【作者】 贾艳宗；

【导师】 马沛生；

【作者基本信息】 天津大学 ， 化学工艺， 2004， 硕士

【摘要】 聚3-羟基丁酸酯(PHB)是一种生物可完全降解塑料。3-羟基丁酸和3-羟基丁酸乙酯是合成PHB的主要单体,目前尚未工业化生产,因此研究PHB单体的合成工艺具有重要的实用价值。3-羟基丁醛液相氧化合成3-羟基丁酸在0.5L环流反应器内进行,详细考察了反应器的结构参数对氧化收率的影响。确定最佳反应器结构为:内外管高度比h/H=0.40,内外管管径比d/D=0.71,填料体积占反应物系总体积4.0%,开孔率50%的圆形渐缩式喷嘴。在上述最佳反应器内进行反应,温度60℃,压力1 MPa,氧气进气量0.018m3/h,溶剂乙酸乙酯用量为3-羟基丁醛质量的100%,催化剂醋酸钴用量为3-羟基丁醛质量的0.5%,反应4.5h,3-羟基丁酸的平均收率为88.9%。为工程放大,设计了4 L环流反应器,研究了3-羟基丁醛氧化反应在放大情况下的反应规律。正交实验表明:反应时间对氧化反应收率有显著影响,溶剂用量和进气速度对收率有一定的影响。由正交实验及外延实验确定的最佳氧化条件为:溶剂乙酸乙酯用量为3-羟基丁醛质量的140%,氧气进气量0.16 m3/h,压力1 MPa,温度60℃,催化剂醋酸钴用量为3-羟基丁醛质量的0.5%,在此条件下反应5h,平均收率为88.1%,初步解决了环流反应器的放大效应。研究了3-羟基丁酸酯化工艺,采用固体超强酸SO42-/Fe2O3催化合成3-羟基丁酸乙酯,最佳工艺条件:3-羟基丁酸1.0mol,无水乙醇1.2mol,固体超强酸10.0g,环己烷50 mL,56.3g氧化钙(或92.3g分子筛或17.1g硫酸镁),反应3h,3-羟基丁酸乙酯的平均收率达95.5%。并初步探索了3-羟基丁酸甲酯的合成条件。更多还原

【Abstract】 3-Hydroxybutyric acid and ethyl 3-hydroxybutyrate are the main monomers forproducing PHB, an important biodegradable plastic. By far, they have not beenproduced on commercial scale. Therefore, the synthesis of PHB monomers is of greatimportance.In this paper the effects of the structure parameters of the 0.5L loop reactor onthe oxidation of 3-hydroxybutanal were studied. The optimal structures are the ratioof inner and outer tube diameter (d/D) being 0.71, the ratio of inner and outer tubeheight(h/H) being 0.40, sparger with 50% porosity, the volume ratio of filler toreaction mass being 4.0%. In the optimum loop reactor, with pressure being 1MPa,temperature being 60 ℃, oxygen flow rate being 0.018m3/h, the mass ratio of solventand catalyst cobalt acetate to 3-hydroxybutanal being 100%, 0.5%, reaction timebeing 4.5h, the average yield was 88.9%.3-Hydroxybutic acid was synthesized in another 4L loop reactor designed andmanufactured. The orthogonal analysis showed that reaction time was the mostremarkable effect factor for the yield. The minor factors are the solvent amount andthe reaction pressure. The optimal reaction conditions are: time being 5h, pressurebeing 1MPa, oxygen flow rate being 0.16m3/h, temperature being 60 ℃, mass ratio ofsolvent and catalyst cobalt acetate to 3-hydroxybutanal being 140%, 0.5%respectively. Under the above conditions, the average yield was 88.1%.Preparation of ethyl 3-hydroxybutyrate from 3-hydroxybutyric acid and ethanolwas studied. The yield of ethyl 3-hydroxybutyrate could reach 95.5% under thefollowing conditions: 3-hydroxybutyric acid 1.0 mol, ethanol 1.2mol , SO42-/Fe2O310g, cyclohexane 50 mL, CaO56.3 g (or 92.3g molecular sieve or 17.1g MgSO4),time 3h. The synthesis method of methyl 3-hydroxybutyrate was primarilydetermined.更多还原