短链醇中生物质基糠醛和羟甲基糠醛的催化转化研究

发布时间：2018-05-23 22:14

  本文选题：短链醇 + 糠醛　； 参考：《天津理工大学》2017年硕士论文

【摘要】：目前,由于化石燃料大量消耗所引起的环境污染和能源短缺等问题影响着社会的可持续发展,因此,探究生物质可再生资源的高效转化方法已逐渐成为化工领域的一个重要课题。其中,糠醛和5-羟甲基糠醛(5-HMF)作为重要的生物质基平台化合物,经过合适的转化过程可以制备出多种高附加值化学品和液体燃料。因此,开展短链醇中糠醛和5-HMF的催化转化研究具有重要的科学意义和广泛的应用前景。本论文中,首先研究了短链醇溶剂中糠醛的催化氧化-缩合反应过程,使用的催化体系为过渡金属的CoxOy-N@K-10与CuO-CeO_2两种纳米材料。研究发现,在“正丙醇-糠醛-氧气”反应体系中,以CoxOy-N@K-10和Cs2CO3组成催化剂体系,于0.3MPa O_2压力下,140oC条件下反应4 h后,糠醛转化率为75.1%,主产物2-甲基-3-(2-呋喃基)丙烯醛的选择性可达92.8%。进而,详细考察了CuO-CeO_2催化剂和K2CO3助剂对糠醛催化转化的促进情况;结果发现,在0.3 MPa O_2氛围中,140oC条件下反应4h,糠醛的转化率为85.4%,主产物2-甲基-3-(2-呋喃基)丙烯醛的选择性可达95.3%。另外,还分别研究了反应助剂,反应溶剂,以及反应温度和时间对氧化缩合的影响,在对催化剂进行FT-IR、XRD、BET、SEM、TEM、NH3-TPD等表征测试的基础上,结合对照实验的数据和反应现象,提出了糠醛与正丙醇之间发生氧化缩合反应的反应机理。接下来,论文研究了5-HMF的催化氧化过程;借助液相沉淀法制备了Cu-MnO_2,Cr-MnO_2,V-MnO_2,Mo-MnO_2,Mg-MnO_2,Ca-MnO_2,Al-MnO_2等离子掺杂型氧化锰催化剂,详细考察了短链醇中催化剂的类型、反应温度和反应时间对于5-HMF选择性氧化制备2,5-呋喃二甲醛(DFF)的影响情况;研究发现,以乙醇为溶剂,使用Cu-MnO_2作催化剂,于0.3MPa O_2压力下,140oC条件下反应5 h时的效果最佳;原料5-HMF的转化率为86.0%,主产物DFF的选择性可达96.1%。并且,还针对Cu-MnO_2催化剂进行了5次循环实验,发现5-HMF的转化率始终可以保持在70%以上,说明催化剂具有良好稳定性。最后对不同金属离子掺杂的氧化锰催化剂进行了XRD、BET、SEM、TEM等表征测试,合理解释了不同类型催化剂与氧化反应结果之间的关系。
[Abstract]:At present, the problem of environmental pollution and energy shortage caused by the large amount of fossil fuel consumption affects the sustainable development of the society. Therefore, the efficient transformation method of exploring biomass renewable resources has gradually become an important topic in the field of chemical industry. Among them, furfural and 5- hydroxymethyl furfural (5-HMF) are important biomass based platforms. A variety of high value added chemicals and liquid fuels can be prepared by appropriate conversion process. Therefore, the research on catalytic conversion of furfural and 5-HMF in short chain alcohols has important scientific significance and wide application prospects. In this paper, the catalytic oxidation condensation reaction process of furfural in short chain alcohols was first studied, and the process of catalytic oxidation condensation reaction of furfural in short chain alcohol solution was studied. The catalytic system used as a transition metal CoxOy-N@K-10 and CuO-CeO_2 two kinds of nanomaterials. It is found that in the reaction system of "positive propyl alcohol furfural oxygen", the catalyst system is composed of CoxOy-N@K-10 and Cs2CO3, under the pressure of 0.3MPa O_2 and the reaction of 4 h under 140oC condition, the conversion rate of furfural is 75.1%, and the main product 2- methyl -3- (2- furyl) propylene The selectivity of aldehyde can reach 92.8%., and the catalytic conversion of CuO-CeO_2 catalyst and K2CO3 promoter on furfural catalytic conversion is investigated in detail. The results show that in the atmosphere of 0.3 MPa O_2, the reaction 4H is 4h, the conversion rate of furfural is 85.4%, the selectivity of the main product 2- methyl -3- (2- furyl) acrolein can reach 95.3%.. The effects of additives, reaction solvents, reaction temperature and time on the oxidation condensation were tested on the basis of the characterization tests of FT-IR, XRD, BET, SEM, TEM, NH3-TPD, and the reaction mechanism of the oxidation condensation reaction between the furfural and the propanol was proposed. Then, the thesis studied the 5-HMF The catalytic oxidation process of Cu-MnO_2, Cr-MnO_2, V-MnO_2, Mo-MnO_2, Mg-MnO_2, Ca-MnO_2, Al-MnO_2 plasma doped manganese oxide catalyst was prepared by the liquid phase precipitation method. The influence of the catalyst type, reaction temperature and reaction time on the preparation of 2,5- furan two formaldehyde (DFF) by the selective oxidation of 5-HMF was investigated in detail. It is found that with ethanol as the solvent and using Cu-MnO_2 as the catalyst, under the pressure of 0.3MPa O_2, the reaction is best when the reaction is 5 h under the condition of 140oC, the conversion rate of 5-HMF is 86%, the selectivity of the main product DFF is 96.1%. and the 5 cycles of the Cu-MnO_2 catalyst have been carried out, and the conversion rate of 5-HMF can always be kept at 70%. The catalyst has good stability. Finally, the characterization tests of XRD, BET, SEM and TEM are carried out for the manganese oxide catalysts doped with different metal ions. The relationship between different types of catalysts and the results of oxidation is explained.
【学位授予单位】：天津理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626.11

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