TWI309582B - Mesoporous material and use thereof for the selective oxidation of organic compounds - Google Patents

Mesoporous material and use thereof for the selective oxidation of organic compounds Download PDF

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TWI309582B
TWI309582B TW092125646A TW92125646A TWI309582B TW I309582 B TWI309582 B TW I309582B TW 092125646 A TW092125646 A TW 092125646A TW 92125646 A TW92125646 A TW 92125646A TW I309582 B TWI309582 B TW I309582B
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Taiwan
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metal
transition metal
compound
group
catalyst
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TW092125646A
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TW200409672A (en
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Thomas Maschmeyer
Zhiping Shan
Jacobus Cornelis Jansen
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Abb Lummus Global Inc
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    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

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1309582 (1) 玖、發明說明 【發明所屬之技術領域】 本發明關於一種中孔材料，特別是催化材料，及中孔 材料用於有機化合物（特別是烴類）之選擇性氧化的用 途0 【先前技術】 已知多種方法及催化劑用於有機化合物之選擇性氧化 作用上。例如 ’ USP 5 94 8 683 ( Koermer et al.)揭示—種 用於在一氧化碳存在下未飽和烴類之選擇性氧化作用的催 化性材料。該催化性材料包括磷酸化氧化鈽，藉由混合氧 化鈽顆粒與磷酸鹽之溶液，然後將自溶液分離出之顆粒鍛 燒而製得。 USP 5811599 (Alive et al.)揭示一種在鈦矽酸鹽催 化劑存在下使用過氧化氫水溶液氧化烴類的方法。 USP 5 7 07 9 1 7 ( Geus et al.)揭示一種用於將烴類選 擇性氧化之催化劑，其包括將以一或多種金屬氧化物及 釩-磷氧化物爲主之載體分散於載體表面上。該方法包括 氧化及還原相。烴類與催化劑在還原相接觸及以氧化及未 氧化形式吸附至催化劑上。經負載之催化劑然後饋至氧化 相，其中在氣態氧之存在下形成所需產物’隨後將之分 離。 對於烴類及其他有機化合物之選擇性氧化上仍然需要 一改良方法及催化劑。 -5- 1309582 (2) 【發明內容】 此處所提供之材料包括基於微孔及中孔計具有至少 9 7體積°/。中孔之非晶型多孔無機氧化物，及至少一種選自 一或多種過渡金屬及一或多種貴金屬之催化活性金屬。此 處亦提供一種製造該材料之方法及該材料作爲有機化合物 之選擇性氧化作用之催化劑的用途。 此處所提供之方法及催化劑係用於具有高選擇性之烴 類或其他有機化合物之選擇性氧化作用。 【實施方式】 本發明催化劑包括結構上實質爲中孔之三維、穩定、 多孔無機氧化物材料。該材料具有非晶型但規則化（擬晶 型）結構。中孔材料述於U SP 6 3 5 8 4 8 6 B 1，其全文倂入 本文爲參考資料。催化劑進一步包括一或多種貴金屬及/ 或一或多種過渡金屬。 本發明非晶型無機氧化物材料通常包括中孔及微孔。 微孔定義爲具有直徑小於約2 nm之孔洞。中孔定義爲具 有直徑約2 n m至約5 0 n m之孔洞。本案無機氧化物材料 具有中孔至少約9 7體積％，較佳至少約9 8體積％。 一種製備較佳孔洞之包含二氧化矽的催化劑載體之方 法述於 USP 6358486 B1。較佳催化劑之平均中孔尺寸以 Nz-孔率計測量爲約2 nm至約25 nm。通常，中孔無機氧 化物之製備如下：加熱（1 )於水中之無機氧化物前驅 1309582 (3) 物，及（2 )有機誘導劑之混合物，使有機誘導劑與氧化 物前驅物或自前驅物產生之氧化物物種充分混合，及較佳 在其上形成氫鍵。 起始物質通常爲非晶型材料，及由一或多種無機氧化 物（如氧化矽或氧化鋁）與額外金屬氧化物或無額外金屬 氧化物所組成。矽或鋁原子可被如下催化活性過渡金屬原 子替代，如鈦、釩、銅、锆、錳、鋅、鉻、鉬、鎢、鎳、 鈷、鐵等。過渡金屬之重量組成較佳高至約6 0 %，更佳約 0 · 00 1 %至約20%，基於催化劑之總重計。額外金屬在開始 製備包含中孔結構之製程前可視情況加入。例如，可製備 包含過渡金屬烷氧化物、矽或鋁烷氧化物（如原矽酸四乙 酯“ TEOS”，或三異丙氧基鋁）及有機誘導劑之均勻合成 混合物。然後將合成混合物老化、乾燥、及鍛燒至產生中 孔結構。