度可在一廣泛範圍内選擇。通常,所應 用之氧氣濃度將處於總饋料莫耳%、更通"至^ 莫耳%之範圍内。 飽和烴包含(例如)甲貌及乙烧。除非在本文中另外說 明’否則飽和烴可以相對於總饋料而言為至多80莫耳%、 尤其至多75莫耳%之量存在,且通常其係以基於相同算法 117072.doc -28- 200744749 為=3。莫:耳%、更通常至少4。莫耳%之量存在。 或婦煙氧:此係因為其係由於浠烴及/ 再循環物料流_之饋料=且 化劑活性具有不利影響…氧化‘二“通,對催 有利地為(例如)低於2莫耳;氧::…對於總饋料而言 至!莫耳%之範圍内/耳I較佳低於1莫耳%,或在〇·2 惰性氣體包括例如氮氣或氬氣。除非在本文中另外說 明,否則惰性氣體可以3〇 之漢度存在於饋料中。。莫耳/❶通“。至-莫耳% "本發明之環氧化方法可為基於空氣或基於氧氣的,參看 ,,ΚΐΓ"'〇11ΐΐη6Γ Enc^i〇Pedia of Chemical Technology·. , f 3 T,第9卷’ 1980’第445_447頁。在基於空氣之方法中, 私用工氣或田含氧乳之空氣作為氧化劑源;而在基於氧氣 之方法中’採用高純度(至少95莫耳%)氧氣作為氧化劑 源。目前多數環氧化工薇係基於氧氣的,且在本發明之特 定實施例的實%中其為㈣。本發明之其他實施例的優勢 在於可將空氣作為氧化劑源饋入製程中。 可使用選自-廣泛範圍之反應溫度來進行環氧化製程。 該反應溫度較佳處於15〇至34(rC之範圍内,更佳在18〇至 325 C之範圍内。通常,存在於第一熱交換通道中之熱轉 移液體可具有通常低於該反應溫度0 5至1〇〇c之溫度。 该環氧化製程較佳在如於製程微通道21〇之上游端22〇處 量測處於1000至3 500 kPa範圍内的壓力下進行。 117072.doc -29- 200744749 離開含有環氧化催化劑之製程微通道區之烯烴氧化物係 包含在可進一步包含未反應烯烴、未反應氧氣及其他諸如 二氧化碳之反應產物的反應混合物中。通常,在反應產物 中稀經氧化物之含量一般處於1至25莫耳%、更通常2至20 莫耳%、尤其2至5莫耳%之範圍内。 4 %氧化製程可包含使包含相對於總饋料而言總量為至 >、0莫耳/。之稀煙及氧氣的饋料發生反應。在該實施例 中,烯烴及氧氣可以相對於總饋料而言為至少80莫耳%、 尤其至少90莫耳%、更尤其至少95莫耳%且相對於總饋料 而吕通常為至多99.5莫耳%、尤其至多99莫耳%之總量存 在於饋料中。烯烴與氧氣之莫耳比可處於3至_、尤其4 至50更尤其5至20之範圍内。飽和烴及惰性氣體可大體 j不存在。如本文中所用,在該内容中,,大體上不存在,,意 f饋料中之飽和烴之量相對於總饋料而言為至多10莫耳 =^其至多/莫耳%、更尤其至多2莫耳%,且饋料中之 氣體之里相對於總饋料而言為至多丨〇莫耳%、尤其至 =莫耳Λ、更尤其至多2莫耳%。在該特定實施例中:、使 使%聽反應混合物中之㈣氧化物之量處於斗至以 程條Γ =5至12莫耳%(例如6至lG莫耳%)之範圍内之製 麻、θ。如本文中所述較佳將該包括稀煙氧化物之環氧化 反應混合物加以驟冷。 二 ==Γ用可使饋料發生反“便使_ 可為至=且Γ9。莫耳%之條件,轉化率 莫耳/。,且氧氣轉化率可為至少90莫耳%。詳 117072.doc -30- 200744749 吕之’在該實施例中,庐 至多50莖… 11枓可包含相對於總饋料而言量為 主夕5〇4耳%的烯烴 η 且该饋料可另外包含飽和烴 (作為壓載軋體)及惰性 ^ L 虱體。