【作者】 王永福；

【导师】 高鹏飞； 孙自瑾；

【作者基本信息】 山西大学 ， 化学工程， 2017， 硕士

【摘要】 丁二酮肟作为一种重要的化学原料在实际生产和科学研究中有重要的用途。丁二酮肟不仅可作为螯合剂来测定与分析金属离子,还可以作为氧化还原指示剂和色谱分析试剂。工业上合成丁二酮肟的方法主要采用丁酮-羟胺法,即是以亚硝酸钠、乙醇、丁酮、盐酸和羟胺单磺酸钠为原料合成的。首先亚硝酸钠与乙醇在硫酸存在的情况下发生反应生成亚硝酸乙酯。然后亚硝酸乙酯和丁酮发生化学反应生成中间产物丁二酮单肟,反应过程中以盐酸作为催化剂。最后,羟胺单磺酸钠与丁二酮单肟在加热的条件下发生反应生成丁二酮肟。然而,工业上丁二酮肟的合成方法存在产物分离困难、原料易腐蚀和原料易爆等缺点,还会污染环境。因此,有必要研究新的方法来实现丁二酮肟的绿色、高效合成。自从钛硅分子筛合成以来,由于钛硅分子筛/H₂O₂体系对多种有机化合物（酮类和酚类）具有选择性氧化,所以在催化环己酮的氨肟化反应、苯酚的羟基化反应和烯烃的环氧化等反应中表现出良好的催化性能,并实现了工业化应用。钛硅分子筛在环己酮氨肟化反应中的成功应用为一步合成丁二酮肟提供了理论和实践支撑。但是,关于钛硅分子筛催化丁二酮氨肟化反应的研究还没有相关的文献报道。本论文主要以H₂O₂作为氧化剂,以钛硅分子筛（TS-1、Ti-MWW和Ti-MOR）为催化剂,探究了钛硅分子筛催化丁二酮氨肟化反应过程中的反应条件对合成丁二酮肟的影响,通过改变反应过程中反应底物与催化剂的用量、反应时间、反应温度等反应条件,从而获得最优的反应条件。采用XRD、氮物理吸附、紫外可见漫反射光谱（UV-Vis DRS）、扫描电子显微镜（SEM）、傅立叶红外光谱（FT-IR）及表面接触角等对催化剂TS-1、Ti-MWW、Ti-MOR的织构、结构性质进行了表征。本论文的主要结论有:（1）钛硅分子筛催化丁二酮氨肟化反应过程中的反应温度优选30℃,最佳的反应时间为2.0h,催化剂的用量优选2.0g。丁二酮氨肟化反应过程中溶剂优选乙醇;（2）反应过程中过氧化氢的进料方式为连续进料,反应底物丁二酮、NH₃、H₂O₂的最佳物质的量比为丁二酮:NH₃:H₂O₂=1:3:2;（3）催化剂TS-1的催化活性和表面疏水性能优于Ti-MOR和Ti-MWW。更多还原

【Abstract】 Diacetyldioxime is an important chemical reagent.Diacetyldioxime can be used in the analysis and determination of metal ions as chelating agents,analytical reagents,redox indicators and chromatographic an alytical reagents and so on.The method for synthesis of diacetyldioxime in industry mainly adopt hydroxylamine method to produce diacetyldioxime,which is synthesized by butanone,ethanol,nitrite and hydroxylamine sodium sulfonate.Firstly,the ethyl nitrite is synthesized with ethanol reacts and nitrous acid in the existence of sulfuric acid.In the next place,Hydrochloric acid as catalyst,the 2,3-Butanedionemonoxime is synthesized with ethyl nitrite and methyl ethyl ketone.Conclusively,the reaction of hydroxylamine sulfonic acid sodium with 2,3-Butanedionemonoxime was produced under the condition of heating to produce diacetyldioxime.However,the synthesis method of diacetyldioxime in industry has many disadvantages,such as difficult separation of products,easy corrosion of raw materials and explosive materials and so on.Therefore,it is necessary to develop a new way for synthesizing diacetyldioxime.Since the synthesis of titanium silicon molecular sieve,because of the titanium silicon molecular sieve and H₂O₂ system not only has the selective oxidation of various organic compounds but also shows good catalytic performance in the reaction of cyclohexanone,hydroxylation of phenol and epoxidation of olefins,titanium silicon molecular sieve have industrialized.The successful application of titanium silicalite molecular sieve in cyclohexanone oxime reaction provides a theoretical and practical support for the synthesis of diacetyldioxime.However,the research on the ammoximation of 2,3-butanedione over titanium silicalite sieves has not been reported.In this paper,hydrogen peroxide was used as oxidant,TS-1、Ti-MOR and Ti-MWW was used as catalysts,The effect of reaction conditions was studied on the synthesis of diacetyldioxime on the 2,3-butanedione ammoximation in the existence of titanium silicalite sieves.The reaction conditions include the amount of catalyst and2,3-butanedione,reaction time and temperature,the amount of solvent and so on.The texture and structural properties of TS-1,Ti-MWW and Ti-MOR were characterized by using X-ray diffraction（XRD）,DRS UV-vis,nitrogen-adsorption,FT-IR spectroscopy,spectroscopyscanning electron microscopy（SEM）and surface contact angle and so on,and the nexus was researched between the structure and performances of the catalysts.The primary results are as follows:（1）The appropriate reaction temperature of the 2,3-butanedione ammoximation over titanium silicalite sieves is 30℃,the appropriate reaction time is 2.0h and the amount of catalyst of t he preparation of the reaction of butyl ketone is 2.0g.The optimum solvent is ethanol on the ammoximation of 2,3-butanedione over titanium silicalite sieves.（2）The feed ratio of hydrogen peroxide in the process of the synthesis of diacetyldioxime is a continuous feed.The appropriate amount of substance ratio of 2,3-butanedione,ammonia and hydrogen peroxide is 1:3:2.（3）The hydrophobic property of titanium silicalite molecular sieve catalyst TS-1 was stronger than that of titanium silicalite molecular sieve catalyst Ti-MOR and titanium silicalite molecular sieve catalyst Ti-MWW.The catalytic performance of titanium silicalite molecular sieve TS-1 catalyst was higher than that of titanium silicalite molecular sieve Ti-MWW and Ti-MOR on the ammoximation of 2,3-butanedione over titanium silicalite sieves.更多还原