合成混合物之乾燥可以如下方式進行：加熱合成 混合物至乾燥溫度約50°C至約150°C (較佳60°C至約120 °C ) 一足夠時間以移除水及/或揮發有機液體。經乾燥混 合物之鍛燒可以如下方式進行：加熱經乾燥混合物至鍛燒 溫度約3 0 0 °C至約1 〇 0 0 °C (較，基約4 0 0 °c至約7 0 0 °c )— 足夠時間以形成中孔結構。鍛燒時間典型爲約2小時至約 4 0小時，至少部分視鍛燒溫度而定。加熱移除水及/或 揮發有機化合物之後及鍛燒之前，有一選擇性步驟：將經 乾燥混合物在容器中於溫度約1 30°c至約200°c下加熱約 2小時至約9 6小時。此步驟可用於操控最終組成物之中 孔尺寸、表面積及孔洞體積。 -7- (4) 1309582 並且’製備材料後，在系統中之陽離子可視情況被其 他離子取代’如鹼金屬（例如鈉、鉀、鋰等）。 形成中孔之有機誘導劑較佳爲多元醇（g 1 y c 〇 1 )(包 括二或多個羥基之化合物），如丙三醇、二甘醇、三甘 醇、四甘醇、丙三醇等，或者由三乙醇胺、硕戊環、四伸 乙基五胺、及二甘醇二苯甲酸酯。較佳地，誘導劑具有沸 點至少約1 5 0°c。 中孔催化劑載體爲擬晶型材料（即以現今X射線繞 射技術沒有觀察到結晶）。中孔壁厚較佳約3 nm至約2 5 nm。由BET (N2)測得之催化劑載體表面積較佳約400 m2/g至約1 200 m2/g。催化劑孔洞體積較佳約0.3 cm3/g 主約 2.2 c πι 3 / g。 &混合期間，適當選取之活性金屬與誘導劑（如三乙 醇胺、或 “TEA”）形成錯合物。將錯合物以及作爲形成 中孔誘導劑之自由有機化合物（如TEA )乾燥。之後，在 1 段'燒期間’錯合物被分解，及將任何有機物種移除。則過 # ®均勻地塗覆於中孔之內表面。視過渡金屬之負載而 & ’ $些過渡金屬之配位狀態可加以控制。大部分活性位 址係兹@ ^ _ $易進入的，因爲活性位址多位於中孔表面。另外， S 維 Φ 21 系統亦可促進粒子內之質傳。 t ^不含過渡金屬之無機氧化物載體可進一步倂入催 化性有％ Ώ #量之一或多種貴金屬以加以改良，該貴金屬如金 (Αιι ) Λ '銀（Ag )、鉑（Pt )、鈀（Pd )、銥（Ir )、铑 (Rh ), '釕（Ru )、銶（Re )、或餓（Os )。這些貴金 -8- 1309582 (5) 屬可形成具有1 0 n m或更小直徑之中孔的奈米尺寸顆粒。 貴金屬之重量百分比基於催化劑總重計可高至約60%，較 佳約0.1 %至約4 0 %。 可用任何適當方法將貴金屬倂入無機中孔氧化物，如 离隹子交換或者以可溶、可分解之貴金屬化合物的溶液浸 胃’然後加以淸洗、乾燥，及使經浸漬無機氧化物進行如 锻燒之處理以分解貴金屬化合物，因而製得在無機氧化物 孔洞中具有自由貴金屬之經活化催化劑。適當貴金屬化合 物包括如硝酸鹽、氯化物、銨錯合物等。 經貴金屬浸漬之無機氧化物催化劑的淸洗係視情況以 水進行以移除一些陰離子。將催化劑乾燥以移除水及/或 其他揮發性化合物可藉由將催化劑加熱至乾燥溫度約5 0 °c至約1 9 0 °C而完成。锻燒至活化催化劑可在約1 5 0 t至 約6 0 〇°C溫度下進行一足夠時間而達成。通常，鍛燒可進 行2至40小時，至少部分視鍛燒溫度而定。 所得催化劑可用於述於下之選擇性氧化方法： A)烯烴之環氧化以製得環氧化物。適當烯烴包括C 2 至C 2 〇不飽和烴化合物，如乙烯、丙烯、丁烯（1 - 丁烯、 2 -丁烯、異丁烯）、丁二烯 '戊烯、直鏈或支鏈己烯、；u 辛烯、環己烯等。氧化劑包括氧、含氧氣體、過氧化氫 (H2〇2 )、氮氧化物、有機氫過氧化物、有機過酸等。環 氧化作用典型在溫度約30°C至約30(TC (較佳5(TC至約 2 5 0 °C )、壓力約1大氣壓至約4 〇巴、及空間速度約1 〇 WHSV至約2000 WHSV下進行。反應在氣相、液相或混 1309582 (6) 合（氣體/液體）相中進行。 B) 烷類之部分氧化以製得酮或醇衍生物。適當烷類 包括丙院、丁院、戊院、環己院等。適當氧化劑包括氧、 含氧氣體、過氧化氫（H202 )、氮氧化物、有機氫過氧化 物、及有機過酸。烷類之部分氧化至酮典型地在溫度約0 °C至約2 0 0 °c、壓力約1巴至約3 0巴、及空間W H S V速 度約100 hr·1至約1 00,000 hr·1下進行。醇之產生通常在 溫度約60 °C至約450 °C及壓力高至約60巴下進行。反應 可在氣相、液相或混合相中進行。 C) 醇之部分氧化。適當醇包括，例如，苄醇.、苯乙 醇、苯酚、及肉桂醇。適當氧化劑包括氧、含氧氣體、過 氧化氫、氮氧化物、有機氫過氧化物、及有機過酸。例 如，苯甲醛可藉由使用此處所揭示包含例如銅之催化劑在 約3 0 0 °C至約5 0 0 °C及壓力高至約2 0巴下部分氧化苄醇而 製得。 D) 將羥基加至芳族環結構之芳族化合物的羥基化作 用。該芳族化合物較佳包括苯及甲苯，雖然亦可使用其他 芳族化合物。適當氧化劑包括氧、含氧氣體、過氧化氮、 氮氧化物 '有機氫過氧化物、及有機過酸。苯氧化成苯酚 及甲苯氧化成甲酚可在溫度2 5 °C至5 0 0 °C及壓力高至6 5 巴下進行。該方法亦可在蒸餾塔反應器於溫度範圍高於 1 0 0 °C至2 7 0 °C及苯分壓約〇 · 1 at m至約4 5 at m下進行。 E) 用氨（NH3)及過氧化氫或氧化氮進行酮之肟化 作用（a m m ο X i m a t i ο η )以產生脂。適當之酮包括’例如， -10 - 1309582 (7) 丙酮、甲基乙基酮（MEK)、苯乙酮、環己酮、環十二烷 酮等。反應條件典型包括溫度約2 5 t至約丨5 〇它（較佳 4 〇 °C至約12 0 °C ) ’及壓力約！至i 〇大氣壓（較佳1至5 大氣壓）。 本發明之不同特徵以下列實例說明之。使用裝有石璺 單色光鏡之P h i 1 i p s p W 1 8 4 0繞射儀之C u κ α輻射記錄X 射線粉末繞射圖。樣品在0 · 5 - 4 〇。之2 Θ範圍以0.0 2 °階度 掃描之。