通常,使用製程條件以僮# 細烴轉化率或氧氣轉㈣為至少95 “便使 ,耳%,更尤其至少99莫…太耳尤其至少98莫 „ ^ 莫耳本文中所用,轉化率為經 ” 轉化反應物相對於饋料中之反岸物之旦&曰甘 久應初之里的罝,其以莫耳〇/〇 表不。烯烴之轉化率較佳為、 ^ )兵耳/〇,尤其至少98莫 耳扁,更尤其至少99莫耳% •日条友 • 士 旲斗/g ,且虱軋可至少部分地加以補 充。饋料中相對於稀煙而+ 那/工而a過里虱氣之存在有助於達成 烴之高轉化率。例如,在饋料中氧氣比烯烴之莫耳比可為 至少1·〇1,通常至少i.05,尤1 凡冉主J 1.1,更尤其至少12 ; 且例如至夕5,尤其至多3,更尤其至多2。在該實施例 中’在稀烴至㈣氧化物之轉化中達成相對較高的選擇 率。如本文中所用,選擇率為所形成之稀煙氧化物相對於 經轉化烯烴之量的量,其以莫耳%表示。此外,如此高之 _ _轉化率使得該製程可經濟地以單程模式進行,其意謂 不應用未轉化反應物之再循環;且可將空氣饋入環氧化製 程中,其意謂有效地消除對於空氣分離單元之需要。 在本發明之實施中,包括烯烴氧化物之反應產物可藉由 與熱父換流體之熱父換而驟冷。該驟冷可在製程微通道 210之第二區340中#由與存在於一或多第二熱交換通道 350中之熱交換流體熱交換㈣行。通f,可將包括稀煙 氧化物之反應產物的溫度降至至多25〇。〇、更通常至多 225 C、較佳在20至200 C範圍内、更佳在5〇至19〇。〇範圍 117072.doc -31 - 200744749 内尤其在80至18〇。(:範圍内之溫度。該驟冷可導致 至2〇〇t '尤其70至16〇。(:範圍内之溫度降低。驟冷可實現 增加環氧化製程饋料中之烯烴氧化物及氧氣之總量,且消 除=載氣體之需要或減少環氧化製程饋料中的壓載氣體 之里驟冷之又一結果為所產生之烯烴氧化物為較純淨產 ^ 物,包含較少醛及羧酸雜質。 在一些實施例中,環氧化製程可包含: •:、如上文中所述,在-微通道反應器之一或多個製程微通 道210之第—區㈣中所含有之環氧化催化劑存在的情況下 使包含稀烴及氧氣之饋料發生反應,藉此形成包含稀煙氧 化物及一氧化碳之第一混合物; _以如上文中所述之相同方式,在設置於第一區240下游 之该或該等製程微通道21〇之中間區44〇中藉由與熱交 體之熱交換將該第一混合物驟冷,及 、" -在設置於中間區440下游之該或該等製程微通道21〇之第 • 二區340中使該經驟冷之第一混合物轉化,以形成包含烯 煙氧化物及1,2-碳酸酯之第二混合物。 由經驟冷之包含烯烴氧化物及二氧化碳之第一混合物形 ,成包含烯烴氧化物及!,2_碳酸醋之第二混合物的轉化通常 包含使至少一部分存在於第一混合物中之烯烴氧化物與至 少一部分存在於第一混合物中之二氧化碳反應以形成^ 碳酸酯。通常,存在於第一混合物中之二氧化碳為環氧化 反應中共形成之二氧化碳。存在於第一混合物中之二氧化 碳的莫耳量相對於每莫耳存在於該第一混合物中之烯烴氧 117072.doc -32- 200744749 化物而言可處於〇.〇1至1莫耳%、尤其〇〇2至〇.8莫耳%、更 尤其0·05至0.6莫耳%之範圍内。用於烯烴氧化物與二氧化 石厌之轉化的合適催化劑可為(例如)在苯乙烯/二乙烯苯共聚 物基質上包含鹵化第四鱗基團或鹵化第四銨基團之樹脂, 其中該i化物可尤其為氯化物或溴化物。用於該轉化之該 4 催化劑自 T. Nishikubo,A. Kameyama,J. Yamashita 及 M.
