TWI412403B - 一種由供體用過環氧化催化劑中再利用錸之方法 - Google Patents
一種由供體用過環氧化催化劑中再利用錸之方法 Download PDFInfo
- Publication number
- TWI412403B TWI412403B TW095148637A TW95148637A TWI412403B TW I412403 B TWI412403 B TW I412403B TW 095148637 A TW095148637 A TW 095148637A TW 95148637 A TW95148637 A TW 95148637A TW I412403 B TWI412403 B TW I412403B
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- Taiwan
- Prior art keywords
- epoxidation catalyst
- catalyst
- donor
- weight
- epoxidation
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 287
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 227
- 238000000034 method Methods 0.000 title claims abstract description 136
- 229910052702 rhenium Inorganic materials 0.000 title description 21
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title description 21
- 150000001336 alkenes Chemical class 0.000 claims abstract description 66
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000008569 process Effects 0.000 claims abstract description 45
- 150000000180 1,2-diols Chemical class 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims description 110
- 239000000203 mixture Substances 0.000 claims description 89
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 79
- 230000008021 deposition Effects 0.000 claims description 79
- 229910052707 ruthenium Inorganic materials 0.000 claims description 79
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 62
- 239000007788 liquid Substances 0.000 claims description 61
- 238000011084 recovery Methods 0.000 claims description 56
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 45
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 125000002947 alkylene group Chemical group 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 17
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- 230000001186 cumulative effect Effects 0.000 claims description 16
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- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052715 tantalum Inorganic materials 0.000 claims description 4
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000012018 catalyst precursor Substances 0.000 claims description 3
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
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- 229910052719 titanium Inorganic materials 0.000 claims description 3
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- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
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- 229910052741 iridium Inorganic materials 0.000 claims 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- PDGYMUBNWUUWEI-UHFFFAOYSA-N strontium zirconium Chemical compound [Sr].[Zr] PDGYMUBNWUUWEI-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 22
- 239000001301 oxygen Substances 0.000 abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001569 carbon dioxide Substances 0.000 abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 11
- 239000011541 reaction mixture Substances 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
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- 150000002739 metals Chemical class 0.000 description 19
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 14
- -1 ammonium carboxylate Chemical class 0.000 description 14
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- 239000010948 rhodium Substances 0.000 description 11
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
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- 239000012298 atmosphere Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 238000000184 acid digestion Methods 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