使用裝有LaB6纖絲爲電子來源之philips CM30T電子顯微鏡在3 00 kV操作以進行透射式電子顯微 照相（TEM)。用 Quantachrome Autosorb-6B 在 77 K 下 測量氮吸收等溫線。使用B H J模型計算中孔度。除非另 外說明 > 所有組成份數以重量計。 實例1 用下文所述製程製備及測量本發明包含鈦之催化劑。 首先，將1.1份正丁氧基鈦（！[V)與35.0份原矽酸四乙 酯（“TEOS”）混合。然後，將 25.3 份三乙醇胺 (“TEA”）加至上述混合物，同時加以攪拌。攪拌1小時 後，將2 1 . 3份去離子水逐滴加至上述混合物’同時加以 攪拌。攪拌另一小時後，將1 7.3份氫氧化四乙基銨 (“TEA OH”）（ 25% )逐滴加至上述混合物。最終均勻混 合物在室溫下老化24小時，在1 〇〇°C乾燥24小時，然後 在700t：於空氣中以1°C miiT1之速率鍛燒1〇小時。 所得材料之X R D圖示於圖1 a，該圖顯不角度2 θ於約 -11 - 1309582 (8) 1 . 〇 °下僅在〇 . 5。及2 · 5 °間出現強譜峰，此表示該產物爲 中孔結構材料。圖1 B爲所得材料之TEM圖。圖1 B顯示 彎曲且迂迴曲折之孔洞不規則相連而形成三維孔洞網絡。 用氮吸收測量所得材料之BET表面積爲約9 1 7 m2/g。從 圖2知所得材料之平均中孔直徑爲4 · 5 nm，及總孔洞體積 爲約 〇 . 8 9 c m3 / g。
接著，使用第三丁基氫過氧化物爲氧化劑在4 0 X：於 N2中進行環己烁環氧化的反應以顯示催化活|性。反應混 合物由1份催化劑、9 · 6份環己烯（9 9 %，使用前用無水 MgS〇4乾燥之）及13.2份二氯甲烷（99% )組成。用氣相 層析（WAX 52 CB )分析樣品。6小時後’約45.6%環己 烯被轉變，選擇率幾乎爲1 00%。總頻率（定義爲每小時 每莫耳鈦中環己烯之轉變莫耳數）爲20.2 1Γ1。 比較例A 所用含鈦催化劑並非根據本發明，而係根據述於先前 記載（L.Y. Chen, G.K. Chuah，S. Jaenicke, Catal. Lett. 50 (1988) 107.)加以合成，以Ti-MCM-41表示。其具有 BET表面積爲934 m2/g及平均孔洞直徑爲約3.3 nm。在 與實例1相同條件下試驗，顯示總頻率僅爲3.6 1Γ1，此表 示所得環己烯轉變率比由實例1催化劑所得環己烯轉變率 低 2 0%。 實例2 -12- 1309582 Ο) 將金之奈米尺寸顆粒加至實例1所製 由將 0.34重量份 HAuC14· 4H20加至 AuC14_水溶液。將之加熱至70t，及藉由 液將其pH調整至約7.0。然後將2份實 於上述溶液中，再將pH調整至7.0。懸i 化1小時，用蒸餾水淸洗3次，在100 °C 及最後在3 0 0 °C下鍛燒4小時。 丙烯之蒸氣相環氧化成氧化丙烯係在 直固定床石英反應器中進行。反應物進料 %之 C3H6、H2及 02於.Ar中，氣相ί (GHSV )爲 1 000 0 h—1 ml g·1 (催化劑） 在1 2 0 °C。進料及產物用線上氣相層析 3 · 5 %丙烯轉變成氧化丙烯，選擇率約9 6 % 實例3 根據如下所述U S P 6,3 5 8,4 8 6實例1 料： 首先，將1 . 3重量份異丙氧基鋁溶於 四丙基鋁（4〇% )水溶液中。接著，將 (9 7 % )及1 4.0份水混合。將τ E A水性 1 0 g / m i η )加至含銘混合物，並同時攪伴 份 TEOS(98%)逐滴（4-6 g/min)加至 同時攪拌。最終混合物在室溫下老化4 覆於一盤上以形成高度ι·〇-ΐ·2公分之一 備之催化劑。藉 4 0 0份水中製得 加入N a Ο Η水溶 例1催化劑懸浮 字液在70°C下老 下乾燥2小時， 塡充催化劑之垂 包含各10體積 S小時空間速度 。反應溫度維持 (GC )分析。約 製程合成含矽材 3 9 . 1份氫氧化 4 7.8 8 份 TEA 混合物逐滴（8 · 。最後，將3 3 . 1 所得混合物，並 8小時·，將之塗 層，及在靜態空 -13- 1309582 (10) 氣爐中於1 00°C下乾燥1 8小時。所得材料在空氣中使用 如下所述步驟鍛燒：以加熱速率1 °c /min將材料加熱至 5〇〇 c ’然後靜止4小時，然後以加熱速率11 /min加熱 至5 5 0 °C，之後’靜止1 0小時。 所得材料用如下方式製備含銀催化劑：藉由浸漬至 A gN Ο 3水溶液材料中。浸漬後，材料在2 5 〇乞下鍛燒4小 時。經浸漬催化劑用ICP分析及顯示約3〇·5%之銀含量。 含銀催化劑維持在一大氣壓22〇 °c下之微流反應器 中。反應物流包含20體積％乙烯、40體積％氧:及40體積 %氮。總反應物流之GHSV爲4,5 00 h〆1。用氣體層析分 析產物。在1小時內，乙烯之轉變率達丨9.8 %，至環氧乙 院之選擇率爲約2 9 %。 實例4
1 · 7份正丁氧基鈦（IV ) (99%)與 1 〇 6份 Τ Ε Ο S (98% )混合。然後將77份TEA ( 97% )與58份去離子 水之混合物逐滴加至上述混合物中，並同時攪拌。約攪拌 1小時後’將63份TEAOH ( 25% )逐滴加至混合物。合 成混合物中S i / Ti莫耳比爲丨〇 〇。最終均勻混合物在室溫 下老化2 4小時=在9 8 °C下乾燥2 4小時，然後在6 5 0。(：下 方< 空熟中以1 C / m i η速率锻燒1 〇小時。所得材料X r d .圖 示於圖3。 實例5 -14- 1309582 (11) 除了使用3.4重量份正丁氧基鈦（I v )及混合物中 s i / τ i比爲5 0外’進行與實例4相同之製程。所得材料 XRD圖示於圖3。 實例6 除了使用8.6重量份正丁氧基鈦（iv )及混合物中 s i / T i比爲2 0外’進行與實例4相同之製程。所得材料 XRD圖示於圖3。 