i〇moi5 j〇urnai of P〇lymer Science, Pt. A. Polymer Chemist’ 939 _ 947 (1993)中已知,該參考文獻以引用 之方式併入本文中。用於烯烴氧化物與二氧化碳之轉化的 其他合適催化劑為(例如)_化第四鱗、鹵化第四銨及特定 金屬鹵化物。-實例為碘化甲基三丁基鱗。溫度可處於30 至200。。、尤其5(^15〇。。之範圍内。如上文中描述在第二 饋料通道處所量測,壓力可處於500至3500 kPa之範圍 内。通ΐ ’至少50莫耳%、尤其至少8〇莫耳%、更尤其至 少9〇莫耳%之二氧化碳經轉化,例如至少98莫耳%,^在 本發明之實施中,通常至多99 9莫耳%者經轉化。 =烯煙氧化物之環氧化反應混合物可自 =反:器中退出’且使用習知方法及習知設備: 式口〜理。分㈣統可提供㈣氧化物 烯烴:任何未轉化氧氣、任㈣载氣體及二氧化碳= 離為如水之水性萃取流體可用於分離該等組份二 烴氧化物之經富集萃取流體S有坤 化物。所產生之烯烴氧化步處理以回收烯煙氧 蒸餾或萃取而回收。勺°集萃取流體例如藉由 包含任何未轉化婦煙、任何未轉化氧 117072.doc -33- 200744749 -、任何壓載氣體及二氧化碳且其中稀烴氧化物含 混合物可經萃取以至少部分地移除二氧化碳。所得的低二 乳化碳=量之混合物可加以壓縮、乾燥且再循環以作 發明之環氧化製程的饋料組份。 在本么曰月之環氧化製程中所I生之焊煙氧化物可藉由羽 知方法而轉化為!,2_二醇、•碳酸g旨或^ 胺0
轉化為1,2-二醇或丨,2_二醇醚可包含(例如)以熱方法或藉 由使用可為酸性催化劑或鹼性催化劑之催化劑使環氧乙烷 與水反應。例如,對於主要製造丨,^二醇且較次要製造 1,2-二醇醚而言,烯烴氧化物可在酸性催化劑(例如基於總 反應混合物為0.5至1.0%〜之硫酸)存在情況下,在5〇至 70°C及100 kPa絕對壓力下與十倍莫耳濃度之過量水發生液 相反應;或較佳在無催化劑存在情況下,在丨3〇至24〇。〇及 2000至4000 kPa絕對壓力下發生氣相反應。該大量水之存 在可有利於1,2-二醇之選擇性形成,且可充當反應放熱之 散熱物質(sink),有助於控制反應溫度。若水之比例降 低,則反應混合物中1,2-二醇醚之比例升高。由此所產生 之- —醇鱗可為二醚、三鱗、四醚或後續_。可藉由以 醇(尤其為第一醇,諸如甲醇或乙醇)取代至少一部分水來 使烯烴氧化物轉化,從而製備可選1,2-二醇醚。 藉由使烯烴氧化物與二氧化碳反應,可使烯烴氧化物轉 化為相應1,2-碳酸酯。若須要,則可藉由隨後使丨,2_碳酸 酯與水或醇反應以形成1,2-二醇,從而製備1,2-二醇。關 117072.doc -34- 200744749 於適用方法,參考US-A-6080897,該案以引用之方式併入 本文中。 轉化為垸醇胺可包含使烯烴氧化物與胺(諸如氨、燒基 胺或二烷基胺)反應。可使用無水氨或氨水。無水氨通常 用於協助單烷醇胺之製造。關於適用於使烯烴氧化物轉化 為烷醇胺之方法,可參考例如US-A-4845296,該案以引用 之方式併入本文中。 1,2-二醇及二醇醚(例如乙二醇、Li丙二醇及乙二 4醚)可用於多種工業應用,例如用在食品、飲料、煙 草化妝131:7、熱塑性聚合物、固化樹脂系統、清潔劑、熱 轉移系統等領域中。碳酸醋(例如碳酸乙二醋)可用作 稀釋劑’尤其用作溶劑。舉例而t,乙醇胺可用於天然氣 之處理(,,脫硫,,)。 除非另外才曰定’否則本文中所提及之有機化合物,例如 烯L醇1,2 —醇、1,2·二醇_、12-碳酸_、乙醇胺及 有機鹵化物’通常具有至多4G個碳原子,更通常至多2〇個 碳原子’尤其至多10個碳原子,更尤其至多6個碳原子。 通常’該等有機化合物具有至少一個碳原子。如本文中定 義,碳原子數(亦即碳數)之範圍包括對範圍界限指定之數 目° 下列實例意欲說明本發明之優勢而不意欲不當地限制本 發明之範疇。 實例 -1划珂貫施本發明之一實 U7072.doc -35 - 200744749 一微通道反應器將包含製程微通道、第一熱交換微通 道、第二熱交換微通道及第一饋料通道。該等製程微通道 將包含一上游端、一第一區及一第二區。 第一區將適於與在第一熱交換微通道中流動之熱交換流 體進行熱交換。第二熱交換微通道將包含兩組適於與第二 區進行熱交換之第二熱交換微通道,以便在第二區之下游 部分可達成相較於第二區之上游部分更低之溫度。饋料微 通道將經由孔終止於製程微通道之第一區中。該等孔將以 大致相等之距離朝向第一區之下游方向自微通道之上游端 設置至第一區長度之三分之二,且在垂直方向上該等孔將 以大致相等之距離大致越過製程微通道之整個寬度而設 置。 第一區將包含環氧化催化劑,其包含經沈積於微粒載體 材料上之銀、銖、鎢、鉋及鋰。該微粒載體材料將為具有 1.5 m2/g之表面積、〇·4 ml/g之總孔隙體積及特定孔徑分佈 (該孔徑分佈使得具有〇·2至1〇 μχη範圍内之直徑之孔隙為總 孔隙體積之95%且具有〇·3至1〇 μπι範圍内之直徑之孔隙為 包含在具有0.2至10 μιη範圍内之直徑之孔隙中的孔隙體積 的9 2 %以上)的α氧化銘。 該微通道反應器將根據自WO-A-20〇4/099113及其中所 引用之參考文獻已知的方法而組裝。在組裝之後,以將藉 由研磨及師分可自 CRI Catalyst Company,Houston, Texas, USA獲得之市售HS_PLUS環氧化催化劑而製備的微粒環氧 化催化劑填充該第一區。為填充該第一區,將經研磨且_ 117072.doc -36- 200744749 分之催化劑於甲醇中之分散體㈣人該第—區巾,且將甲 :自該第一區移除。銀之量為35〇kg/m3反應器體積,反應 杰體積係由該等微通道為該環氧化催化劑所佔據部分之橫 截面積及總長度所界定的總體積。 一將藉由與在第-熱交換微通道中流動之熱交換流體之熱 广換而在220 C下加熱第_ 1,同時經由設置於製程微通 道之上游端處的-開口饋人乙稀。氧氣與氣乙燒之混合物
