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Thesis Advisor李春山 ; 刁琰琰
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Discipline化学工程
Keyword乙烯 氢甲酰化 丙醛 动力学 反应工艺
Other Abstract

丙醛是生产精细化学品的重要原料之一,可生产丙酸、丙醇、三羟甲基乙烷等中间体,并能进一步生产醇酸树脂和乙噻嗪,亦可应用于食品、涂料、轻纺、饲料、橡胶助剂方面的精细化学品。乙烯氢甲酰化是目前丙醛生产的主要工业化技术。本文研究了以甲苯为溶剂乙烯氢甲酰化均相反应制备丙醛的反应规律,并首次将管式反应工艺应用于该反应过程的研究,与釜式反应工艺相比,反应器结构简单,易于密封,连续化运行能力增强。采用间歇釜式反应装置研究了乙烯氢甲酰化反应合成丙醛的反应规律,考察了催化剂浓度、配体浓度、反应时间、反应温度及压力等反应条件对反应性能的影响,得到优化的工艺条件为反应温度100 ℃,反应压力2 MPa,催化剂用量0.0135 g,三苯基膦0.0387 g,甲苯10 mL,H2:C2H4:CO = 1:1:1(mol)。在该条件下,反应时间2 h,乙烯转化率与丙醛选择性均大于99 %,TOF为11000 h-1。进一步固定催化剂、配体和甲苯的用量,进行了反应宏观动力学的研究,得到三种原料气的反应级数分别为:一氧化碳(a)-0.93,乙烯(b)0.96,氢气(c)0.63;反应活化能为55 kJ/mol。在反应规律研究基础上,设计、建立了管式反应器模试连续反应装置,实现了稳定化连续运行。优化条件下,乙烯转化率平均为77 %;丙醛选择性为99 %;冷凝液产量 300 g/h。


one of important raw materials for fine chemical industry, propionaldehyde is used to produce some intermediates, such as propionate, propanol and trimethylolethane. These intermediates are further used to produce alkyd resin, ethiazide, and the fine chemicals as the additives for foods, paints, fodders, textiles, rubber and so on. Ethylene hydroformylation is the main industrial production route for propionaldehyde.In this research, homogeneous ethylene hydroformylation in toluene solvent had been carried on, and tubular reactor was firstly used for this reaction. Compared with tank reactor, the tubular reactor has simpler structure, easier sealing technology and better continuous running ability.The influences of concentration of catalyst and ligand, reaction temperature, reaction time and reaction pressure on this reaction were studied using a batch tank reactor. The optimum reaction conditions were that the molar ratio of H2, C2H4 and CO is 1:1:1; the amounts of catalyst, triphenylphosphineand and toluene were 0.0135 g, 0.0387 g and 10 mL respectively; the reaction temperature was 100 ℃; the reaction pressure was 2 MPa. Under the optimum reaction for 2 h, both ethylene conversion and propionaldehyde selectivity were over 99 %, and the TOF was as high as 11000 h-1.Fixing the amount of catalyst, ligand and toluene, the kinetics of the reaction was further studied. The reaction orders of CO, C2H4 and H2 were -0.93, 0.96 and 0.63 ,respectively. The activation energy of the reaction was 55 kJ/mol.Based on the results of the reaction rule, the tubular reactor was designed and built. The stable continuous operation was realized on the tubular reactor. Under the optimum reaction conditions, the average conversion of ethylene and selectivity to propionaldehyde was 77 % and 99 % respectively, and the collection amounts of the liquid products reached 300 g/h. 

Document Type学位论文
Recommended Citation
GB/T 7714
杨普. 乙烯氢甲酰化合成丙醛反应规律及工艺研究[D]. 北京. 中国科学院研究生院,2015.
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