實例7 除了使用I?.2重里份正丁氧基欽（IV)及混合物中 s i / T i比爲]〇外’進行與實例4相同之製程。所得材料 XRD圖示於圖3。 從實例4 -7可看出’將適當量欽化合物加至起始合成 混合物中可輕易控制本發明催化劑材料中鈦負載。實例 4 -7中所得材料之X RD圖顯示這些材料爲中孔的。 實例8 首先，將1 .2重量份乙醯基醋酮酸鉻（III )與34.5 份TEOS ( 98% )混合。然後，將25份TEA ( 97% )逐滴 加至上述混合物，並同時攪拌。攪拌1小時後，將1 8.8 份去離子水逐滴加至上述混合物，並同時攪拌。另攪拌I 小時後’將2 0 · 5份氫氧化四乙基銨（2 5 % )逐滴加至上述 混合物。最終均勻混合物在室溫下老化2 4小時，在1 0 〇 1309582 (12) °C下乾燥2 4小時。經乾燥凝膠在壓力鍋於1 8 01：下加熱8 小時’最後在6 5 0 °C於空氣中以1 °C m i ιΓ 1之速率鍛燒1 〇 小時。 圖4顯示此材料之XRD圖，顯示角度2Θ在約1.3。出 現強譜峰。氮吸附顯示表面積爲6 1 8 m 2 / g，孔洞體積〇 . 6 7 cm3/g及平均孔洞尺寸直徑5·5 ηιη。這些數據顯示實例8 含鉻材料在結構上爲中孔。此材料於實例1相同條件下測 試作爲環己稀環氧化作用之氧化劑。於6小時後，約4 6 % 環己烯轉變至環己烯環氧化物，選擇率約94%。 上述說明包含很多特定條件，這些特定條件不應視爲 本發明範圍之限定，而應僅視爲本發明較佳具體例之例 示。熟悉此項技藝人士可於本發明範疇及精神內想.到其他 可能的改變，如所附申請專利範圍所示。 【圖式簡單說明】 下文所述具體例參見圖式，其中： 圖1 A示實例1催化劑材料之X射線繞射圖。 圖1B示實例1催化劑材料之透射式電子顯微鏡影 像。 圖2示實例1催化劑材料之孔洞體積及孔洞大小數 據。 圖3示實例4、5、6及7催化劑材料之X射線繞射 圖。 圖4示實例8催化劑材料之X射線繞射圖’。 -16-

Claims (1)

1309582 (1) 拾、申请專利範圍 1 . 一種材料，其包含： a) 具有基於微孔及中孔計至少97體積❶/。中孔之非晶 型、多孔無機氧化物，該中孔係互相連接的’以及 b) 至少一種選自一或多種過渡金屬及一或多種貴金 屬之催化活性金屬。 2 _如申請專利範圍第1項之材料，其中該過渡金屬 係選自鈦 '釩、銅、銷、錳、鋅、鐵、鎳、鈷、鉻、鉬及 鎢。 3 .如申請專利範圍第1項之材料，其中該貴金屬係 選自金、銀、鉑、鈀、銥、铑、釕、鍊、及餓。 4.如申請專利範圍第1項之材料，其中催化活性金 屬爲金或銀。 5 ·如申請專利範圍第1項之材料，其中催化活性金 屬爲鉻。 6 .如申請專利範圍第1項之材料，其中催化活性金 屬爲鈦。 7 _如申請專利範圍第1項之材料，其中非晶型多孔 無機氧化物的X射線繞射圖具有在〇 · 5。及2 · 5。間之2 θ譜 峰。 8 ·如申請專利範圍第1項之材料，其中非晶型多孔 無機氧化物包含至少98體積％中孔。 9 ·如申請專利範圍第1項之材料，其中，中孔尺寸 範圍約2 n m至約2 5 n m。 -17- 1309582 (2) 10. 如申請專利範圍第1項之材料，其中無機氧化物 爲氧化矽。 11. 如申請專利範圍第1項之材料，其中無機氧化物 爲氧化銘。 12. 如申請專利範圍第1項之材料，其中組成物中過 渡金屬含量高至約60重量％。 1 3 .如申請專利範圍第1項之材料，其中組成物中過 渡金屬含量約0.001重量％至約20重量％。 14.如申請專利範圍第1項之材料，其中組成物中貴 金屬含量高至約60重量％。 1 5 .如申請專利範圍第1項之材料，其中組成物中貴 金屬含量約〇 .】重量％至約4 0重量％。 16. 一種製備催化劑的方法，其包括下列步驟： a )將至少一種無機氧化物來源及至少一種中孔形成 劑以及選擇性一或多種催化活性過渡金屬來源混合，形成 合成混合物； b )乾燥該合成混合物； c )將經乾燥混合物加熱至鍛燒溫度一段足夠時間， 以形成具有至少97體積％中孔之非晶型載體結構；以及 d )將至少一種催化活性貴金屬及/或過渡金屬倂入 催化劑中。 1 7 .如申請專利範圍第1 6項之方法，其中無機氧化 物係選自氧化鋁及氧化矽。 1 8 .如申請專利範圍第1 7項之方法，其中無機氧化 -18- 1309582 (3) 物來源係選自烷氧基矽及烷氧基鋁。 1 9.如申請專利範圍第1 8項之方法，其中烷氧基矽 爲原矽酸四乙酯，烷氧基鋁爲異丙氧基鋁。 2 0 .如申請專利範圍第1 6項之方法，其中藉由將包 含過渡金屬之化合物與步驟a)中無機氧化物之來源混合以 形成合成混合物，而將催化活性過渡金屬倂入催化劑中。 2 1 ·如申請專利範圍第1 6項之方法，其中在將經乾 燥合成混合物加熱至鍛燒溫度的步驟c)之後，藉由將包含 過渡金屬之化合物倂入催化劑中，而將催化活性過渡金屬 倂入催化劑中。 22.如申請專利範圍第1 6項之方法，其中過渡金屬 係运自駄、釩、銅、銷、猛、辞 '絡、鉬、鎢.、錬、鈷、 及鐵。 2 3 ·如申請專利範圍第2 〇項之方法，其中包含過渡 金屬之化合物爲鈦之烷氧化物。 24.如申請專利範圍第23項之方法，其中鈦之烷氧 化物爲正丁氧基鈦。 25_如申請專利範圍第〗6項之方法，其中將經乾燥 合成混合物加熱至鍛燒溫度包括將經乾燥合成混合物加熱 至溫度約1 2 0 °c至約2 0 0。(：約，2小時至約9 6小時。 2 6 .如申請專利範圍第1 6項之方法，其中貴金屬係 選自金、銀、鉑、鈀、銥、鍺、釕、鍊' 及餓。 21 如申請專利範圍第1 6項之方法，其中將至少一 種催化活性貴金屬或過渡金屬倂入催化劑中之步驟d)係 -19 - 1309582 (4) 包括以貴金屬及/或過渡金屬之可溶、可分解化合物的溶 液浸漬非晶型載體結構，之後，使貴金屬化合物及/或過 渡金屬化合物分解。 2 8.如申請專利範圍第2 7項之方法’其中使貴金屬 化合物及/或過渡金屬化合物分解的步驟包括在足夠使貴 金屬化合物及/或過渡金屬化合物分解之溫度下鍛燒經貴 金屬及/或過渡金屬浸漬之非晶型載體。 