TW201244822A - Preparation of ruthenium supported on mesoporous MCM-41 and its application in hydrogenation of p-xylene - Google Patents

Preparation of ruthenium supported on mesoporous MCM-41 and its application in hydrogenation of p-xylene Download PDF

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TW201244822A
TW201244822A TW100117028A TW100117028A TW201244822A TW 201244822 A TW201244822 A TW 201244822A TW 100117028 A TW100117028 A TW 100117028A TW 100117028 A TW100117028 A TW 100117028A TW 201244822 A TW201244822 A TW 201244822A
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mcm
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ruthenium
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Chung-Sung Tan
Yu-Wen Chen
Hsin-Wei Lin
Clive Hsu Yen
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Univ Nat Central
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Description

201244822 and the conversion method, this process is very efficient of p-xylene is improved significantly. 四、指定代表圖： 無指定代表圖 五、本案若有化學式時’請揭示最能顯示發明特徵的化學式 六、發明說明： 【發明所屬之技術領域】 本發明係關於運用超臨界流體(supercritiea]l nuid& SCF)技術製備奈米金屬觸媒，尤其有關將釕奈米金屬沉積在一種 中孔洞二氧化矽MCM-41做為觸媒的方法，本發明揭示一種以化 流體沉積法製備釕承載於中孔洞MCM_41之奈米金屬觸媒，及於 =二曱苯氫化反應之方法;其包括製備奈米觸媒方法一：選用金屬 前驅物為乙醯丙酮釕（Ruthenium Acetylacetonate，Ru(acac)〇 而觸媒擔體為MCM-41，製備1 wt·%至1〇 wt.%奈米釕觸媒，先以 適量之溶劑（例如：四氫呋喃)將配好的金屬前驅物與擔體於超音 波震盪，再將溶劑抽乾後，即得到分散良好的粉末；將此粉末置 入高壓反應器中，升溫到100 t至3〇〇。當溫度升至反應溫度 時’通入預先混合之30 bar至100 bar氫氣與80 bar至300 bar 二氧化碳。或製備奈米觸媒方法二：選用金屬前驅物為 Bis(2, 2, 6, 6-tetramethyl- 3, 5-heptanedionato) (l’5-cyclo〇ctadiene)ruthenium，Ru(cod)(tmhd)2，而觸媒擔體 為MCM-41，製備1 wt.%至10 wt.%奈米釕觸媒。將配好的金屬前 驅物與擔體置入高壓反應器中，升溫到1〇〇°c至3〇〇。(：。當溫度升 至反應溫度時，通入預先混合之3〇 bar至100 bar氫氣與80 bar 至300 bar二氧化碳。其以化學流體沉積法製備之觸媒，能均勻 地將奈米金屬粒子含浸至中孔洞基材中，相對於傳統觸媒製程能 201244822
» I f效節省時間並提高反應轉化率。此製備之觸媒用於對二甲苯之 匕，其中釕對MCM-41之重量百分比介於1 wt·%至1〇 wt. %，氫 氣壓力介於10 bar至100 bar，溫度介於20°C至l〇〇°c。 【先前技術】 ，聚對笨二甲酸乙二醇脂(p〇lyethylene terephthalate)，簡 稱PET)為常用的塑膠原料之一，在近年來大量使用下已造成環境 相當士^負擔。PET具有極佳的熱及化學穩定性，直接氫化pET 中的苯環，以獲得生物可分解之高分子聚合物面臨相當大的難 -般PET製程上通常是將對二曱苯(p—Xylene)氧化而獲得對 本二曱酸(Terephthalic Acid，簡稱TPA) ’再將TPA進行聚合反 應形成PET。如果將p—xylene進行苯環氫化，以獲得不含苯環之 严應物:即 I，4-對環己烷二曱酸(1，4_Cycl〇hexanedicarb〇xylic Acid，簡稱1，4-CHDA) ’再以1，4-CHDA氧化形成的單體進行聚合 反應得到，物可分解之高分子聚合物。本研究以化學流體沉積 法，也就歧料遍所熟知的超臨界流體來製備奈米金屬觸媒。 由於超臨界流體的特殊师只餘制溫度和壓力就可達成，所以 ^對於-般傳統溶液製備法有所優勢。當操作溫度及壓力超過物 質的臨界溫度及臨界壓力時，此時為超臨界趙。在本發明中將 選用一氧化碳當作超臨界流體介質。相較於一般製程，選用臨 f流體二氧化碳當作賴具有如下_:⑴操作溫度低；⑵綠 色溶劑；（3)不破壞擔體結構；⑷高質傳擴散係數；⑸操作、 來多重視’其操作要點概括為··⑴金屬前驅物 ^選擇，⑵猎由超臨界流體將金屬前驅物溶解；⑶前驅物 ^界流體協助下進行單體表面的擴散及吸附；⑷麵分離 妷程序；（5)對金屬前驅物進行還原反應。