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Classifications
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- 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
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Description
本申請案係關於一種由供體用過環氧化催化劑中再利用錸之方法。
錸為極其昂貴之貴金屬錸具有多種用途。錸之一種用途係作為環氧化催化劑上之促進劑。
美國專利第5,739,075號('075專利)描述一種製備適用於製備環氧乙烷之含銀催化劑的方法。該方法沈積大量包括銀及促進量之錸之物質於多孔耐火支撐物上。'075專利亦描述以供沈積於支撐物上之可溶解的錸化合物。參看col.13,11.2-32。
令人遺憾地,在形成所要烯烴氧化物期間,環氧化催化劑經受效能下降,其本身由環氧化催化劑活性之損失及選擇性之損失來表示。回應於活性之損失,可增加環氧化反應溫度以便維持烯烴氧化物之生產速率。商業反應器之操作通常關於反應溫度而受限。當達到適用之溫度極限時,烯烴氧化物之生產速率得以下降或烯烴氧化物之生產得以中斷以將現有環氧化催化劑饋料換成新鮮饋料。新鮮的包含錸之催化劑饋料非常昂貴。
已進行一些努力來使環氧化催化劑再生。例如,美國專利第4,529,714號描述一種使用於製備環氧乙烷之含銀載體催化劑再生的方法,其包含用包含鉀、銣或銫組份及還原劑之溶液來處理鈍化之催化劑。
需要一種降低使用錸作為環氧化催化劑上之促進劑組份之成本的方法。
本發明提供一種由包含用過環氧化催化劑之供體中再利用錸之方法。
本發明亦提供一種製備包含由包含用過環氧化催化劑之供體中回收之錸的環氧化催化劑的方法。
本發明提供一種由供體用過環氧化催化劑中再利用錸之方法,該方法包含:提供包含包括錸之用過環氧化催化劑的供體,該供體之累積環氧烷產量為每立方公尺用過環氧化催化劑0.16千噸("kT")或更多;使該供體與水性液體接觸以產生錸耗乏之供體及包含經萃取之錸之水性萃取物;分離該水性萃取物與該錸耗乏之供體;及使用該經萃取之錸作為後續製程中錸之來源。
本發明亦提供一種使一或多種烯烴環氧化之方法,其包含在根據本發明製備之環氧化催化劑的存在下使包含一或多種烯烴之饋料反應。
本發明亦提供一種產生1,2-二醇、1,2-二醇醚、1,2-碳酸酯或烷醇胺的方法,該方法包含將烯烴氧化物轉化為1,2-二醇、1,2-二醇醚、1,2-碳酸酯或烷醇胺,其中該烯烴氧化物已藉由在根據本發明製備之環氧化催化劑的存在下環氧化一或多種烯烴的方法獲得。
本申請案提供一種降低使用錸作為環氧化催化劑上之促進劑組份之成本的方法。
在一實施例中,該方法有利地由供體用過環氧化催化劑中回收且再利用錸。
在一實施例中,包含得自錸回收法之水性萃取物的沈積混合物係用於沈積經萃取之錸於受體上。在此實施例中,該受體可為新鮮載體物質或用過環氧化催化劑。
在一實施例中,將經萃取之錸自錸回收法期間所產生之水性萃取物中分離。經分離之錸(稱為"回收之錸")可用於多種目的。在一實施例中,該回收之錸為獨立產品。在一實施例中,回收之錸係用於產生沈積混合物以沈積回收之錸於受體上。在一實施例中,該受體可為新鮮載體物質或用過環氧化催化劑。
該方法之優勢在於其可減少處理用於洗滌用過環氧化催化劑之水性液體的需要,藉此降低處理及環境成本。
該方法亦具有降低獲得新鮮錸或新鮮含錸催化劑之成本的優勢。
本申請案之錸回收法可用於由多種包含錸之用過環氧化催化劑中回收錸。在一實施例中,該用過環氧化催化劑包含包括基本量之一或多種11族金屬的載體物質。在一有利實施例中,該11族金屬為銀。在一實施例中,該用過環氧化催化劑包含以下各物之一或多者:錸、錸共促進劑、及/或一或多種其他元素,如下所述。
本文中有時共同使用之字組"摻雜物"係指錸、一或多種11族金屬、一或多種錸共促進劑,且係指沈積於受體載體物質或受體用過環氧化催化劑上的任何其他元素。
通常,該環氧化催化劑在環氧化反應條件下為固體。在環氧化反應進行長時間後,環氧化催化劑變為用過的。如本文所使用,"用過"之環氧化催化劑係指累積環氧烷產量為每立方公尺用過環氧化催化劑0.16千噸("kT")或更多的環氧化催化劑。
環氧化催化劑之活性及/或選擇性一般隨累積環氧烷產量之增加而降低。在一實施例中,累積環氧烷產量為每立方公尺用過環氧化催化劑0.2 kT或更多。在一實施例中,累積環氧烷產量為每立方公尺用過環氧化催化劑0.3 kT或更多。在一實施例中,累積環氧烷產量為每立方公尺用過環氧化催化劑0.45 kT或更多。在一實施例中,累積環氧烷產量為每立方公尺用過環氧化催化劑0.7 kT或更多。在一實施例中,累積環氧烷產量為每立方公尺用過環氧化催化劑1 kT或更多。
在某些實施例中,用過環氧化催化劑為在新鮮時展示啟始條件下之啟始活性及啟始選擇性的催化劑,且該用過環氧化催化劑展示選自由以下效能下降組成之群的一或多種效能下降:(a)選擇性較啟始條件下之啟始選擇性降低2%或更多;及(b)活性較啟始條件下之啟始活性降低10℃或更多。本文中,長時間之使用並非催化劑會變成"用過"之唯一原因。舉例而言,"用過"環氧化催化劑可已中毒或者鈍化。在一有利實施例中,"用過"環氧化催化劑由於相對較大之累積環氧烷產量而具有降低之活性及/或選擇性。
在特定實施例中,用過環氧化催化劑展示選擇性較啟始條件下之啟始選擇性降低5%或更大。在另一實施例中,用過環氧化催化劑展示選擇性較啟始條件下之啟始選擇性降低8%或更大。在另一實施例中,用過環氧化催化劑展示選擇性較啟始條件下之啟始選擇性降低10%或更大。
在環氧化催化劑變為用過後,該用過環氧化催化劑可經受本申請案之錸回收法。
在本申請案中,字組"萃取物"或其派生詞有時係關於錸回收法使用。字組"萃取物"或其派生詞僅出於簡便而使用。除非明確規定,否則不應將字組"萃取物"或其派生詞之使用理解為限制回收錸之方法。
錸回收法包含提供包含一些錸之供體用過環氧化催化劑,在足夠高的溫度下使該供體用過環氧化催化劑與一定量之水性液體接觸足夠長的時間以產生錸耗乏之供體及包含經萃取之錸之水性萃取物。該程序可重複例如另外一或多次。
在一實施例中,得自錸回收法之一或多種水性萃取物的組合包含供體上最初存在之錸之量的大部分。在一實施例中,得自錸回收法之該一或多種水性萃取物的組合包含供體上最初存在之錸之量的75重量%或更多。在一實施例中,得自錸回收法之該一或多種水性萃取物的組合包含供體上最初存在之錸之量的85重量%或更多。
該供體m水性液體之接觸通常於高溫下進行。該高溫一般足以有助於由供體催化劑中回收錸。在一實施例中,該水性液體僅為水。在一實施例中,高溫為50℃或更高。在一實施例中,高溫為100℃或更低。將混合物加熱一段時間以有效地由供體中回收至少一部分錸且產生包含經萃取之錸的水性萃取物。
使經加熱之混合物冷卻。合適之冷卻溫度足夠低以便安全地自錸耗乏之供體中分離水性萃取物。在一實施例中,冷卻溫度為60℃或更低。在一實施例中,冷卻溫度為55℃或更低。在一實施例中,冷卻溫度為50℃或更低。
當經加熱之混合物充分冷卻後,回收水性萃取物。在一實施例中,該水性萃取物係簡單地自錸耗乏供體中傾析。視水體積及所要之回收%而定,可重複該程序。
在一實施例中,用於回收錸之水性液體的重量大體上與自其中回收錸之供體的重量相同。在此實施例中,進行多次萃取可為合意的。本實施例需要更長的時間及更多的工作以進行1:1 w/w萃取。然而,本實施例具有下列優勢:三次1:1 w/w萃取通常可以相對濃之水性萃取物形式回收大部分(若非大體上全部)供體上最初存在之錸。
在一實施例中,使用過量之水性液體。合適之量可變化。舉例而言,該過量可為水性液體比供體用過環氧化催化劑2:1 w/w或更大。在本實施例中,較少萃取回收相對較大量之錸,但產生較稀之萃取物。由於本實施例需要較多設備及工作來處理較多稀釋物,因此其為次佳實施例。
合適之水性液體僅包括水。合適之水性液體亦可包含添加劑。合適之添加劑包括例如鹽、酸、鹼、過氧化物、有機稀釋劑及其類似物。
包含於水性溶液中之合適鹽包括例如銨鹽及鹼金屬之鹵化鹽。
合適之銨鹽包括例如硝酸銨、醋酸銨、羧酸銨、草酸銨、檸檬酸銨、氟化銨及其組合。合適之鹽亦包括其他類型之硝酸鹽,例如鹼金屬之硝酸鹽,諸如硝酸鋰。合適之鹼金屬鹵化鹽包括例如氯化鈉、溴化鈉、碘化鈉、氯化鉀、溴化鉀、碘化鉀、氯化鋰、溴化鋰、碘化鋰、氯化銫、溴化銫、碘化銫、氯化銣、溴化銣、碘化銣及其組合。
