Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/10674
標題: 氯化鋁酸鹽離子液體在環烷烴異構化之應用
Application of Chloroaluminate Ionic Liquids on Cycloalkane Isomerization
作者: 黃銘郁
黃銘郁, Ming-Yu Huang
關鍵字: chloroaluminate ionic liquids;氯化鋁酸鹽離子液體;cycloalkane;isomerization;環烷烴;異構化反應
出版社: 材料科學與工程學系所
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摘要: 
本論文主要是利用酸性氯化鋁酸鹽離子液體做為觸媒,用於環烷烴異構化反應研究。主要研究方向是(1)合成外向型四氫雙環戊二烯,也就是高能燃料JP-10,(2)異構化合成金剛烷,(3)以插層之蒙脫土為擔體,製備負載型離子液體,進行異構化反應研究,(4)開發新的擬固定床離子液體反應器。其詳細探討可分為四個部分,如下:
第一部份 利用不同可調酸性之氯化鋁酸鹽離子液體(chloroaluminate ionic liquids)當觸媒,進行內向型四氫雙環戊二烯(endo-tetrahydrodicyclopentadiene, endo-THDCPD)異構化合成外向型異構物(exo-isomer,高能燃料JP-10)反應研究。觸媒活性及選擇性可利用調整離子液體中三氯化鋁(AlCl3)之莫耳分率達最適化。由設計適當的觸媒系統及反應條件,許多副反應例如結構重組、烷化、裂解、雙聚合等反應之副產物可減至最少。最佳觸媒系統是選用1-丁基-3-甲基-咪唑氯化物(1-butyl-3-methylimidazolium chloride)和0.6-0.65莫耳分率三氯化鋁所製備的離子液體。使用最適化觸媒系統,內向型四氫雙環戊二烯在50 °C可快速進行異構化反應,轉化率高達98.9%,並具有100%外向型四氫雙環戊二烯產品選擇性。離子液體當觸媒之壽命亦進行反應測試,在使用多次後,其反應活性並沒有明顯的減少。
第二部分 利用氯化鋁酸鹽離子液體當觸媒將外向型四氫雙環戊二烯異構化,以合成金剛烷(Adamantane, ADM)。在使用吡啶氯化氫(pyridine hydrochloride) 和0.65莫耳分率三氯化鋁所製備的離子液體,70 °C反應6小時,金剛烷的產率可達21.9%。在此反應條件下金剛烷的選擇性為66%,產物很容易和觸媒分離。在此亦提出內向型/外向型四氫雙環戊二烯在酸性觸媒下的異構化反應機構,四氫雙環戊二烯會經由一個帶陽電荷的碳原子,轉變成金剛烷主產物,或進行開環反應合成十氫萘 (decalin) 或其他飽和十碳雙環副產物。
第三部分 將具有不同長度烷基鹵化鹽經由離子交換插層進入蒙脫土層間結構,其中1-十六碳基-3-甲基咪唑氯化物 (1-hexadecyl-3-methylimidazolium chloride)、十六碳基三甲基銨鹽溴化物 (hexadecyltrimethylammonium bromide)、雙十六碳基雙甲基銨鹽溴化物(dihexadecyldimethylammonium bromide)、三丁基十六碳基磷鹽溴化物(tributylhexadecylphosphonium bromide)插層後,可使矽酸鹽層間距由12 Å撐開至37–41 Å(由X射線繞射測得)。改質後黏土先用吡啶氯化氫和三氯化鋁混合物預處理,再含浸氯化鋁酸鹽離子液體觸媒,最後將內向型四氫雙環戊二烯異構化合成外向型異構物。新開發的黏土擔體離子液體觸媒對主產品具有相當定量轉化率及選擇性,並可重複多次使用
第四部分:針對氯化鋁酸鹽離子液體在環烷烴異構化反應之特性,開發新的擬固定床離子液體反應器,並進行內向型四氫雙環戊二烯異構化反應研究。由於離子液體觸媒和反應物及產物具有相當不同之比重及不互溶特性,此液體觸媒可像固定床之固體觸媒固定在媒床不動,而在連續式反應中產物能通過並和觸媒自動分離。在此新的反應器中,觸媒高度45公分,反應物以小液滴狀由觸媒底部浮到頂部約5-6秒,在80 °C下,內向型四氫雙環戊二烯的轉化率約為10.7%,主產品外向型四氫雙環戊二烯的選擇性為100%。增長反應管長度、增加回流時間、或反應管加入填充物應可有效提高反應轉化率。

Chloroaluminate ionic liquids (ILs) were used as acidic catalysts for isomerization of cycloalkane. The main studies were (1) producing exo-tetrahydrodicyclopentadiene, exo-THDCPD, also called high energy fuel JP-10, (2) producing adamantane (ADM), (3) preparation of supported chloroaluminate IL catalyst with intercalated montmorillonite clay as support, and studied on isomerization, (4) developing a new pseudo-fixed bed IL reactor. The thesis is divided into four parts:
Part 1 The isomerization of endo-tetrahydrodicyclopentadiene (endo-THDCPD) to its exo-isomer (JP-10) has been investigated by using chloroaluminate ionic liquids (ILs) as catalysts. Undesirable by-products derived from side-reactions could be minimized by appropriate catalyst design and adjustment of the reaction conditions. The catalyst system was further optimized by selecting 1-butyl-3-methylimidazolium chloride as the basic IL and adding 0.60~0.65 mole fraction of AlCl3 as the promoter. Using the optimized catalyst system, the isomerization of endo-THDCPD to exo-THDCPD proceeded at a fast rate at 50 C with 98.9% conversion and 100% selectivity. The catalyst longevity has been demonstrated by recycling the IL several times without a noticeable reduction in catalytic activity.