Zhang等人[J· Supercrit. Fluids，第38卷(2006)，第252? 二頁臨；二氧化碳製將金屬前驅物帶入孔洞擔體表面 〆疋咼77 這個程序包括了將金屬前驅物溶入超臨界二氣 化碳内和基質浸泡在溶液内。之後將金屬前驅物還原至金= 201244822 子，有三種程序： 直接加入如醇類或氫氣的還原劑進入超臨界流體還原金屬。 b. 直接升高溫度將金屬還原。 ' c. 先將壓力洩至常壓’在通入還原劑如氫氣或空氣將金屬還原。 以化學流體沉積法進行觸媒製備’因為不會有乾燥程序\'所 以並不會有一般傳統方式的所造成的反向的作用力使得有機金屬 分子向外擴散’而形成核殼型式的觸媒。當採用超臨界流體沈積 法所製備的觸媒因不會有此現象發生’而會形成均勻分佈的觸 媒’藉此可以提升反應的速率。Dhepe等人[Phys. Qiem. Chem. Phys.第5卷，第5565至5573頁]以Rh、Pt雙金屬以化學流體沉 積方法含浸至HMM-1與FSM-16，對比於傳統含浸方法。傳統方法 只能將金屬粒子附著於顆粒外面，而以超臨界c〇2挟帶 物，能有效的將奈米金屬粒子含浸至中孔洞之孔道；金以·: ，粒子的分散性。Chatterjee 等人[Adv· Synth. Catal 第=48 ^(2006)第1580至1590頁]以化學流體沉積方法將奈米金粒 f至MCM-48擔體巾’在他們的研究巾指丨，絲金的粒子大小 =界二氧化碳的密度紅比_。先前的專利文獻中，未有如 $明以超臨界流體之方法製備釕金屬分散於中孔則cm_4i分子 師之方法’及將其應餘對二甲笨航反應之方法。 【發明内容】 ί::，要其目：二 k升金屬奈料奸賴财齡散性。 初進而 本發明的屬】供化對4苯的方法，其中使用 或f、去〇、金U觸媒’進而提升對二甲苯氫化之速率。 子沉積發=t依本發明内容所完成的將金屬奈米粒 a) 夕中的方法，該方法包含下列步驟： ί二ί前驅物，其在超臨界二氧化碳中有良好的溶解 X果溶解度不高的話，亦可先加入些許的共溶劑，並 201244822 利用超音波震盪加速其溶解； b) 將該金屬前驅物和中孔洞二氧化矽載體一起置於高壓爸 内； 其特徵在於該方法包含下列步驟： c) 將氫氣和二氧化碳預先混合於儲壓槽中，並於到達反應溫 度之條件後’直接通入高壓釜中;或 Φ 先通入二氧化碳於高壓釜中，待金屬前驅物溶解後，再將 預混好的氫氣和二氧化碳通入高壓釜中。 本發明在步驟d)之後進一步包含： e) 將製備好的觸媒用於對二曱苯的氫化反應。 【實施方式】 實施方式1 : 本發明揭示一種以化學流體沉積法製備釕承載於中孔洞 MCM-41之奈米金屬觸媒，及於對二曱苯氫化反應之方法；其包括製 備奈米觸媒方法:選用金屬前驅物為乙醯丙酮釕(Rutheni um
Acetylacetonate，Ru(acac)3)而觸媒擔體為 MCM-41，製備 1 wt.% 至10 wt.%奈米釕觸媒，先以適量之溶劑（例如：四氫呋喃）將配好 的金屬前驅物與擔體於超音波震盪，再將溶劑抽乾後，即得到分 散良好的粉末；將此粉末置入高壓反應器中，升溫到1〇〇充至300 °C。當溫度升至反應溫度時，通入預先混合之3〇 bar至1〇〇 bar 虱氣與80 bar至300 bar二氧化碳。 實施方式2 : 本發明揭示一種以化學流體沉積法製備釕承載於中孔洞 MCM-41之奈米金屬觸媒，及於對二甲苯氫化反應之方法；其包括製 備奈米觸媒方法：選用金屬前驅物為Bis(2, 2, 6, 6-tetramethy卜 3,5-heptanedionato)(l, 5-cyc1ooctadiene)ruthenium > Ru(codXtmhd)2，而觸媒擔體為 MCM-41，製備 1 wt.°/。至 10 wt.0/0 奈米釕觸媒。將配好的金屬前驅物與擔體置入高壓反應器中，升 201244822 溫到100 C至300 °c。當溫度升至反應、、w声睹 =4⑽^氫氣與8° -至3°:二氧 =合之 至中體 ==製備之觸媒’能均句地將奈米金屬粒子含浸 至中孔洞基材中，相對於傳統觸製、 氮氣壓力介於至⑽ 可以結果(圖一)’Ru的粒子大小約在2. ， 月楚的看顺鑲嵌在顧_41孔道中。比較傳統含浸法和 机體》儿積法兩種不同製備法之Ru/MCM_41，TEM圖（圖一、二）可以 看出化學趙沉積法魄由財超臨界二氧化韻獅下， ^子能有效的含浸至孔道巾，且具有較佳的分散性。而相反的在 傳統含浸法下的結果’較容易導致金屬粒子聚集的現象。在平均 的金屬顆粒大小，化學流體沉積法Ru觸媒約在2.6 nm;傳統方法 約為3.0 nm (表一）。比較於對二甲苯氫化的結果(表二），在相同 條件下化學流體沉積法觸媒之Ru/MCM_41轉化率高達1〇〇%，而傳 統方法含浸的Ru/MCM-41卻只有13%左右。另外一方面，化學流體 沉積法觸媒比傳統製備法觸媒的TOF值高出7倍之多。 表一比較兩種製備法Ru/MCM-41奈米金屬特性
Ru loading (weight %) Average size (nm) BET surface area (m2/e) Ru/MCM-41 (C02) 4.8 2.6 ±0.5 1068 Ru/MCM-41 (conventional) 4.2 3.0 ±0.8 899 表二比較兩種製備法Ru./MCM_41氫化p-xylene反應性 conversion % TON TOF (hr'1) Ru/MCM-41 (C02) 100 2380 1428 Ru/MCM-41 (conventional) 13.7 309 185 201244822
I I 【圖式簡單說明】 圖一化學流體沉積法製備Ru/MCM-41之TEM圖 圖二傳統方法製備Ru/MCM-41之TEM圖 【主要元件符號說明】 無主要元件符號說明