包含於水性液體中之合適的有機稀釋劑包括例如以下各物之一或多者:甲醇、乙醇、丙醇、異丙醇、四氫呋喃、乙二醇、乙二醇二甲醚、二乙二醇二甲醚、二甲基甲醯胺、丙酮或甲基乙基酮。
合適之酸包括例如硝酸、碳酸、醯基鹵、硫酸、羧酸、檸檬酸、乳酸、草酸、醋酸及其組合。合適之鹼的實例包括例如鹼金屬氫氧化物、氫氧化銨、氫氧化烷基銨及其組合。合適之鹼金屬氫氧化物包括例如氫氧化銫、氫氧化鉀、氫氧化鋰、氫氧化鈉及其組合。
在一實施例中,水性液體為硝酸銨水溶液。在一有利實施例中,水性液體僅為水。若水性液體僅為水,則水可有利地為去離子水。
由供體用過環氧化催化劑中回收錸之方法可為分批方法。在一實施例中,該方法為連續萃取方法。在一實施例中,該方法使用逆流萃取來執行。熟習此項技術者將認識到該等程序之多種合適之變化。
在一實施例中,水性萃取物中所存在之經萃取之錸係用作後續製程中錸之來源。在一實施例中,將經萃取之錸自水性萃取物中分離以產生回收之錸,且回收之錸係用作後續製程中錸之來源。
為產生回收之錸,可使用任何合適之分離方法將經萃取之錸自水性萃取物中分離。在一實施例中,經萃取之錸藉由使水性萃取物與離子交換樹脂床接觸自水性萃取物中分離。在另一實施例中,水性萃取物之水性部分可例如藉由選自下列方法組成之群的方法移除:昇華、蒸餾、濃縮及其組合。以下僅出於說明之目的更詳細描述前述方法。
在一實施例中,使水性萃取物穿過離子交換樹脂床且回收之錸藉由用適當之試劑洗滌該樹脂床來分離。合適之試劑包括例如酸性水溶液。用於酸性水溶液中之合適酸的實例包括例如硝酸、硫酸、鹽酸及其混合物。
若水性萃取物呈酸性,或若添加酸以保持水性萃取物呈酸性,則可便利地中和水性萃取物以獲得呈可溶錸鹽形式之回收之錸。可溶錸鹽包括例如高錸酸銨、高錸酸鋰、高錸酸銫及其組合。
在一實施例中,萃取物之水性部分係藉由昇華及/或蒸餾水性萃取物來移除以產生氧化錸。參看例如Kirk-Othmer,Concise Encyclopedia of Chemical Technology
(第4版1999年)第1759-1760頁,其以引用的方式併入本文中。以該方法獲得之氧化錸非常純淨且可用於多種應用中。
在一實施例中,藉由昇華及/或蒸發獲得之氧化錸可用水溶解以形成高錸酸。在一實施例中,將藉由昇華及/或蒸發獲得之氧化錸用鹼溶解以形成可溶高錸酸鹽。
在一實施例中,水性萃取物之水性部分係藉由濃縮移除。舉例而言,水性萃取物之水性部分可藉由蒸發移除以產生所要濃度的錸、高錸酸或可溶高錸酸鹽。在一實施例中,對濃縮或蒸發之水性萃取物就錸及其他組份加以分析。
使用錸回收法回收之錸可用於多種應用中。不管錸為水性萃取物中之經萃取之錸或回收之錸,此均為正確的。如上所示,回收之錸可採用多種形式。實例包括氧化錸及/或包含錸、高錸酸或可溶高錸酸鹽之溶液。
在一實施例中,回收之錸以獨立產品形式使用。作為獨立產品,可將回收之錸及/或包含回收之錸之溶液(例如)售予錸供應者以供多種應用使用。
在一實施例中,回收之錸及/或包含回收之錸之溶液可用於製備超級合金及/或超級合金之保護塗層。超級合金及/或超級合金之保護塗層係用於在使用期間經受高溫之組件構造中。該等組件之實例為多種類型之渦輪。參看例如美國專利第7,005,015號,標題為"High-temperature-resistant component and process for producing the high-temperature-resistant component",其以引用的方式併入本文中。
在一實施例中,水性萃取物其本身為沈積混合物或用於製備將錸沈積於支撐物上的沈積混合物。在一實施例中。該支撐物為用過環氧化催化劑。在另一實施例中,該支撐物為新鮮環氧化催化劑之載體物質。在本實施例中,經萃取之錸係沈積於受體上,且無需將經萃取之錸自水性萃取物中分離。本實施例具有下列優勢:由於稀釋劑係用作沈積混合物之整體部分,因此無需自水性萃取物中加工或處理稀釋劑。
在一實施例中,該沈積混合物包含包括回收之錸之水性液體。
在一實施例中,除經萃取及/或回收之錸之外,沈積混合物亦包含一或多種11族金屬為有利的。在一有利實施例中,該11族金屬為銀。
在一實施例中。該沈積混合物進一步包含一或多種選自下列各物之組份:額外的新鮮錸、11族金屬、錸共促進劑、其他元素及其混合物。在一實施例中,該沈積混合物包含包括下列各物之水性萃取物:經萃取之錸、銀、一或多種錸共促進劑及/或一或多種其他元素。
若使用經萃取及/或回收之錸來製備新鮮環氧化催化劑,則摻雜物之沈積產生催化有效之環氧化催化劑以催化烯烴及氧之轉化而產生環氧烷。若使用經萃取及/或回收之錸使受體用過環氧化催化劑復原,則摻雜物之沈積產生展示一或多種改良之復原環氧化催化劑,該等改良包含較受體用過環氧化催化劑增加之選擇性及增加之活性。
以下更詳細描述沈積混合物及沈積方法。
合適之沈積方法包括例如浸漬、離子交換及其類似方法。合適之浸漬法包括例如真空浸漬及孔體積浸漬。在一實施例中,沈積方法為浸漬。在一實施例中,沈積方法為真空浸漬。
錸回收法及/或沈積法可在環氧化反應器內部或外部執行。在一實施例中,錸回收法係使用逆流萃取來執行。
若經萃取或回收之錸待沈積於受體用過環氧化催化劑上,則在沈積前洗滌受體用過環氧化催化劑儘管非必須的,但可為合意的。受體用過環氧化催化劑之洗滌一般在有效地自受體用過環氧化催化劑中移除大部分可溶摻雜物及/或可離子化物質且產生經洗滌之受體用過環氧化催化劑的條件下進行。
在一實施例中,由洗滌供體用過環氧化催化劑所得之水性萃取物可與銀或銀沈積混合物組合以產生組合之沈積混合物。在一實施例中,此組合之沈積混合物係用於沈積經萃取之錸及銀於供體用過環氧化催化劑上,藉此產生復原環氧化催化劑。
再次提及洗滌程序,該洗滌試劑可為水性液體。在一實施例中,該水性液體包含一或多種諸如鹽之添加劑。包含於水性液體中之合適之鹽包括例如銨鹽。合適之銨鹽包括例如硝酸銨、醋酸銨、羧酸銨、草酸銨、檸檬酸銨、氟化銨及其組合。合適之鹽亦包括其他類型之硝酸鹽,例如鹼金屬之硝酸鹽,諸如硝酸鋰。在一實施例中,該水性液體包含一或多種有機稀釋劑。包含於水性液體中之合適的有機稀釋劑包括例如以下各物之一或多者:甲醇、乙醇、丙醇、異丙醇、四氫呋喃、乙二醇、乙二醇二甲醚、二乙二醇二甲醚、二甲基甲醯胺、丙酮、甲基乙基酮、或其混合物。
在一實施例中,該水性液體僅為水。在另一實施例中,該水性液體為硝酸銨水性溶液。
若受體係經洗滌,則洗滌可在任何合適的溫度下進行。在一實施例中,受體係在高溫下,例如在30℃至100℃之溫度下洗滌。在一實施例中,該高溫為35℃至95℃。洗滌可包含使受體與水性液體接觸一段時間。
該接觸時間並不重要,只要該接觸時間足以自受體移除可溶摻雜物及/或可離子化物質即可。在一實施例中,接觸時間可為24小時或更少。在一實施例中,接觸時間可為10小時或更少。在一實施例中,接觸時間為5小時或更少。在一實施例中,接觸時間為1小時或更多。在一實施例中,接觸時間為0.25小時或更多。在一實施例中,接觸時間為0.05小時或更多。
在接觸時間過後,移除包含由受體中瀝濾之物質的液體。該洗滌可重複例如兩次或三次,直至流出物之組成不變。流出物可經處理及/或分離及/或純化,使得流出物中所存在之所有11族金屬及錸均可用於後續製程中。若受體係經洗滌,則經洗滌之受體在進一步處理前可藉由在一定溫度下並歷時足以移除剩餘洗滌溶液的時間加熱乾燥。
乾燥經洗滌受體並非必需。然而,乾燥通常在100℃至300℃之溫度下進行一段時間。時間長短並不重要。在一實施例中,乾燥時間為10小時或更少。在一實施例中,乾燥時間為5小時或更少。在一實施例中,乾燥時間為0.25小時或更多。在一實施例中,乾燥時間為0.05小時或更多。在一實施例中,催化劑係在催化劑烘箱中在流動空氣下於250℃下乾燥15分鐘。
在一實施例中,將一些受體顆粒添加至過量硝酸銨溶液中以形成漿液。合適之硝酸銨溶液的硝酸銨濃度為85重量%或更少。
在高溫下加熱所得漿液。合適之溫度包括例如80℃至90℃。在一實施例中,將高溫維持一段時間。合適之時間為例如1小時或更多。在一實施例中,受體顆粒係在處置之前乾燥。在一實施例中,將受體顆粒添加至新鮮的過量硝酸銨溶液中,且於例如80℃至90℃的高溫下再次加熱。再次將溫度維持一段時間。其後,將硝酸銨溶液傾析且在室溫下(通常15℃至25℃)將受體顆粒浸泡於另一過量硝酸銨溶液中。在一實施例中,重複該室溫處理。
在沈積一或多種摻雜物之前無需乾燥受體。在一實施例中,如前所述將該經洗滌之受體乾燥。