Part 2 Adamantane (ADM) was synthesized by isomerization of exo-THDCPD using chloroaluminate ILs as the catalyst. The yield of ADM was optimized to obtain 21.9% under the conditions of 70 C for 6 h and pyridine hydrochloride/AlCl3 at an AlCl3 mole fraction of 0.65. Under these conditions, the selectivity of ADM was 66% and the product mixture was easily recovered from the IL catalyst phase. It is proposed that endo-/exo- isomerization occurs via a carbocation mechanism leading to ADM, the main product, with ring-opening to decalin and other C10H18 by-products.
Part 3 Various halide salts with different alkyl lengths were allowed to intercalate into the layer structure of sodium montmorillonite clay through an ion exchange reaction. Intercalation of 1-hexadecyl-3-methylimidazolium chloride, hexadecyltrimethylammonium bromide, dihexadecyldimethylammonium bromide, and tributylhexadecylphosphonium bromide could expand the spacing of the silicate layers from 12 Å to 37~41 Å (measured by X-ray diffraction). The modified clays were pretreated with the pyridine hydrochloride/AlCl3 mixture and used for suitably supporting a chloroaluminate IL catalyst for the isomerization of endo-THDCPD into the corresponding exo-isomer. Nearly quantitative conversion to the desired product and nearly quantitative selectivity were observed for the newly developed clay-supported IL catalysts, which were proven to be recyclable.
Part 4 Base on the special properties of chloroaluminate IL on isomerization of cycloalkane, a new pseudo-fixed bed IL reactor was developed and studied for isomerization of an endo-THDCPD. With very different density and immiscible properties between IL catalyst and reactant/product, the liquid catalyst is as immobile as solid catalyst in fixed bed, and product passes through and separate from catalyst automatically at continue reaction. For the new reactor with 45 cm height of liquid catalyst, the reactant droplet floats from bottom to top of the IL was about 5-6 s, the isomerization of endo-THDCPD proceeded with 10.7% conversion and 100% selectivity of exo-THDCPD at 80 C. Elongating IL column, increasing cycle time and filling packing in the column all can effectively improve conversion for each pass through the column reactor.
URI: http://hdl.handle.net/11455/10674
Appears in Collections:材料科學與工程學系

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