(以體積計3 ppm)將經由饋料通道饋人。氧氣與乙稀之莫 :比將為1:1。離開第一區且進入製程微通道之第二區的 此a物將在第一區中以兩個步驟被初始驟冷至1 $〇。〇之溫 度且後驟冷至8G°C之溫度。乙稀及氧氣之溫度及饋料速 率將經調整以便使乙烯之轉化率為97莫耳%。接著,將調 整氧氣與氯乙烷之混合物中氯乙烷之量,以便優化對環氧 乙烧之選擇性。 可猎由移除二氧化碳及未轉化氧氣及乙烯來純化該環氧 乙烷富集產物。經純化環氧乙烷可使用水而轉化以得到乙 二醇。 【圖式簡單說明】 圖1展示一微通道反應器及其主要構成之示意圖。 圖2展示一包含製程微通道及熱交換通道之重複單元及 其在用於本發明之實施時之操作之典型實例的示意圖。本 發明之微通道反應器可包含複數個該等重複單元。 【主要元件符號說明】 100 微通道反應器 117072.doc •37- 200744749
102 製程頂蓋 104 製程微通道 108 製程腳座 110 熱交換頂蓋 112 熱交換腳座 114 箭頭 116 箭頭 210 製程微通道 220 上游端 230 下游端 240 第一區 250 第一熱交換通道 260 第一饋料通道 280 第一孔 340 第二區 350 第二熱交換通道 360 第二饋料通道 380 第二孔 440 中間區 450 第三熱交換通道 117072.doc -38 -
Claims (1)
- 200744749 十、申請專利範圍: i.-種在-微通道反應器之—或多個製程微通道中 氧化催化劑之方法,該方法包含: 衣 ;只催化背ij於基本上無水之稀釋劑中之分散體系引入 該或該等製程微通道中,及 移除至少一部分該稀釋劑。 2·如請求項1之方法,其中該稀釋劑為液體稀釋劑,且具 有相對於該稀釋劑重量而言至多5%w之水含量。 、 一求員2之方法,其中該水含量相對於該稀釋劑重量 4. 如請求項2或3之方法’其中存在於該液體稀釋劑中之催 化劑之量相對於該催化劑與該液體稀釋劑之總重量而言 係處於1至50% w之範圍内。 5.如請求項4之方法’丨中該存在於該液體稀釋劑中之催 化劑之量相對於該催化劑與該液體稀釋劑之總重量而言 係處於2至3 0%w之範圍内。 6. 8. 如請求項1之方法’其中該稀釋劑為存在於該等製程微 通道中時處於露點溫度以上之氣體稀釋劑。 士明求項6之方法’其中存在於該氣體稀釋劑中之催化 ,之量按照該催化劑重量相對於該氣_釋劑體積而計 异係處於10至5〇〇 g/l之範圍内。 h求項7之方法’其中該存在於該氣體稀釋劑中之催 =之量按照該催化劑重量相對於該氣相稀釋劑體積而 什异係處於22至3〇0g/1之範圍内。 117072.doc 200744749 9 ·如請求項1至8中 任—項之方法,其中存在於該分散體系 内VA化劑的平均粒徑心〇係處於〇.1至100 μηι之範圍 10 ·如請求項9夕士 、 方去,其中該平均粒徑d50係處於〇.5至5〇 μπι之範圍内。 11 ·如請求項1 $ ; Λ 士 h 任一項之方法,其中該催化劑為能夠 P -有大小為該製程微通道最小尺寸之至多50%之 開口的ASTM筛之微粒材料。 h求項11之方法’其中該催化劑為能夠穿過一且有大 小為該製程微通道最小尺寸之至多 /、 之微粒材料。 "3〇/〇^^^AS™^ 13.如請求項丨至12中任—項之方法,发 ,,..^ 八千垓方法包含以催 化劑填充床之形式裝置該催化劑。 14·如請求項1至13中任一項之方法, 一 八M 其中經沈積之第11族 至屬之量係處於10至5〇〇 kg/m3反庫 竭益體積之範圍内,反 應器體積係由該等微通道為該環氣 乳化催化劑所佔據部分 之橫截面積及總長度所界定的總體積。 15·如請求項14之方法,其中經沈積 Λ , 、弟11族金屬之量係處 於50至400 kg/m3反應器體積之範囹 、、 ^ 内,反應器體積係由 έ亥荨微通道為該環氧化催化劑所彳上# 蜊所佔據部分之橫截 總長度所界定的總體積。 /、戰曲積及 1 6·如請求項1至1 5中任一項之方法, ”中该催化劑包含银 作為該第11族金屬。 3 m 1 7 ·如睛求項16之方法’其中έ亥催化兩| ^另外包含包括一或多 117072.doc -2- 200744749 種選自鍊、鎢、鉬、枚芬甘、曰人^ 士 八 鉬鉻及其化合物之元素的促進劑組 伤且另外包含選自鐘、鉀、絶及其混合物之驗金屬。 is. —種用於烯烴環氧化之方法,其包含: 藉由如請求Jg 1 g Ί q + ^ t σ〇 、 、至17中任一項之方法在一微通道反應 為之;或多個製程微通道中裝置環氧化催化劑,及 在f置於-或多個製程微通道中之該環氧化催化劑存 的’月况下j吏包含該烯烴及氧氣之饋料發生反應。 19.如請求項18之方法,其中該饋料包含相對於總饋料而古 總量為至少50莫耳%之該稀煙及氧氣。 。 2〇·如清求項18或19夕古、ί » 方法,其中该方法包含使包含該烯烴 =氣之饋料發生反應,及使用可使該浠烴之轉化率或 忒虱氣之轉化率為至少9〇莫耳%之條件。 21·如請求項18至20中任一 貝之方法,其中該方法另外包合 在该等製程微通道之下游Ρ φ 卜游&中將該反應產物驟冷。 22·如請求項2 1之方法,1中 八Τ鑌方法另外包含在一或多個製 程微通道中使該經驟冷 " 一 7 <夂應產物轉化,以形成包含該 烯烴氧化物及i,2-碳酸酿之混合物。 23. —種用於製備1?2_二醇 1,2-一知醚、丨,孓碳酸酯或烷醇 胺之方法,該方法包含·· 抑精由士^項1至17中任一項之方法在-微通道反應 "、之一或夕個製程微通道中裝置環氧化催化劑, 在裝置於-或多個製程微通道中之該環氧化催化劑存 在的情況下,使包含歸烴及氧氣之饋料發生反應以得到 烯烴氧化物,及 117072.doc 200744749 使用水、醇、二氧化碳或胺使該烯烴氧化物轉化以形 成孩1,2-二醇、該1,2_二醇醚、該ι,2-碳酸酯或該烧醇 胺。 24·如請求項1 8至23中任一項之方法,其中該烯烴包含乙 烯。 25· —種適用於烯烴環氧化之反應器,該反應器為一包含一 或多個已裝置呈催化劑填充床形式之環氧化催化劑於其 中之製程微通道的微通道反應器,且其中該環氧化催化 劑包含第11族金屬,其中該第U族金屬之量係處於1〇至 500 kg/m3反應器體積之範圍内,反應器體積係由該等微 通道為該環氧化催化劑所佔據部分之橫截面積及總長度 所界定的總體積。 26. 如請求項25之反應器,其中經沈積之第u族金屬之量係 處於50至400 kg/m3反應器體積之範圍内,反應器體積係 由該等微通道為該環氧化催化劑所佔據部分之橫截面積 及總長度所界定的總體積。 27. 如請求項25或26之反應器,其中該催化劑包含銀作為該 第11族金屬。 28. 如請求項27之反應器,其中該催化劑另外包含包括一或 多種選自銖、鎢、鉬、鉻及其混合物之元素的促進劑組 份,且另外包含選自鐘、_、铯及其混合物之驗金屬。 117072.doc