接著使用此項技術中已知之方法將該一或多種摻雜物沈積於受體上。可參考US-A-5380697、US-A-5739075、EP-A-266015及US-B-6368998,其以引用的方式併入本文中。在一實施例中,該等方法包括用包含陽離子11族金屬-胺錯合物與還原劑的液體混合物浸漬微粒載體物質。
在一實施例中,將回收之錸沈積於選自由新鮮催化劑載體物質及用過環氧化催化劑組成之群的受體上。該受體可包含或可不包含基本量之錸。若受體為新鮮催化劑載體物質,則受體可不包含基本量之錸。若受體為用過環氧化催化劑,則受體可包含基本量之錸。經萃取或回收之錸可在沈積其他摻雜物之前、同時或之後沈積於受體上。若經萃取或回收之錸與11族金屬均沈積,則一般形成環氧化催化劑。若僅經萃取或回收之錸沈積,則一般形成環氧化催化劑之催化劑前驅體。
在一實施例中,受體係與沈積混合物接觸,該沈積混合物包含在回收錸期間由一或多種供體用過環氧化催化劑或由受體環氧化催化劑本身所產生的水性萃取物。在另一實施例中,受體係與使用回收之錸所製得回收之錸沈積混合物接觸,該回收之錸已在錸回收法期間自水性萃取物中分離。在沈積混合物與受體接觸一段時間後,將稀釋劑或液體組份移除,於該受體上留下至少一部分經萃取或回收之錸。
合適之回收之錸的沈積混合物通常包含溶解或分散於液體中之回收之錸。合適之液體可包括例如得自供體或受體用過環氧化催化劑之水性萃取物。合適之液體亦可包括例如水或水性有機稀釋劑。合適之水性有機稀釋劑係上文中關於洗滌程序而加以描述者。可沈積回收之錸之形式對於本發明並不重要。舉例而言,回收之錸可合適地以氧化物或氧陰離子形式提供,例如以錸酸鹽或高錸酸鹽形式、以鹽或酸形式提供。供沈積回收之錸用之較佳溶液為高錸酸銨溶液。
在特定實施例中,在移除液體組份之前,可使回收之錸沈積混合物與受體保持接觸達一段接觸時間。接觸時間之持續時間並不重要。合適之接觸時間係在上文中關於洗滌程序而加以描述者。
在一實施例中,受體係在與本文所述之一或多種沈積混合物接觸前抽空一段時間。在一實施例中,將受體抽空至760 mm Hg(大氣壓力)以下。在一實施例中,將受體抽空至250 mm Hg或更低。在一實施例中,將受體抽空至200 mm Hg或更低。在一實施例中,將受體抽空至1 mm Hg或更高。在一實施例中,將受體抽空至5 mm Hg或更高。在一實施例中,將受體抽空至10 mm Hg或更高。較佳係將受體抽空至20 mm Hg或更高。
在一實施例中,在抽空受體後使沈積混合物與受體接觸。在一實施例中,當受體與沈積混合物接觸時保持真空。在該實施例中,在受體與沈積混合物接觸後釋放真空。
若受體為用於製備新鮮環氧化催化劑之載體物質,則沈積於載體物質上之經萃取或回收之錸的量通常產生之錸總量為250毫莫耳/公斤新鮮環氧化催化劑或更少。在一實施例中,錸總量為50毫莫耳/公斤新鮮環氧化催化劑或更少。在一實施例中,錸總量為25毫莫耳/公斤新鮮環氧化催化劑或更少。在一實施例中,錸總量為15毫莫耳/公斤新鮮環氧化催化劑或更少。在一實施例中,錸總量為10毫莫耳/公斤新鮮環氧化催化劑或更少。
若受體為用過環氧化催化劑,則沈積以復原用過環氧化催化劑之組份一般稱為為"額外"組份或"復原"組份。此名稱將額外或復原組份與用過環氧化催化劑上最初存在之任何基本量之相同組份區分。
若受體為用過環氧化催化劑,則受體可包含或可不包含基本量之錸。為沈積復原之經萃取或回收之錸,可保持受體與沈積混合物接觸達足以用沈積混合物浸漬受體用過環氧化催化劑之孔,產生中間受體的接觸時間。特定之接觸時間一般對浸漬並不緊要。合適之接觸時間為0.1分鐘或更多。典型接觸時間為30秒或更多。實際上,接觸時間一般為一分鐘或更多。在一實施例中,接觸時間為3分鐘或更多。
接觸時間屆滿後,可使用任何已知方法將中間受體自液體組份中分離。舉例而言,液體組份可簡單地自中間受體傾析或汲取。為更快速地分離,液體組份可藉由機械方式來移除。合適之機械方式包括振動、離心及其類似方式。中間受體可允許乾燥或可暴露於乾燥條件下。
無論來源如何,沈積於用過環氧化催化劑上之錸有時稱為"復原錸"。復原錸之量一般以復原環氧化催化劑之重量計為0.1毫莫耳/公斤或更多。在一實施例中,復原錸之量以相同基準計為2毫莫耳/公斤或更多。在一實施例中,復原錸之量以相同基準計為50毫莫耳/公斤或更少。在一實施例中,復原錸之量以相同基準計為20毫莫耳/公斤或更少。
該沈積可進行一次以上,例如兩次或三次,以實現所要量之復原錸的沈積。
受體可包含或可不包含基本量之一或多種11族金屬。若受體為用於產生新鮮環氧化催化劑之載體物質,則受體通常不包含基本量之一或多種11族金屬。若受體為用過環氧化催化劑,則受體通常包含基本量之一或多種11族金屬。
該一或多種11族金屬可選自由銀、金及其組合組成之群。在一實施例中,該11族金屬包含銀。
如藉由硝酸消化及銀滴定所量測,當11族金屬之含量以新鮮環氧化催化劑之重量計為10 g/kg或更多時,新鮮環氧化催化劑展示可觀的催化活性。在一實施例中,11族金屬之含量以相同基準計為50 g/kg或更多。在一實施例中,11族金屬之含量以相同基準計為100 g/kg或更多。在一實施例中,11族金屬之含量以相同基準計為500 g/kg或更少。在一實施例中,11族金屬之含量以相同基準計為400 g/kg或更少。
若受體為用過環氧化催化劑,且11族金屬為銀,則沈積於受體上之額外銀的量以用過環氧化催化劑之重量計為0.2重量%或更多。在一實施例中,沈積之額外銀以相同基準計為0.5重量%或更多。在一實施例中,沈積之額外銀以相同基準計為1重量%或更多。在一實施例中,沈積之額外銀以相同基準計為5重量%或更多。在一實施例中,沈積之額外銀以相同基準計為8重量%或更多。在一實施例中,沈積之額外銀以相同基準計為10重量%或更多。在一實施例中,沈積之額外銀以相同基準計為12重量%或更多。
在一實施例中,錸係在該一或多種11族金屬或陽離子11族金屬組份沈積的同時或之後沈積於受體上。若陽離子11族金屬組份沈積,則陽離子11族金屬組份的至少一部分得以還原。
可藉由使受體與11族金屬沈積混合物接觸使該一或多種11族金屬沈積於該受體上。合適之11族沈積混合物包含含有分散之11族金屬的液體,例如11族金屬溶膠。該方法包含例如藉由蒸發移除液體,而將該一或多種11族金屬留在受體上。在一有利實施例中,沈積混合物為包含該一或多種11族金屬之化合物或錯合物之溶液。
在一有利實施例中,11族金屬為銀,且該沈積混合物為銀沈積混合物。在該實施例中,銀沈積混合物一般為包含一或多種銀化合物或銀錯合物之溶液。
該沈積可進行一次以上,例如兩次或三次,以實現所要量之該一或多種11族金屬的沈積。該11族金屬沈積混合物可包含諸如分散劑及穩定劑之添加劑。可在移除液體後藉由例如在100℃至300℃,尤其150℃至250℃之溫度下於惰性氣氛(例如氮或氬)或含氧氣氛(例如空氣或包含氧及氬之混合物)中加熱來移除該等添加劑。
可藉由使受體與包含液體及陽離子11族金屬組份的陽離子11族沈積混合物接觸來將一或多種陽離子11族金屬組份沈積於受體上。將陽離子11族沈積混合物之液體組份移除。還原劑可在應用陽離子11族沈積混合物之前、同時或之後應用。
通常,該陽離子11族沈積混合物可包含陽離子11族金屬組份及還原劑,在此情況下移除液體及執行陽離子11族金屬組份之至少一部分的還原可同時實現。該沈積可進行一次以上,例如兩次或三次,以實現所要量之陽離子11族金屬的沈積。該陽離子11族金屬組份包括例如非錯合或錯合11族金屬鹽,尤其陽離子11族金屬-胺錯合物。
在移除液體組份後,可在100℃至900℃,尤其150℃至300℃之溫度下於惰性氣氛(例如氮或氬)或含氧氣氛(例如空氣或包含氧及氬之混合物)中加熱浸漬之受體。該加熱一般將影響陽離子11族金屬-胺錯合物之至少一部分的還原。陽離子11族金屬-胺錯合物之實例為與單胺或二胺,尤其1,2-伸烷基二胺錯合之陽離子11族金屬。合適之胺的實例為乙二胺、1,2-丙二胺、2,3-丁二胺、乙醇胺及氫氧化銨。可使用高級胺,例如三胺、四胺及五胺。還原劑之實例為草酸鹽、乳酸鹽及甲醛。
對於包含陽離子11族金屬-胺錯合物及還原劑之陽離子11族沈積混合物的其他細節可參考US-A-5380697、US-A-5739075、EP-A-266015及US-B-6368998,其以引用的方式併入本文中。
尤其有利的銀沈積混合物包括例如包含額外陽離子銀金屬-胺錯合物之溶液。實例2中描述有利陽離子銀金屬-胺錯合物溶液之製備。
使銀沈積混合物與受體接觸。接觸時間可變化。合適之接觸時間包括例如1分鐘或更多。在一實施例中,接觸時間可為24小時或更少。溫度及壓力可變化。
在一有利實施例中,受體係如先前所述抽空,且其後使其與11族沈積混合物接觸。在該實施例中,接觸時間可縮短。溫度可高達95℃。在一實施例中,溫度係在10℃至80℃範圍之內。