2 9 如申請專利範圍第2 8項之方法，其中使貴金屬 是金或銀。 30·如申請專利範圍第1 6項之方法，其中中孔形成 劑係選自丙三醇、二甘醇、三甘醇、四甘醇、丙二醇、三 乙醇胺、硯戊環、四伸乙基五胺、及二甘醇二苯甲酸酯。 3 1 ·如申請專利範圍第1 6項之方法，其中將至少一 種催化活性貴金屬及/或過渡金屬倂入之步驟d)係包括 將催化活性貴金屬及過渡金屬倂入催化劑。 3 2. —種將有機化合物選性氧化之方法，其包括： 在部分氧化反應條件下，於包含以中孔及微孔計至少 9 7體積％之非晶型多孔無機氧化物以及至少—種選自一或 多種過渡金屬及一或多種貴金屬的催化活性金屬的催化劑 存在下，使有機化合物與氧化劑接觸。 3 3 .如申請專利範圍第3 2項之方法，其中有機化合 物爲烯烴，選擇性氧化方法包括將烯烴環氧化以產生對應 環氧化物。 3 4 ·如申請專利範圍第3 3項之方法，其中烯烴係選 -20- 1309582 (5) 自乙嫌、丙稀、1-丁烯、2-丁烯、異丁烯、丁二烯、戊 燒、己稀、1-辛嫌、及環己烯，氧化劑係選自氧、含氧氣 體、過氧化氫、氮氧化物、有機氫過氧化物、及有機過 酸’反應條件包括溫度約5〇t：至約25〇t，壓力約1大氣 壓至約60巴，及空間速度約1〇 WHSV至約2000 WHSV。 3 5 .如申請專利範圍第3 2項之方法，其中催化活性 金屬係選自鈦、鉻、釩、金及銀。 3 6 .如申請專利範圍第3 2項之方法，其中有機化合 物爲烷烴，選擇性氧化方法爲將烷烴部分氧化以產生對應 酮或醇。 3 7 _如申請專利範圍第3 6項之方法，其中烷烴係選 自丙焼丙院.、」院、戊院、及環己院，氧化劑係選自氧、 含氧氣體 '過氧化氫、氮氧化物、有機氫過氧化物、及有 機過酸，反應條件包括溫度約0 °C至約2 0 0 °C、壓力約1 巴至約30巴、’及空間速度約100 hr·1至約1 000 hr·1下進 行。 3 8 .如申請專利範圍第3 2項之方法，其中有機化合 物爲酮，選擇性氧化方法爲將酮i亏化（amm〇ximation_)以 產生對應肟。 39.如申請專利範圍第38項之方法，其中酮係選自 丙酮、甲基乙基酮、苯乙酮、環己酮、及環十二烷酮，氧 化劑爲過氧化氫或氮氧化物’其與氨混合，反應條件包括 溫度約25°C至約1 5〇°C ’及壓力約1大氣壓至約1 〇大氣 -21 - 1309582 (6) 壓。 40.如申請專利範圍第 物爲芳族化合物，選擇性氧 化，以將至少一羥基加至芳S 4 1 .如申請專利範圍第 合物係選自苯及甲苯，氧化f 化氫、氮氧化物、有機氫過^ 件包括溫度1251至約5 00 °C 4 2.如申請專利範圍第 過渡金屬係選自鈦、釩、及I 43.如申請專利範圍第 貴金屬爲金或銀。 3 2項之方法，其中有機化合 化方法爲將芳族化合物羥基 ΐ環結構。 4 0項之方法，其中該芳族化 係選自氧、含氧氣體、過氧 I化物、及有機過酸，反應條 ，壓力高至6 5巴。 3 2項之方法，其中催化活性 r 0 3 2項之方法，其中催化活性 -22-
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Publication number Priority date Publication date Assignee Title
US7608747B2 (en) * 1999-09-07 2009-10-27 Lummus Technology Inc. Aromatics hydrogenolysis using novel mesoporous catalyst system
US6906208B2 (en) * 1999-09-07 2005-06-14 Abb Lummus Global Inc. Mesoporous material and use thereof for the selective oxidation of organic compounds
US6930219B2 (en) * 1999-09-07 2005-08-16 Abb Lummus Global Inc. Mesoporous material with active metals
US6835686B2 (en) * 2001-07-05 2004-12-28 Millennium Specialty Chemicals Catalyst system and process for rearrangement of epoxides to allylic alcohols
US7132093B2 (en) * 2002-06-05 2006-11-07 UNIVERSITé LAVAL Mesoporous mixed oxide materials as a new class of SO2 resistant catalysts for hydrocarbon oxidation
US7985400B2 (en) * 2004-01-26 2011-07-26 Lummus Technology Inc. Method for making mesoporous or combined mesoporous and microporous inorganic oxides
US7091365B2 (en) * 2004-03-08 2006-08-15 Abb Lummus Global Inc. Process for olefin epoxidation and co-production of nylon precursor
US7678955B2 (en) 2005-10-13 2010-03-16 Exxonmobil Chemical Patents Inc Porous composite materials having micro and meso/macroporosity