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TW95147794A TW200745072A (en) | 2005-12-22 | 2006-12-20 | A process for the preparation of a chemical derivable from an olefin oxide, and a reactor suitable for such a process |
TW95147796A TW200730517A (en) | 2005-12-22 | 2006-12-20 | Method for regenerated epoxide catalyst preparation |
TW95147792A TW200738661A (en) | 2005-12-22 | 2006-12-20 | A process for the preparation of an olefin oxide or a chemical derivable from an olefin oxide, and a reactor suitable for such a process |
TW95147793A TW200734317A (en) | 2005-12-22 | 2006-12-20 | A process for the preparation of an olefin oxide or a chemical derivable from an olefin oxide |
TW95147798A TW200738662A (en) | 2005-12-22 | 2006-12-20 | A process for the preparation of an olefin oxide or a chemical derivable from an olefin oxide, and a reactor suitable for such a process |
TW095148637A TWI412403B (zh) | 2005-12-22 | 2006-12-22 | 一種由供體用過環氧化催化劑中再利用錸之方法 |
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EP (2) | EP1979093A2 (zh) |
JP (10) | JP2009521498A (zh) |
KR (10) | KR20080082986A (zh) |
CN (10) | CN101384569A (zh) |
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FR (9) | FR2895401A1 (zh) |
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MX (10) | MX2008007849A (zh) |
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TW (11) | TW200728294A (zh) |
WO (11) | WO2007076407A2 (zh) |
ZA (7) | ZA200610750B (zh) |
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- 2006-12-20 GB GB0625415A patent/GB2433739A/en not_active Withdrawn
- 2006-12-20 JP JP2008547747A patent/JP2009521498A/ja not_active Withdrawn
- 2006-12-20 BE BE2006/0637A patent/BE1017795A3/fr not_active IP Right Cessation
- 2006-12-20 WO PCT/US2006/062401 patent/WO2007076394A2/en active Application Filing
- 2006-12-20 KR KR1020087017103A patent/KR20080080181A/ko not_active Application Discontinuation
- 2006-12-20 WO PCT/US2006/062398 patent/WO2007076392A2/en active Application Filing
- 2006-12-20 CN CN2006800523436A patent/CN101336135B/zh active Active
- 2006-12-20 JP JP2008547748A patent/JP2009521499A/ja not_active Withdrawn
- 2006-12-20 KR KR1020087018008A patent/KR101374910B1/ko not_active IP Right Cessation