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  1. 201244822 • t 七、申請專利範圍： 1. 一種以化學流體沉積法製備釕承載於MCM-41之中孔洞奈米金 屬觸媒之方法，其包括製備奈米觸媒方法一：選用金屬前驅物 為乙醯丙酮釕（Ruthenium acetylacetonate，Ru(acac)3)而觸 媒擔體為MCM-41，製備1 wt. %至10 wt. %奈米釕觸媒，先以適 量之溶劑（例如：四氫呋喃）將配好的金屬前驅物與擔體於超音 波震盪，再將溶劑抽乾後，即得到分散良好的粉末；將此粉末 置入高壓反應器中，升溫到100 °C至300 °C。當溫度升至反 應溫度時，通入預先混合之30 bar至100 bar氫氣與80 bar 至300 bar二氧化碳；或製備奈米觸媒方法二：選用金屬前驅 物為 Bis(2, 2, 6, 6-tetramethyl- 3, 5-heptanedionato) (1，5-cyclooctadiene)ruthenium，Ru(cod)(tmhd)2，而觸媒擔 體為MCM-41，製備1 wt. °/Q至l〇 wt. %奈米釕觸媒。將配好的金 屬前驅物與擔體置入高壓反應器中，升溫到1〇〇 °C至300 °C; 當溫度升至反應溫度時，通入預先混合之3〇 bar至100 bar 氫氣與80 bar至300 bar二氧化碳。 λ 一種氫化對二曱苯的方法，其中使用申請專利範圍第1項所製 備的釕金屬奈米觸媒’其中釕對1^〇|_41之重量百分比介於1 敗％至10 wt· % ’氫氣壓力介於1〇 bar至100 bar，溫度介於 2〇°C 至 100。(：。
TW100117028A 2011-05-13 2011-05-13 釕承載於中孔洞ｍｃｍ－４１奈米金屬觸媒之方法及於對二甲苯氫化反應之應用 TWI418405B (zh)

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US9861960B2 (en) * 2013-10-18 2018-01-09 Exxonmobil Chemical Patents Inc. Hydrogenation catalyst, its method of preparation and use
US9862657B2 (en) 2014-12-03 2018-01-09 Uop Llc Methods for selectively hydrogenating substituted arenes with supported organometallic catalysts
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