US7655827B2 (en) * 2006-05-16 2010-02-02 Chevron Phillips Chemical Company Lp Selective isomerization of olefins to alkenes using a mesoporous catalyst
KR100709557B1 (ko) * 2007-01-02 2007-04-20 한국과학기술연구원 입상 지르코늄 나노 메조구조체의 제조방법
JP5176426B2 (ja) * 2007-03-16 2013-04-03 住友化学株式会社 シクロアルカノール及び／又はシクロアルカノンの製造方法
US9144765B2 (en) 2007-05-18 2015-09-29 Shell Oil Company Reactor system, an absorbent and a process for reacting a feed
AR066574A1 (es) * 2007-05-18 2009-08-26 Shell Int Research Un sistema reactor, un proceso de produccion de oxido de olefina 1,2-diol 1,2-diol eter , 1,2-carbonato o alcanolamina
KR101573085B1 (ko) 2007-05-18 2015-11-30 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 반응기 시스템, 흡수재 및 공급물을 반응시키는 방법
EP2092980A1 (en) * 2008-02-22 2009-08-26 ExxonMobil Research and Engineering Company Aromatic hydrogenation catalysts comprising Ti-MCM-41 and platinum group metals and aromatic hydrogenation process
WO2009140318A1 (en) 2008-05-15 2009-11-19 Shell Oil Company Process for the preparation of an alkylene carbonate and an alkylene glycol
CA2723988A1 (en) 2008-05-15 2009-11-19 Shell Internationale Research Maatschappij B.V. Process for the preparation of alkylene carbonate and/or alkylene glycol
US7812201B2 (en) 2008-10-01 2010-10-12 Targa Resources, Inc. Process and catalyst for converting alkanes
CN101703932B (zh) * 2009-10-23 2011-07-27 北京工业大学 用于催化消除VOCs的Pd和Pt负载介孔氧化锰的制备方法
EP2493837B1 (en) * 2009-10-29 2014-04-23 University College Cardiff Consultants Ltd. Hydrocarbon selective oxidation with heterogenous gold catalysts
KR101841689B1 (ko) * 2009-10-30 2018-03-29 삼성전자주식회사 메조 기공성 복합 촉매 및 그의 제조방법
WO2012005825A1 (en) * 2010-07-09 2012-01-12 Sumitomo Chemical Company, Limited Process for producing olefin oxide
JP2013505989A (ja) * 2010-07-09 2013-02-21 住友化学株式会社 酸化オレフィンの製造方法
US8791040B2 (en) 2010-11-03 2014-07-29 Fina Technology, Inc. Catalysts containing nano-materials and methods of making and using same
WO2012094120A1 (en) * 2011-01-05 2012-07-12 Sumitomo Chemical Company, Limited Process for producing olefin oxide
WO2012094121A1 (en) * 2011-01-05 2012-07-12 Sumitomo Chemical Company, Limited Process for producing olefin oxide
EP2682206A4 (en) * 2011-03-04 2014-09-17 Toyota Motor Co Ltd METAL PARTS, CATALYST FOR THE PURIFICATION OF PURIFICATION AND MANUFACTURING METHOD THEREFOR
CN103687847B (zh) * 2011-07-13 2019-04-02 宇部兴产株式会社 异氰酸酯化合物的制造方法
EP2749352B1 (en) 2011-08-23 2019-11-06 Toyota Jidosha Kabushiki Kaisha Exhaust gas purification catalyst, and method for producing same