- 2006-12-20 DE DE102006060395A patent/DE102006060395A1/de not_active Withdrawn
- 2006-12-20 DE DE102006060348A patent/DE102006060348A1/de not_active Withdrawn
- 2006-12-20 RU RU2008130081/04A patent/RU2008130081A/ru not_active Application Discontinuation
- 2006-12-20 NL NL2000385A patent/NL2000385C2/nl not_active IP Right Cessation
- 2006-12-20 TW TW95147795A patent/TW200744748A/zh unknown
- 2006-12-20 NL NL2000384A patent/NL2000384C2/nl not_active IP Right Cessation
- 2006-12-20 WO PCT/US2006/062404 patent/WO2007076397A2/en active Application Filing
- 2006-12-20 NL NL2000392A patent/NL2000392C2/nl not_active IP Right Cessation
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- 2006-12-20 IN IN2734DE2006 patent/IN2006DE02734A/en unknown
- 2006-12-20 CA CA002634324A patent/CA2634324A1/en not_active Abandoned
- 2006-12-20 KR KR1020087017675A patent/KR20080077028A/ko not_active Application Discontinuation
- 2006-12-20 RU RU2008130083/04A patent/RU2008130083A/ru not_active Application Discontinuation
- 2006-12-20 JP JP2008547755A patent/JP2009525163A/ja not_active Withdrawn
- 2006-12-20 CA CA002572366A patent/CA2572366A1/en not_active Abandoned
- 2006-12-20 CA CA002634332A patent/CA2634332A1/en not_active Abandoned
- 2006-12-20 JP JP2008547756A patent/JP2009521501A/ja not_active Withdrawn
- 2006-12-20 NL NL2000391A patent/NL2000391C2/nl not_active IP Right Cessation
- 2006-12-20 TW TW95147794A patent/TW200745072A/zh unknown
- 2006-12-20 BR BRPI0620253-5A patent/BRPI0620253A2/pt not_active IP Right Cessation
- 2006-12-20 DE DE102006060352A patent/DE102006060352A1/de not_active Withdrawn
- 2006-12-20 CA CA002571808A patent/CA2571808A1/en not_active Abandoned
- 2006-12-20 JP JP2008547752A patent/JP2009524596A/ja not_active Withdrawn
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- 2006-12-20 DE DE102006060353A patent/DE102006060353A1/de not_active Withdrawn
- 2006-12-20 RU RU2008130082/04A patent/RU2008130082A/ru not_active Application Discontinuation
- 2006-12-20 GB GB0625418A patent/GB2433501A/en not_active Withdrawn
- 2006-12-20 CA CA002571812A patent/CA2571812A1/en not_active Abandoned
- 2006-12-20 CA CA002571986A patent/CA2571986A1/en not_active Abandoned
- 2006-12-20 RU RU2008130080/04A patent/RU2008130080A/ru not_active Application Discontinuation
- 2006-12-20 BE BE2006/0634A patent/BE1017792A3/fr not_active IP Right Cessation
- 2006-12-20 JP JP2008547741A patent/JP2009525842A/ja active Pending
- 2006-12-20 DE DE102006060396A patent/DE102006060396A1/de not_active Withdrawn