或者或另外,該一或多種11族金屬可藉由此項技術中已知之氣相沈積技術沈積於受體上。
受體可包含或可不包含基本量之一或多種錸共促進劑。
在一實施例中,將一或多種錸共促進劑沈積於新鮮環氧化催化劑之載體物質上。
沈積於新鮮環氧化催化劑之載體物質上的錸共促進劑之量通常產生以新鮮環氧化催化劑之總重量計0.01毫莫耳/公斤或更多的錸共促進劑總量。在一實施例中,沈積於載體物質上的錸共促進劑之量通常產生以相同基準計0.1毫莫耳/公斤或更多的錸共促進劑總量。在一實施例中,沈積於載體物質上的錸共促進劑之量通常產生以相同基準計0.2毫莫耳/公斤或更多的錸共促進劑總量。
在一實施例中,沈積於載體物質上的錸共促進劑之量通常產生以相同基準計200毫莫耳/公斤或更少的錸共促進劑總量。在一實施例中,沈積於載體物質上的錸共促進劑之量通常產生以相同基準計50毫莫耳/公斤或更少的錸共促進劑總量。在一有利實施例中,沈積於載體物質上的錸共促進劑之量通常產生以相同基準計25毫莫耳/公斤或更少的錸共促進劑總量。
若受體為用過環氧化催化劑,則受體係經復原。在本實施例中,受體用過環氧化催化劑可包含基本量之錸共促進劑。在本實施例中,復原過程可沈積額外量之一或多種復原錸共促進劑於受體上。
合適之復原錸共促進劑可選自包含選自下列元素之元素的組份:鎢、鉻、鉬、硫、磷、硼及其混合物。較佳地,該復原錸共促進劑係選自包含鎢、鉻、鉬、硫及其混合物之組份。有利地,該復原錸共促進劑包含鎢。用於沈積鎢之有利共促進劑沈積混合物包含鎢酸銨溶液。
若受體為用過環氧化催化劑,則沈積於受體用過環氧化催化劑上之各復原錸共促進劑的量以復原環氧化催化劑之總重量計一般為0.01毫莫耳/公斤或更多。在一實施例中,沈積之各復原錸共促進劑之量以相同基準計為0.1毫莫耳/公斤或更多。在一實施例中,沈積之各復原錸共促進劑之量以相同基準計為40毫莫耳/公斤或更少。在一實施例中,沈積之各復原錸共促進劑之量以相同基準計為20毫莫耳/公斤或更少。若復原錸共促進劑為鉬,則沈積之復原鉬之量以相同基準計可為10毫莫耳/公斤或更少。
一或多種其他元素亦可沈積於受體上。受體可包含或可不包含基本量之該一或多種其他元素。
合格的其他元素可選自下列元素之群:氮、氟、鹼金屬、鹼土金屬、鈦、鉿、鋯、釩、鉈、釷、鉭、鈮、鎵、鍺及其混合物。較佳地,鹼金屬係選自鈉、鋰、鉀、銣、銫及其混合物。最佳地,鹼金屬係選自鋰、鉀、銫及其混合物。較佳地,鹼土金屬係選自鈣、鋇、鎂及其混合物。
其他元素可以任何形式沈積。例如,鹼金屬及/或鹼土金屬之鹽為合適的。合適之液體其他元素沈積混合物包含包括一或多種溶解或分散於液體中之其他元素的組份。合適之水性液體及沈積程序係在上文中關於錸加以描述。在一有利實施例中,用於沈積一或多種鹼金屬及/或一或多種鹼土金屬之其他元素沈積混合物為金屬氫氧化物溶液。
包含其他元素之組份的沈積可在其他摻雜物沈積之前、同時或之後實現。可沈積於受體上之多種其他元素之量係在下文描述。除非另作說明,否則認為如本文所使用之環氧化催化劑中所存在之鹼金屬的量為其可在100℃下以去離子水由環氧化催化劑中回收之範圍內的量。萃取方法包括藉由在100℃下於20 ml份去離子水中加熱環氧化催化劑之10公克樣品5分鐘對其加以萃取三次,且藉由使用已知之方法(例如原子吸收光譜)來測定組合之萃取物中之相關金屬。
除非另作說明,否則認為如本文所使用之環氧化催化劑中所存在之鹼土金屬的量為其可在100℃下用10重量%於去離子水中之硝酸由環氧化催化劑中萃取之範圍內的量。萃取方法包括藉由用100 ml份10重量%硝酸煮沸10公克催化劑樣品30分鐘(1 atm,亦即101.3 kPa)對其加以萃取,且使用已知之方法(例如原子吸收光譜)來測定組合之萃取物中之相關金屬。例如在US-A-5801259中描述合適之萃取及量測程序,該案以引用的方式併入本文中。
若受體為用於製備新鮮環氧化催化劑之載體物質,則通常沈積該一或多種其他元素以產生以新鮮環氧化催化劑重量計0.25毫莫耳/公斤或更多之總量。在一實施例中,沈積該一或多種其他元素以產生以相同基準計100毫莫耳/公斤或更少之總量。其他元素可以任何形式提供。
若受體為用過環氧化催化劑,則除鋰以外之其他復原元素的量以復原環氧化催化劑計可為1毫莫耳/公斤或更多。在一實施例中,其他復原元素之量以相同基準計為50毫莫耳/公斤或更少。
若其他復原元素包含一或多種鹼金屬,則除鋰以外之復原鹼金屬的總量以相同基準計一般為0.1毫莫耳/公斤或更多。在一實施例中,除鋰以外之復原鹼金屬的總量以相同基準計為0.2毫莫耳/公斤或更多。在一實施例中,除鋰以外之復原鹼金屬的總量以相同基準計為50毫莫耳/公斤或更少。在一實施例中,除鋰以外之復原鹼金屬的總量以相同基準計為30毫莫耳/公斤或更少。
若鋰用作復原鹼金屬,則復原鋰之總量以相同基準計為1毫莫耳/公斤。在一實施例中,復原鋰之總量以相同基準計為100毫莫耳/公斤或更少。
若沈積復原銫,則復原銫之量以相同基準計為0.1毫莫耳/公斤或更多。在一實施例中,復原銫之量以相同基準計為0.2毫莫耳/公斤或更多。在一實施例中,復原銫之量以相同基準計為1毫莫耳/公斤或更多。在一實施例中,復原銫之量為以相同基準計為50毫莫耳/公斤或更少。在一實施例中,復原銫之量為以相同基準計為30毫莫耳/公斤或更少。在一實施例中,復原銫之量為以相同基準計為10毫莫耳/公斤或更少。
若添加復原鹼土金屬,則復原鹼土金屬的有利量以相同基準計為1毫莫耳/公斤或更多。在一實施例中,復原鹼土金屬之量以相同基準計為100毫莫耳/公斤或更少。
將摻雜物沈積於載體物質上之方法在此項技術中已知,且該等方法可應用於本發明之方法的實踐中。可參考US-A-5380697、US-A-5739075、EP-A-266015及US-B-6368998,其以引用的方式併入本文中。合適地,該等方法包括用包含陽離子11族金屬-胺錯合物及還原劑的液體混合物浸漬微粒載體物質。
若受體為用過環氧化催化劑,則復原過程產生展示增加之選擇性、增加之活性或其組合的復原環氧化催化劑。如本文所使用,選擇性為所形成之烯烴氧化物的量相對於所轉化之烯烴的量,其以莫耳-%來表示。
有利地,該復原環氧化催化劑展示選擇性較受體用過環氧化催化劑之選擇性增加1莫耳-%或更多。在一實施例中,復原環氧化催化劑展示選擇性在相同基準上增加5莫耳-%或更多。在一實施例中,復原環氧化催化劑展示選擇性在相同基準上增加7莫耳-%或更多。更有利地,復原環氧化催化劑展示選擇性在相同基準上增加10莫耳-%或更多。甚至更有利地,復原環氧化催化劑展示選擇性在相同基準上增加12莫耳-%或更多。
在一實施例中,復原環氧化催化劑展示較受體用過環氧化催化劑之活性增加。復原環氧化催化劑之增加之活性藉由產生特定量環氧烷所需之溫度("產生溫度")較受體用過環氧化催化劑之產生溫度的降低來證實。產生溫度降低5℃等同於活性增加5℃。
在一實施例中,復原環氧化催化劑之產生溫度較受體用過環氧化催化劑之產生溫度降低2℃或更多。在一實施例中,復原環氧化催化劑之產生溫度在相同基準上降低3℃或更多。在一實施例中,復原環氧化催化劑之產生溫度在相同基準上降低4℃或更多。在一實施例中,復原環氧化催化劑之產生溫度在相同基準上降低5℃或更多。在一實施例中,該產生溫度在相同基準上降低8℃或更多。在一實施例中,該產生溫度在相同基準上降低9℃或更多。
在一實施例中,復原環氧化催化劑之產生溫度在相同基準上降低40℃或更少。在一實施例中,復原環氧化催化劑之產生溫度在相同基準上降低20℃或更少。在一實施例中,復原環氧化催化劑之產生溫度在相同基準上降低15℃或更少。在一實施例中,復原環氧化催化劑之產生溫度在相同基準上降低12℃或更少。在一實施例中,復原環氧化催化劑之產生溫度在相同基準上降低10℃或更少。
在繼先前復原後之環氧化催化劑經再次使用後,用過環氧化催化劑可連續多次復原。在完成復原過程後,包含烯烴及氧氣之饋料可在復原環氧化催化劑的存在下使用任何合適之方法反應。
若受體為新鮮載體物質或用過環氧化催化劑,則該環氧化催化劑包含載體物質。該載體物質可為天然或人造無機材料,且可包括耐火材料、碳化矽、黏土、沸石、炭及鹼土金屬碳酸鹽,例如碳酸鈣。在一有利實施例中,載體物質包含一或多種耐火材料。合適之耐火材料的實例包括例如氧化鋁、氧化鎂、氧化鋯及矽石。在一有利實施例中,載體物質為α-氧化鋁。在本實施例中,載體物質通常包含相對於載體重量至少85重量%,更通常至少90重量%,尤其至少95重量% α-氧化鋁,經常高達99.9重量% α-氧化鋁。α-氧化鋁之其他組份可包含例如矽石、例如鈉及/或鉀組份之鹼金屬組份及/或例如鈣及/或鎂組份之鹼土金屬組份。