CN102527408B (zh) * 2011-12-26 2013-11-27 广州自远生物科技有限公司 一种二甲基砜的制备方法及其固体催化剂
CN103204769B (zh) * 2012-01-13 2015-03-18 中国石油化工股份有限公司 一种由环己醇生产环己酮的方法
US9233944B2 (en) * 2012-06-27 2016-01-12 University Of Kansas Alkylene epoxidation with mesoporous catalysts
US20140016234A1 (en) * 2012-07-13 2014-01-16 Darin D. Lindig Hardened layer on a drive head
PE20150186A1 (es) 2012-08-02 2015-02-27 Sasol Tech Pty Ltd Catalizadores
US9636663B2 (en) 2013-04-24 2017-05-02 Saudi Basic Industries Corporation High productivity catalyst for alkane oxidation to unsaturated carboxylic acids and alkenes
CN105142780A (zh) 2013-04-24 2015-12-09 沙特基础工业公司 用于从烷烃产生不饱和羧酸的负载型催化剂
TW201512180A (zh) * 2013-05-16 2015-04-01 Scient Design Co 用於乙烯氧化物觸媒之載體
KR101460348B1 (ko) * 2013-10-02 2014-11-13 서울대학교산학협력단 중형기공성 니켈-인-알루미나 에어로젤 촉매, 그 제조 방법 및 상기 촉매를 이용한 액화천연가스의 수증기 개질 반응에 의한 수소 가스 제조 방법
CN105688906B (zh) * 2016-01-14 2018-02-09 同济大学 一种用于生物柴油副产物甘油氢解产1,3‑丙二醇的催化剂的制备方法
KR101713279B1 (ko) * 2016-03-24 2017-03-07 삼성전자주식회사 메조 기공성 복합 촉매 및 그의 제조방법
CN107051438B (zh) * 2017-05-12 2019-07-05 中自环保科技股份有限公司 一种含铑催化剂的制备方法及其催化剂
CN109894119B (zh) * 2017-12-08 2022-02-08 中国石油化工股份有限公司 由丁烯制备1,3-丁二烯催化剂的制备方法
CN110065989B (zh) * 2019-06-04 2021-07-06 温州大学 一种利用微孔结构的金属有机骨架材uio-67衍生物吸附水中有机染料的方法
US10809220B1 (en) * 2019-07-10 2020-10-20 Najran University Method for chemical sensing and photocatalysis with silver nanoparticles/mesoporous silicon nanocomposite

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959174A (en) 1971-08-24 1976-05-25 W. R. Grace & Co. Method of selectively producing high pore volume silica gel
EP0987220A1 (en) 1998-09-17 2000-03-22 Technische Universiteit Delft Mesoporous amorphous silicate materials and process for the preparation thereof
US5102643A (en) 1990-01-25 1992-04-07 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis
US5264203A (en) 1990-01-25 1993-11-23 Mobil Oil Corporation Synthetic mesoporous crystalline materials
US5108725A (en) 1990-01-25 1992-04-28 Mobil Oil Corp. Synthesis of mesoporous crystalline material
US5057296A (en) 1990-12-10 1991-10-15 Mobil Oil Corp. Method for synthesizing mesoporous crystalline material
US5110572A (en) 1990-01-25 1992-05-05 Mobil Oil Corp. Synthesis of mesoporous crystalline material using organometallic reactants
US5191148A (en) 1991-05-06 1993-03-02 Mobil Oil Corporation Isoparaffin/olefin alkylation
US5191134A (en) 1991-07-18 1993-03-02 Mobil Oil Corporation Aromatics alkylation process
JPH05242603A (ja) 1992-02-28 1993-09-21 Hitachi Ltd 光ディスクシステム
NL9300737A (nl) 1993-04-29 1994-11-16 Meern Bv Engelhard De Werkwijze voor het selectief oxideren van koolwaterstoffen.