- 2006-12-20 CA CA002571940A patent/CA2571940A1/en not_active Abandoned
- 2006-12-20 RU RU2008130076/04A patent/RU2008130076A/ru not_active Application Discontinuation
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- 2006-12-20 RU RU2008130079/04A patent/RU2008130079A/ru not_active Application Discontinuation
- 2006-12-20 GB GB0625422A patent/GB2433706A/en not_active Withdrawn
- 2006-12-20 CA CA002571960A patent/CA2571960A1/en not_active Abandoned
- 2006-12-20 FR FR0655713A patent/FR2895278A1/fr not_active Ceased
- 2006-12-20 BE BE2006/0631A patent/BE1017789A3/fr not_active IP Right Cessation
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- 2006-12-20 NL NL2000387A patent/NL2000387C2/nl not_active IP Right Cessation
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- 2006-12-20 NL NL2000389A patent/NL2000389C2/nl not_active IP Right Cessation
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- 2006-12-20 BE BE2006/0632A patent/BE1017790A3/fr not_active IP Right Cessation
- 2006-12-20 FR FR0655725A patent/FR2895405A1/fr not_active Ceased
- 2006-12-20 FR FR0655720A patent/FR2895404A1/fr not_active Ceased
- 2006-12-20 BE BE2006/0633A patent/BE1017791A3/fr not_active IP Right Cessation
- 2006-12-20 TW TW95147796A patent/TW200730517A/zh unknown
- 2006-12-20 RU RU2008130078/04A patent/RU2008130078A/ru not_active Application Discontinuation
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- 2006-12-20 TW TW95147792A patent/TW200738661A/zh unknown
- 2006-12-20 DE DE102006060349A patent/DE102006060349A1/de not_active Withdrawn
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- 2006-12-20 TW TW95147793A patent/TW200734317A/zh unknown
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- 2006-12-20 ZA ZA200610754A patent/ZA200610754B/xx unknown
- 2006-12-20 DE DE102006060406A patent/DE102006060406A1/de not_active Withdrawn
- 2006-12-20 WO PCT/US2006/062415 patent/WO2007076404A2/en active Application Filing
- 2006-12-20 KR KR1020087018006A patent/KR20080080215A/ko not_active Application Discontinuation
- 2006-12-20 WO PCT/US2006/062419 patent/WO2007076406A2/en active Application Filing
- 2006-12-20 FR FR0655712A patent/FR2895285A1/fr not_active Withdrawn
- 2006-12-20 WO PCT/US2006/062409 patent/WO2007076400A2/en active Search and Examination
- 2006-12-20 CN CN2006800531837A patent/CN102015669A/zh active Pending
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- 2006-12-20 RU RU2008130077/04A patent/RU2008130077A/ru not_active Application Discontinuation
- 2006-12-20 BE BE2006/0636A patent/BE1017794A3/fr not_active IP Right Cessation