載體物質之表面積相對於載體之重量可合適地為至少0.1 m2
/g,較佳至少0.3 m2
/g,更佳至少0.5 m2
/g,且尤其至少0.6 m2
/g;且該表面積相對於載體之重量可合適地為至多10 m2
/g,較佳至多5 m2
/g,且尤其至多3 m2
/g。應瞭解,如本文所使用之"表面積"係關於藉由如Journal of the American Chemical Society 60(1938)第309-316頁中所述之B.E.T.(Brunauer,Emmett及Teller)方法所測定的表面積。高表面積載體物質(尤其在其為除矽石外視情況包含鹼金屬及/或鹼土金屬組份的α-氧化鋁時)提供改良之效能及操作穩定性。
載體物質之吸水率通常係在0.2 g/g至0.8 g/g,較佳0.3 g/g至0.7 g/g範圍內。鑒於一或多種摻雜物更有效之沈積,較高之吸水率可為有利的。如本文所使用,吸水率係如根據ASTM C20所量測,且吸水率表示為相對於載體重量可經載體孔吸收之水的重量。
微粒載體物質可具有使得直徑在0.2 μm至10 μm範圍內的孔佔總孔體積至少70%的孔尺寸分佈。該相對狹窄的孔尺寸分佈可有助於催化劑之活性、選擇性及壽命之一或多者。壽命可關於維持催化劑活性及/或維持選擇性。如本文所用,孔尺寸分佈及孔體積係如使用Micrometrics Autopore 9200型(130°接觸角,汞之表面張力為0.473 N/m且施用汞壓縮校正)藉由壓汞法至3.0×108
Pa的壓力所量測。
在一有利實施例中,孔尺寸分佈使得直徑在0.2 μm至10 μm範圍內的孔佔總孔體積的75%以上,尤其80%以上,更佳85%以上,最佳90%以上。經常,孔尺寸分佈使得直徑為0.2 μm至10 μm範圍內的孔佔總孔體積的99.9%以下,更經常為99%以下。
在一有利實施例中,孔尺寸分佈使得直徑在0.3 μm至10 μm範圍內的孔佔直徑在0.2 μm至10 μm範圍內孔所含之孔體積的75%以上,尤其80%以上,更佳85%以上,最佳90%以上,尤其高達100%。
通常,孔尺寸分佈使得直徑小於0.2 μm之孔佔總孔體積之10%以下,尤其5%以下。經常,直徑小於0.2 μm之孔佔總孔體積之0.1%以上,更經常0.5%以上。
通常,孔尺寸分佈使得直徑大於10 μm之孔佔總孔體積20%以下,尤其10%以下,更尤其5%以下。經常,直徑大於10 μm之孔佔總孔體積之0.1%以上,尤其0.5%以上。通常,直徑在0.2 μm至10 μm範圍內之孔提供至少0.25 ml/g,尤其至少0.3 ml/g,更尤其至少0.35 ml/g之孔體積。通常,直徑在0.2 μm至10 μm範圍內之孔提供至多0.8 ml/g,更通常至多0.7 ml/g,尤其至多0.6 ml/g之孔體積。
新鮮或復原環氧化催化劑可用於催化環氧化方法。環氧化方法可以多種方式進行。在一實施例中,環氧化方法為氣相方法,亦即饋料於氣相中與以固體物質形式存在之環氧化催化劑(通常於填充床中)接觸的方法。一般而言,該環氧化方法為連續方法。
用於環氧化方法中之烯烴可為任何烯烴。合適之烯烴包括芳族烯烴,例如苯乙烯;或無論共軛與否之二烯烴,例如1,9-癸二烯或1,3-丁二烯。通常,烯烴為單烯烴,例如2-丁烯或異丁烯。在一實施例中,烯烴為單-α-烯烴,例如1-丁烯或丙烯。在一較佳實施例中,烯烴為乙烯。
饋入環氧化製程中之饋料中的烯烴濃度可在寬範圍內加以選擇。通常,饋料中烯烴濃度相對於總饋料將為80莫耳%或更少。在一實施例中,烯烴濃度相對於總饋料將為0.5莫耳%至70莫耳%。在一實施例中,烯烴濃度相對於總饋料將為1莫耳%至60莫耳%。如本文所用,認為饋料為與環氧化催化劑接觸之組合物。
該環氧化方法可基於空氣或基於氧,參看"Kirk-Othmer Encyclopedia of Chemical Technology",第3版第9卷,1980,第445-447頁。在基於空氣之方法中,將空氣或富含氧之空氣用作氧化劑之來源,而在基於氧之方法中,將高純度(95莫耳%或更多)氧用作氧化劑之來源。
饋料中氧之濃度可在寬範圍內加以選擇。然而,在實務上,一般以避免可燃狀態之濃度應用氧。通常,所應用之氧濃度將為總饋料之1莫耳%至15莫耳%,更通常為2莫耳%至12莫耳%。
為保持非可燃狀態,饋料中之氧濃度可隨著烯烴濃度的增加而降低。實際之安全操作範圍視饋料組成而定,且亦視諸如反應溫度及反應壓力之反應條件而定。
饋料中可存在反應改質劑以相對於所要之烯烴氧化物的形成增加選擇性,抑制烯烴或烯烴氧化物至二氧化碳及水的不當氧化。許多有機化合物,尤其有機鹵化物及有機氮化合物可用作反應改質劑。亦可使用氮氧化物、肼、羥胺、氨或其組合。在本申請案不限於理論的情況下,經常認為在烯烴環氧化之操作條件下,含氮反應改質劑為硝酸鹽或亞硝酸鹽之前驅體,亦即其為所謂硝酸鹽形成化合物或亞硝酸鹽形成化合物(參看例如EP-A-3642及US-A-4822900,其以引用的方式併入本文中)。
在一有利實施例中,反應改質劑為有機鹵化物。合適之有機鹵化物包括例如有機溴化物及有機氯化物。在一有利實施例中,有機鹵化物為氯代烴或溴代烴。在一尤其有利實施例中,該反應改質劑係選自氯甲烷、氯乙烷、二氯乙烷、二溴乙烷、氯乙烯及其混合物之群。在一尤其有利實施例中,該反應改質劑為氯乙烷及二氯乙烷。
合適之氮氧化物通式為NOx
,其中x在1至2的範圍內,且包括例如NO、N2
O3
及N2
O4
。合適之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。實例包括硝基甲烷、1-硝基丙烷或2-硝基丙烷。在一有利實施例中,硝酸鹽形成化合物或亞硝酸鹽形成化合物(例如氮氧化物及/或有機氮化合物)連同有機鹵化物,尤其有機氯化物使用。
反應改質劑一般在以相對於總饋料例如至多0.1莫耳%(例如0.01×10- 4
莫耳%至0.01莫耳%)之饋料濃度下使用時有效。在一有利實施例中,若烯烴為乙烯,則反應改質劑係以0.1×10- 4
莫耳%至50×10- 4
莫耳%之濃度存在於饋料中。在另一有利實施例中,反應改質劑係以相對於總饋料0.3×10- 4
莫耳%至30×10- 4
莫耳%之濃度存在於饋料中。
除烯烴、氧及反應改質劑之外,饋料可含有一或多種可選組份,諸如二氧化碳、惰性氣體及飽和烴中之一或多者。二氧化碳為環氧化製程中之副產物。然而,二氧化碳一般對催化劑活性具有不利影響。通常,應避免饋料中之二氧化碳濃度相對於總饋料超過25莫耳%。在一有利實施例中,應避免饋料中之二氧化碳濃度相對於總饋料超過10莫耳%。可採用二氧化碳濃度相對於總饋料低達1莫耳%或更低。
惰性氣體,例如氮氣或氫氣,可以30莫耳%至90莫耳%,通常40莫耳%至80莫耳%之濃度存在於饋料中。
可存在於饋料中之合適之飽和烴包括例如甲烷及乙烷。若存在飽和烴,則其可以相對總饋料之80莫耳%或更少的量存在。在一有利實施例中,飽和烴係以相對於總饋料之75莫耳%或更少之量存在。經常,飽和烴係以相對於總饋料30莫耳%或更多,更經常40莫耳%或更多的量存在。可將飽和烴添加至饋料中以便增加氧之可燃性極限。
可使用選自寬範圍之溫度進行環氧化製程。有利的反應溫度係在150℃至325℃範圍內。在一尤其有利實施例中,反應溫度係在180℃至300℃範圍內。
有利地,環氧化方法係在1000 kPa至3500 kPa範圍內之反應器入口壓力下進行。"GHSV"或氣體每小時空間速度為常溫常壓(0℃,1大氣壓,亦即101.3 kPa)下每小時穿經一單位體積填充催化劑的氣體單位體積。有利地,若環氧化方法為涉及填充催化劑床之氣相方法,則GHSV係在1500 N1/(1.h)至10000 N1/(1.h)範圍內。有利地,該方法以每小時每立方公尺催化劑產生0.5千莫耳至10千莫耳烯烴氧化物之工作速率進行。在一實施例中,該方法以每小時每立方公尺催化劑產生0.7千莫耳至8千莫耳烯烴氧化物之工作速率進行。在一實施例中,該方法以每小時每立方公尺催化劑產生例如5千莫耳烯烴氧化物之工作速率進行。如本文所使用,工作速率為每小時每單位體積催化劑產生之烯烴氧化物的量,且選擇性為相對於轉化之烯烴的莫耳量形成之烯烴氧化物的莫耳量。
可藉由使用此項技術中已知之方法由反應混合物中回收產生之烯烴氧化物,例如藉由將得自反應器出口流之烯烴氧化物吸收於水中,且視情況藉由蒸餾由水性溶液中回收烯烴氧化物。含烯烴氧化物之水性溶液的至少一部分可用於後續製程中以將烯烴氧化物轉化成1,2-二醇或1,2-二醇醚。
環氧化製程中產生之烯烴氧化物可藉由習知之方法轉化成1,2-二醇、1,2-二醇醚、1,2-碳酸酯或烷醇胺。