US5374747A (en) 1993-12-23 1994-12-20 Arco Chemical Technology, L.P. Epoxidation process and catalyst therefore
US5672556A (en) 1994-08-22 1997-09-30 Board Of Trustees Operating Michigan State University Crystalline silicate compositions and method of preparation
US5795555A (en) 1994-11-24 1998-08-18 Alive; Keshavaraja Micro-meso porous amorphous titanium silicates and a process for preparing the same
IN190356B (zh) 1994-12-30 2003-07-19 Council Scient Ind Res
US5622684A (en) 1995-06-06 1997-04-22 Board Of Trustees Operating Michigan State University Porous inorganic oxide materials prepared by non-ionic surfactant templating route
US5853566A (en) * 1995-11-28 1998-12-29 Shell Oil Company Zeolite-beta containing catalyst compositions and their use in hydrocarbon conversion processes for producing low boiling point materials
US5849258A (en) 1996-06-06 1998-12-15 Intevep, S.A. Material with microporous crystalline walls defining a narrow size distribution of mesopores, and process for preparing same
DE19624340A1 (de) 1996-06-19 1998-01-08 Degussa Verfahren zur Herstellung von kristallinen mikro- und mesoporösen Metallsilicaten, verfahrensgemäß erhältliche Produkte und deren Verwendung
EP0918762B1 (en) * 1996-07-01 2001-05-16 The Dow Chemical Company Process for the direct oxidation of olefins to olefin oxides
DE19639016A1 (de) * 1996-09-23 1998-03-26 Basf Ag Mesoporöses Siliciumdioxid, Verfahren zu seiner Herstellung und seiner Verwendung
US6133186A (en) 1997-03-06 2000-10-17 Shell Oil Company Process for the preparation of a catalyst composition
US5948683A (en) 1997-10-18 1999-09-07 Engelhard Corporation Catalyst for selective oxidation of unsaturated hydrocarbons and methods of making and using the same
DE19841142A1 (de) 1998-09-09 2000-03-23 Degussa Kieselsäuren und Metallsilikate mit regelmäßiger Mesoporenstruktur
US6906208B2 (en) 1999-09-07 2005-06-14 Abb Lummus Global Inc. Mesoporous material and use thereof for the selective oxidation of organic compounds
EP1134189A1 (de) 2000-03-16 2001-09-19 Degussa AG Formkörper amorpher, poröser (Metall-)Silikate
ES2181528B1 (es) 2000-03-28 2004-06-16 Universitat De Valencia (Estudi General ) Procedimiento de preparacion de oxidos mixtos porosos, materiales asi obtenidos y sus usos.
FR2816609B1 (fr) 2000-11-14 2003-01-10 Ceca Sa Solides inorganiques mesoporeux, leur procede de preparation et leurs utilisations notamment comme catalyseurs et absorbants

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