- 2006-12-20 GB GB0625420A patent/GB2433705A/en not_active Withdrawn
- 2006-12-20 CN CNA2006800531697A patent/CN101379050A/zh active Pending
- 2006-12-20 IN IN2743DE2006 patent/IN2006DE02743A/en unknown
- 2006-12-20 TW TW95147798A patent/TW200738662A/zh unknown
- 2006-12-20 NL NL2000388A patent/NL2000388C2/nl not_active IP Right Cessation
- 2006-12-20 CN CNA2006800531818A patent/CN101384359A/zh active Pending
- 2006-12-20 CA CA002572018A patent/CA2572018A1/en not_active Abandoned
- 2006-12-20 EP EP06840329.4A patent/EP1986774B1/en active Active
- 2006-12-20 FR FR0655706A patent/FR2895400A1/fr not_active Withdrawn
- 2006-12-20 CN CNA2006800532191A patent/CN101384572A/zh active Pending
- 2006-12-20 JP JP2008547750A patent/JP2009529489A/ja not_active Withdrawn
- 2006-12-20 JP JP2008547745A patent/JP2009521322A/ja active Pending
- 2006-12-20 GB GB0625425A patent/GB2433503A/en not_active Withdrawn
- 2006-12-20 GB GB0625416A patent/GB2433500A/en not_active Withdrawn
- 2006-12-20 CN CNA2006800532558A patent/CN101384573A/zh active Pending
- 2006-12-20 GB GB0625423A patent/GB2433502A/en not_active Withdrawn
- 2006-12-20 IN IN2733DE2006 patent/IN2006DE02733A/en unknown
- 2006-12-20 CN CNA2006800532098A patent/CN101384571A/zh active Pending
- 2006-12-22 TW TW095148637A patent/TWI412403B/zh not_active IP Right Cessation
- 2006-12-22 TW TW95148638A patent/TW200740522A/zh unknown
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2008
- 2008-06-17 MX MX2008007849A patent/MX2008007849A/es not_active Application Discontinuation
- 2008-06-18 IN IN5274DE2008 patent/IN2008DE05274A/en unknown
- 2008-06-19 MX MX2008007999A patent/MX2008007999A/es not_active Application Discontinuation
- 2008-06-19 MX MX2008008025A patent/MX2008008025A/es not_active Application Discontinuation
- 2008-06-19 MX MX2008008024A patent/MX2008008024A/es not_active Application Discontinuation
- 2008-06-19 MX MX2008008023A patent/MX2008008023A/es not_active Application Discontinuation
- 2008-06-19 MX MX2008008000A patent/MX2008008000A/es not_active Application Discontinuation
- 2008-06-19 MX MX2008008015A patent/MX2008008015A/es not_active Application Discontinuation
- 2008-06-19 MX MX2008007998A patent/MX2008007998A/es not_active Application Discontinuation
- 2008-06-19 MX MX2008008001A patent/MX2008008001A/es not_active Application Discontinuation
- 2008-06-19 MX MX2008008026A patent/MX2008008026A/es not_active Application Discontinuation
- 2008-06-23 IN IN5437DE2008 patent/IN2008DE05437A/en unknown
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