轉化成1,2-二醇或1,2-二醇醚可包含例如在熱製程中或藉由使用催化劑(其可為酸性催化劑或鹼性催化劑)使環氧乙烷與水反應。舉例而言,為製備主要1,2-二醇及較少1,2-二醇醚,可在液相反應中在酸催化劑(例如以總反應混合物計0.5重量%-1.0重量%硫酸)存在下在50-70℃、100 kPa之絕對壓力下使烯烴氧化物與十倍莫耳過量之水反應,或較佳在氣相反應中在不存在催化劑下在130℃-240℃及2000 kPa-4000 kPa之絕對壓力下使烯烴氧化物與十倍莫耳過量之水反應。該大量水之存在可有利於選擇性地形成1,2-二醇且可充當反應放熱之散熱器,有助於控制反應溫度。若水之比例下降,則反應混合物中之1,2-二醇醚的比例增加。如此產生之1,2-二醇醚可為二醚、三醚、四醚或其次之醚。替代性1,2二醇醚可藉由用醇,尤其一級醇(諸如甲醇或乙醇)來轉化烯烴氧化物,藉由以醇替代至少一部分水來製備。
烯烴氧化物可藉由使其與二氧化碳反應轉化成相應1,2-碳酸酯。若需要,則可藉由隨後使1,2-碳酸酯與水或醇反應形成1,2-二醇來製備1,2-二醇。就適用之方法而言,參考US-A-6080897,其以引用的方式併入本文中。
1,2-二醇及1,2-二醇醚,例如乙二醇、1,2-丙二醇及乙二醇醚,可用於多種工業應用中,例如食品、飲料、煙草、化妝品、熱塑性聚合物、可固化樹脂系統、清潔劑、熱交換系統等領域。1,2-碳酸酯,例如碳酸乙二酯,可用作稀釋劑,尤其溶劑。乙醇胺可用於例如天然氣之處理("脫硫")中。
除非另外規定,否則本文提及之有機化合物(例如烯烴、醇、1,2-二醇、1,2-二醇醚、1,2-碳酸酯、乙醇胺及有機鹵化物)通常具有至多40個碳原子,更通常至多20個碳原子,尤其至多10個碳原子,更尤其至多6個碳原子。如本文所定義,碳原子數目(亦即碳數)及其他參數之範圍包括對於該等範圍之界限所指定之數目。
環氧化方法、錸回收方法及摻雜物沈積方法可在任何合適之反應器中執行。合適之反應器包括例如一或多個微通道反應器、殼管式熱交換反應器、攪拌槽反應器、氣泡塔或冷凝裝置。本發明涵蓋該等反應器或冷凝裝置之用途,或複數個反應器或冷凝裝置於該等方法中之用途。
有利的反應器包括例如殼管式熱交換器形式之反應器及微通道反應器。在一實施例中,於殼管式熱交換反應器之反應管中執行該(等)方法。在一實施例中,於環氧化反應器中執行該(等)方法。此態樣消除自環氧化反應器中移除環氧化催化劑的需要,且催化劑在復原後可保持於合適的位置以在由烯烴及氧產生烯烴氧化物的其他週期期間使用。
下列實例意欲說明本發明之優勢,且並不意欲不適當地限制由申請專利範圍所定義之本發明之範疇。
下列程序係用於洗滌用過環氧化催化劑以產生經洗滌之用過環氧化催化劑。若用過環氧化催化劑包含錸,則洗滌物可用作包含錸之水性萃取物。未經洗滌或經洗滌之用過環氧化催化劑亦適合用作沈積由供體用過環氧化催化劑中回收之錸的受體。
將140 g用過環氧化催化劑添加至硝酸銨溶液中。將溫度升高至85℃並保持於85±5℃下達1小時。將受體用過環氧化催化劑之顆粒傾析且在250℃下於流動空氣中乾燥15分鐘。將顆粒添加至一份新鮮硝酸銨溶液中且在87.5℃(±5℃)下加熱1小時。傾析硝酸銨溶液,且於室溫下將顆粒浸泡於另一份新鮮硝酸銨溶液中。再次重複室溫處理。最後,在250℃下乾燥顆粒15分鐘。此程序自各別用過環氧化催化劑中移除大部分可溶摻雜物且產生經洗滌之用過環氧化催化劑。
製備原料銀浸漬溶液。在5公升不銹鋼燒杯中,將415公克試劑級氫氧化鈉溶解於2340 ml去離子水中。將溶液溫度調節至50℃。在4公升不銹鋼燒杯中,將1699公克硝酸銀溶解於2100 ml去離子水中。將溶液溫度調節至50℃。在攪拌下將氫氧化鈉溶液緩慢添加至硝酸銀溶液中,同時維持溫度於50℃。將所得漿液攪拌15分鐘。視需要藉由添加NaOH溶液保持溶液pH值於10以上。使用液體移除程序,其包括藉由使用過濾棒移除液體,隨後用等體積之去離子水替代移除之液體。重複此液體移除程序,直至濾液之傳導率降低至90微姆歐/公分。在完成最後一次液體移除循環後,添加1500 ml去離子水且隨後以100公克之增量添加630公克二水合草酸(4.997莫耳),同時攪拌且保持溶液於40℃(±5℃)下。在添加最後130公克二水合草酸期間監控溶液之pH值以確保該pH值長時間不降低至7.8以下。將水用過濾棒自溶液中移除且將漿液冷卻至30℃以下。將732公克92重量%乙二胺(EDA)緩慢添加至溶液中。在此添加期間保持溫度於30℃以下。使用刮刀手動攪拌混合物直至出現足夠的液體以機械攪拌混合物。
實例3及4中使用已使用一年以上之供體用過環氧化催化劑。供體用過環氧化催化劑之累積環氧烷產量為每立方公尺用過環氧化催化劑0.16 kT或更多。用定量之水煮沸定量之供體用過環氧化催化劑且將錸耗乏之供體自水性萃取物中分離。分析萃取物且以回收之錸與用過環氧化催化劑上最初存在之錸總量的比率來計算錸濃度及回收率。
在第一程序中,於100 g等分水中煮沸100 g供體用過環氧化催化劑。將100 g催化劑(含27.9 mg Re)置放於燒杯中且添加100 g去離子水。將水煮沸且使沸騰持續5分鐘。接著使燒杯冷卻至50℃-60℃且將液體自催化劑顆粒中傾析。此程序共重複3次。數據呈現於下表中:
三次用水萃取得到大於99%之錸回收率。
在第二程序中,將100 g實例3之催化劑(含27.9 mg Re)置放於燒杯中且添加200 g之去離子水。將水煮沸且使沸騰持續5分鐘。接著使燒杯冷卻至50℃-60℃且將液體自催化劑顆粒中傾析。分析水性萃取物且以回收之錸與用過環氧化催化劑上最初存在之錸總量的比率來計算錸濃度及回收率。
數據呈現於下表中:
使用較大量之水萃取產生較高之回收率,但產生較稀之萃取物溶液。
將實例3之水性萃取物蒸發且用氫氧化銨溶液處理以產生包含於2 g 25%氫氧化銨中之0.02 g NH4
ReO4
的錸沈積混合物。
用於復原用過環氧化催化劑之組合之沈積混合物係藉由混合錸沈積混合物與下列各物來製備:150公克比重為1.6 g/cc之銀原料溶液;0.06 g溶解於2 g 1:1氨/水中之偏鎢酸銨;及0.2 g溶解於水中之LiOHxH2
O。添加額外的水以將溶液比重調節為1.5 g/cc。將50公克所得溶液與0.2 g 50重量%之CsOH溶液混合以產生組合之沈積混合物。
使兩種受體用過環氧化催化劑之顆粒經受復原方法。受體用過環氧化催化劑之累積環氧烷產量為每立方公尺用過環氧化催化劑0.16 kT或更多。
用過環氧化催化劑中之一者(催化劑A)包含與銀、鋰及銫摻雜之α-氧化鋁。另一用過環氧化催化劑(催化劑B)包含與銀、錸、鎢、銫及鋰摻雜之α-氧化鋁。如藉由硝酸消化及銀滴度所測定,用過催化劑A之銀含量為15%(重量%)或更少。洗滌後,用過催化劑A之經萃取之銫的含量為70。
將30公克經洗滌之用過催化劑A之顆粒抽空至20 mm Hg達1分鐘,且在真空下將實例5之組合之沈積混合物添加至顆粒中。釋放真空且使所得之用過催化劑A的抽空顆粒與組合之沈積混合物接觸3分鐘,產生中間體催化劑A。接著以500 rpm將中間體催化劑A之顆粒離心2分鐘以移除過量之液體。將所得之中間體催化劑A的離心顆粒置放於振動震盪器中且於流動空氣中乾燥以產生復原之催化劑A。
測定復原之催化劑A顆粒之最終組成。復原之催化劑A顆粒包含以復原之催化劑A之總重量計大於20重量%之Ag,及每公克復原之催化劑大於600 ppm經萃取之Cs。如上所述測定復原之催化劑A顆粒中之銀及經萃取之銫的含量。復原之催化劑A顆粒亦包含較用過催化劑A增加之量的錸、鎢及鋰。
測試多種催化劑以測定其催化性質,諸如選擇性及活性。
以下實例中使用下列測試程序。將催化劑粉碎至14至20目尺寸。將3 g至5 g經粉碎之催化劑負載入1/4吋之不銹鋼U形管中。將管浸沒於熔融金屬浴(加熱介質)中,且將末端與氣流系統連接。調節所用之催化劑重量及入口氣流速率以得到如對未經粉碎之催化劑計算之以標準公升/公升/小時(N1/1/h)計的指定氣體每小時空間速度。隨著催化劑填充密度及銀負荷的改變,測試反應器中所負載之催化劑的量改變。
使用如上所述之測試程序對經復原以產生復原之催化劑A的用過環氧化催化劑測試其由含乙烯及氧之饋料產生環氧乙烷的能力。如對未經粉碎之催化劑所計算,氣體每小時空間速度為3300標準公升/公升/小時(N1/1/h)。催化劑負荷係5公克以下。氣流為17 N1/1/h。入口氣壓為1550 kPa。結果於預言性實例8中給出。
