| Abstract: | 1,4-丁二醇及四氫?喃具有廣泛用途且其下游之產品價值高，因此其產?也迅速的增加中，國內現有三家公司生產此二重要石化產品。工業界使用之主要製程有四種，包括以丙烯醇為原?之製程(現為國內大?化工所採用)，在此製程中之丙烯醇先經氫醛化反應產生直鏈之4-羥基丁醛與支鏈之3-羥基2-甲基丙醛等中間產物，其中4-羥基丁醛再經由觸媒催化之氫化反應得到1,4-丁二醇。工業界使用之4-羥基丁醛氫化觸媒為?尼鎳，無法同時生產顯著?之四氫?喃。我們初步研究結果顯示雙?屬核殼式觸媒能有效催化4-羥基丁醛之氫化反應，且能同時生產1,4-丁二醇和多?的四氫?喃。本計畫之主要目的是對雙?屬觸媒催化 4-羥基丁醛氫化反應作?進一步之研究及探討其基本原?，期能發現最適當之雙?屬觸媒及反應條件，如此將可以於一個反應器中能透過反應條件的調整並依市場之需要而同時生產1,4-丁二醇及多?之四氫?喃，以?低四氫?喃(四氫?喃-簡稱THF-是一種重要的有機合成原?和優?的溶劑)之生產成本，?提升我國石化產業的競爭能?。本計畫為期??，將探討含有第VIII 族?屬中雙?屬觸媒之組成、觸媒製備方式、載體及反應條件之改變對於其氫化活性、選擇性及產物中四氫?喃/1,4-丁二醇之莫耳比的影響。 此些雙?屬觸媒將包括多孔性核殼式雙?屬觸媒(第壹?研究之對象)及支撐於碳載體上之雙?屬觸媒(第貳?研究之對象) 。第壹?研究之核殼式雙?屬觸媒之核將為雙?屬?米顆?，此些均勻尺寸的?屬?米顆?係先以高分子加以穩定;核殼式觸媒之殼為多孔性二氧化矽，二氧化矽係用Stober 法塗佈於?屬?米顆?之外;再經過?燒及還原而得到多孔性核殼式觸媒。第貳?研究之碳載體支撐的雙?屬觸媒所使用之碳載體將包括活性碳、中孔?之碳材與?米碳管，?用含浸法、共沉澱法及還原沉積法等製備碳載體支撐之雙?屬觸媒。對於表現優?之雙?屬觸媒，我們將進?各項特性分析，以瞭解觸媒之性質和其催化性能間的關?性。我們亦將建?此些反應之反應動?學，做為瞭解其反應機構及設計和操作反應器的依據。本計畫之完成將有助於對1,4-丁二醇和四氫?喃製程之經濟效?的提昇及幫助我國石化產業高值化之發展，並能使我們對氫化反應觸媒、雙?屬觸媒、核殼式觸媒和碳支撐之觸媒有?進一步之瞭解，所獲得之結果可作為觸媒設計、應用及製備的重要?考。
1,4-butanediol (BDO) and tetrahydrofuran (THF) have extensive use and their downstream products are highly valuable, therefore, their production capacities increase rapidly. The use of allyl alcohol as the raw material is one important process for 1,4-butanediol production. In this process, the hydroformylation of allyl alcohol gives 4-hydrobutyraldehyde and 3-hydro-2-methylpropionaldehyde. After extraction, the hydrogenation of 4-hydrobutyraldehyde gives 1,4-butanediol, catalyzed industrially with nickel-based catalysts. Only small amount of tetrahydrofuran can be produced with the nickel-catalyzed process. In a preliminary study, we found that a core-shell bimetallic catalyst can produce 1,4-butanediol and large amount of tetrahydrofuran (THF) simultaneously. It is therefore possible to manufacture the two important petrochemicals in a single reactor (THF is an important chemical intermediate and a good solvent) , and the ratio of THF/BDO can be adjusted depending on the market demand. In this project, we will study the use of supported bimetallic catalysts for 4-hydrobutyraldehyde hydrogenation in greater details. The two-year project will investigate the effects of composition and structure of supported bimetallic catalyst (containing group VIII noble metals) on their catalytic properties for 4-hydrobutyraldehyde hydrogenation. The first - year study will focus on the porous core-shell bimetallic nano-catalysts, the second-year study will focus on the carbon supported bimetallic catalysts. For the porous core-shell bimetallic nano-catalysts , the nano-metal core will be stabilized by a polymer stabilizer, the shell will be silica. Silica shell will be coated on the core with Stober method. For the carbon supported bimetallic catalysts, the carbon supports include activated carbon, mesporous carbon materials and carbon nanotubes, and the catalysts will be prepared by impregnation, co-precipitation and liquid co-reduction. We will characterize the bimetallic catalysts in order to understand the relationships between catalyst physical properties and their catalytic performances. We will also investigate the hydrogenation kinetics to understand the reaction mechanics and to provide the basis for reactor design and operation. This project can improve the economy benefits of 1,4?butanediol and tetrahydrofuran production process, and can improve our understanding on the core?shell bimetallic / carbon supported bimetallic hydrogenation catalysts. The results obtained in this project can be used as an important guideline for the design, use, and manufacture of selective hydrogenation catalysts. |