使用上述測試程序使測試氣體混合物穿過催化劑床。測試氣體混合物為30體積%之乙烯、8體積%氧氣、5體積%二氧化碳、57體積%氮氣及2.5百萬分之體積份(ppmv)氯乙烷。使溫度於245℃下保持恆定達4小時,且接著對催化劑加以調節以穩定且達成以測試氣體總體積計3.1體積%之環氧乙烷(EO)產量。催化劑負荷為4公克。氣流為17 N1/1/h。入口氣壓為1550 kPa。用過催化劑A與復原之催化劑A之活性℃(activity℃)大體上相同。復原之催化劑A之選擇性比用過催化劑A之選擇性高12%。
將實例3之水性萃取物蒸發且用氫氧化銨溶液處理以產生包含於2 g 25%氫氧化銨中之僅0.05 g以下NH4
ReO4
的錸沈積混合物。
用於製備新鮮環氧化催化劑之組合之沈積混合物係藉由混合錸沈積混合物與下列各物來製備:50.0公克比重為1.6 g/cc之銀原料溶液;0.01 g溶解於1 g 1:1氨/水中之偏鎢酸銨;及0.05 g溶解於水中之LiOH×H2
O。添加額外的水以將溶液比重調節為1.5 g/cc。將50.0公克所得溶液與0.1 g 50重量%之CsOH溶液混合以產生用於製備新鮮環氧化催化劑之組合之沈積混合物。
本實施例中所使用之新鮮載體的吸水性為50 cc/100 g。將30公克α氧化鋁顆粒抽空至20 mm Hg達1分鐘,且在真空下將實例9之組合之沈積混合物添加至顆粒中。接著釋放真空且使所得之α氧化鋁的抽空顆粒與組合之沈積混合物接觸3分鐘,產生中間體新鮮環氧化催化劑。接著以500 rpm將中間體新鮮環氧化催化劑之顆粒離心2分鐘以移除過量之液體。將所得之中間體新鮮環氧化催化劑的離心顆粒置放於振動震盪器中且於流動空氣中乾燥,產生新鮮環氧化催化劑。
測定新鮮環氧化催化劑之最終組成。新鮮環氧化催化劑包含以新鮮環氧化催化劑之總重量計18重量%之Ag。新鮮環氧化催化劑亦產生每公克新鮮環氧化催化劑超過500 ppm經萃取之Cs。如上所述測定新鮮環氧化催化劑之銀及經萃取之銫的含量。新鮮環氧化催化劑亦包含有效量之錸、鎢及鋰。
使用如上所述之測試程序對預言性實例10中製備之新鮮環氧化催化劑測試其由含乙烯及氧之饋料產生環氧乙烷的能力。新鮮環氧化催化劑展示在250℃之溫度下85%或更高之選擇性。
一般熟習此項技術者應認識到可對前述描述進行多種修改。本文所述之實施例僅意謂進行說明且不應將其理解為限制本發明,本發明將於申請專利範圍中加以定義。
Claims (36)
- 一種由供體用過環氧化催化劑中再利用錸之方法,該方法包含:提供一包含包括錸之用過環氧化催化劑的供體,該供體之累積環氧烷產量為每立方公尺該用過環氧化催化劑0.16 kT或更多;使該供體與水性液體接觸以產生錸耗乏之供體及包含經萃取之錸之水性萃取物;分離該水性萃取物與該錸耗乏之供體;及使用該經萃取之錸作為後續製程中之錸之一來源。
- 如請求項1之方法,其進一步包含自該水性萃取物中分離該經萃取之錸以產生回收之錸。
- 如請求項2之方法,其包含藉由一選自由昇華、蒸餾、濃縮及其組合組成之群的程序自該水性萃取物中移除稀釋劑。
- 如請求項2之方法,其包含使該水性萃取物穿過一樹脂床,且由該樹脂床中收集該回收之錸。
- 如請求項1之方法,其進一步包含沈積該經萃取之錸於一受體上以形成環氧化催化劑或環氧化催化劑前驅體。
- 如請求項5之方法,其包含使該受體與包含該水性萃取物之沈積混合物接觸。
- 如請求項2或3之方法,其包含沈積該回收之錸於一受體上以形成環氧化催化劑或環氧化催化劑前驅體。
- 如請求項5或6之方法,其中該受體包含用於製備復原之 環氧化催化劑之用過環氧化催化劑。
- 如請求項1至6中任一項之方法,其中該供體之累積環氧烷產量為每立方公尺該用過環氧化催化劑0.2 kT或更多。
- 如請求項9之方法,其中該供體之累積環氧烷產量為每立方公尺該用過環氧化催化劑0.3 kT或更多。
- 如請求項9之方法,其中該供體之累積環氧烷產量為每立方公尺該用過環氧化催化劑0.45 kT或更多。
- 如請求項9之方法,其中該供體之累積環氧烷產量為每立方公尺該用過環氧化催化劑0.7 kT或更多。
- 如請求項9之方法,其中該供體之累積環氧烷產量為每立方公尺該用過環氧化催化劑1 kT或更多。
- 如請求項1至6中任一項之方法,其中該水性液體係選自由下列各物組成之群:水;包含一或多種選自鹽、酸、鹼及過氧化物之添加劑的水性液體;水性有機稀釋劑;及其混合物。
- 如請求項1至6中任一項之方法,其中該水性液體係由水組成。
- 如請求項8之方法,其進一步包含沈積以該受體用過環氧化催化劑之重量計0.2重量%或更多量之銀。
- 如請求項16之方法,其進一步包含沈積以該受體用過環 氧化催化劑之重量計0.5重量%或更多量之銀。
- 如請求項16之方法,其進一步包含沈積以該受體用過環氧化催化劑之重量計1重量%或更多量之銀。
- 如請求項16之方法,其進一步包含沈積以該受體用過環氧化催化劑之重量計5重量%或更多量之銀。
- 如請求項16之方法,其進一步包含沈積以該受體用過環氧化催化劑之重量計10重量%或更多量之銀。
- 如請求項16之方法,其進一步包含沈積以該受體用過環氧化催化劑之重量計12重量%或更多量之銀。
- 如請求項5或6之方法,其中該受體包含用於製備新鮮環氧化催化劑之載體物質。
- 如請求項22之方法,其進一步包含沈積以該新鮮環氧化催化劑之重量計10 g/kg或更多量之銀於該受體上。
- 如請求項1至6中任一項之方法,其包含在由該供體萃取錸之第一部分的第一萃取條件下使一定重量之該供體與該水性液體之第一等分試樣接觸,產生第一萃取之供體及包含第一量之經萃取之錸的第一水性萃取物;及在產生一或多種包含一或多個額外量之經萃取之錸的額外水性萃取物的另一萃取條件下使該第一萃取之供體與該水性液體之一或多個等分試樣接觸。
- 如請求項24之方法,其中該第一等分試樣及該一或多個等分試樣包含與該供體之重量大體上相同重量之該水性液體。
- 如請求項1至6中任一項之方法,其中經萃取之錸之總量以該供體上最初存在之錸的總量計為75重量%或更多,尤其85重量%或更多。
- 如請求項5或6之方法,其進一步包含沈積一定量之一或多種選自由下列各物組成之群的復原錸共促進劑組份:鎢、鉻、鉬、硫、磷、硼及其混合物。
- 如請求項22之方法,其進一步包含沈積一定量之一或多種選自由下列各物組成之群的錸共促進劑組份:鎢、鉻、鉬、硫、磷、硼及其混合物。
- 如請求項5或6之方法,其進一步包含於該受體上沈積一定量之一或多種選自由下列各元素組成之群的其他復原元素:氮、氟、鹼金屬、鹼土金屬、鈦、鉿、鋯、釩、鉈、釷、鉭、鈮、鎵、鍺及其混合物。
- 如請求項22之方法,其進一步包含於該受體上沈積一定量之一或多種選自由下列各元素組成之群的其他元素:氮、氟、鹼金屬、鹼土金屬、鈦、鉿、鋯、釩、鉈、釷、鉭、鈮、鎵、鍺及其混合物。
- 如請求項5或6之方法,其進一步包含於該受體上沈積一定量之一或多種選自由下列各物組成之群的復原鹼金屬:鋰、鉀、銫及其混合物。
- 如請求項22之方法,其進一步包含於該受體上沈積一定量之一或多種選自由下列各物組成之群的鹼金屬:鋰、鉀、銫及其混合物。
- 如請求項5或6之方法,其進一步包含在沈積該量之錸於 該受體上之前洗滌該受體。
- 一種使一或多種烯烴環氧化之方法,其包含使包含一或多種烯烴之饋料在如請求項5至33之任一項之方法所製備的環氧化催化劑的存在下反應。
- 如請求項34之方法,其中該一或多種烯烴包含乙烯。
- 一種產生1,2-二醇、1,2-二醇醚、1,2-碳酸酯或烷醇胺的方法,該方法包含將烯烴氧化物轉化為該1,2-二醇、該1,2-二醇醚、該1,2-碳酸酯或該烷醇胺,其中該烯烴氧化物已藉由如請求項25或26之使烯烴環氧化之方法獲得。
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TW95147800A TW200744749A (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 |
TW95147795A TW200744748A (en) | 2005-12-22 | 2006-12-20 | A method of installing an epoxidation catalyst in a reactor, 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 |
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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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