【作者】 徐徐；

【导师】 陈小鹏； 王琳琳；

【作者基本信息】 广西大学 ， 林产化学加工工程， 2008， 硕士

【摘要】 以松节油为原料进行催化歧化反应的研究，在线跟踪分析松节油催化歧化反应过程中主要化学组成随时间和温度变化的关系，分析歧化反应产物的组成，寻找最佳歧化反应工艺条件，建立松节油催化歧化反应动力学模型。主要研究成果如下：采用美国Varian CP-3380型气相色谱仪分析松节油歧化产物的组成，色谱条件为BP×5毛细管色谱柱；氮气流速45mL·min^-1；氢气流速30mL·min^-1；空气流速300mL·min^-1；载气柱前压0．07MPa；检测器温度523．15K；汽化室温度523．15K；分流比50：1；进样量0．01μL；灵敏度10；柱温为五阶程序升温通过均匀设计安排实验，考察搅拌转速、催化剂用量、松节油与硫酸的配比、反应温度、反应时间五个因素对松节油催化歧化反应的影响，获得了Pd／C催化歧化松节油的最佳工艺条件为：催化剂用量为0．2％（以松节油重量计）、松节油和硫酸体积比为1．0、反应温度393．15K、反应时间10h、搅拌转速500r·min^-1、N₂保护气，蒎烯平均转化率达98．03％、对伞花烃评产率达61．02％。以Pd／C和20％H₂SO₄为催化剂，在353．15K-393．15K五个水平下，对松节油催化歧化反应动力学进行研究，根据Arrhenius方程，经线性回归得到双环单萜开环异构反应、双环单萜加氢反应和单环单萜脱氢反应的指前因子k₀以及反应活化能E_a，其值分别为k₀₁=6．49×10⁹ h^-1，k₀₃=3．41×10⁸h^-1，k₀₄=6．35×10¹⁰ h^-1；E_α1=77．86kJ·mol^-1，E_α3=71．33 kJ·mol^-1，E_α4=80．18kJ·mol^-1，同时得到它们的反应速率常数分别为k₁=6．49×10⁹ exp（-1126．4／T），k₃=3．41×10⁸ exp（-1031．9／T），k₄=6．35×10¹⁰exp（-1159．9／T）。结果表明，k值随着温度的升高而增大，在所考察温度范围内，单萜烯反应可近似看作一级反应（α₁≈α₃≈α4≈1）。根据建立的动力学方程及关联出的各参数进行模型检验，模型计算值与实验数据吻合良好。更多还原

【Abstract】 The reaction kinetics of catalytic disproportionation of turpentine as raw material was investigated, and on-line tracking analysis for the changes of major chemical components during catalytic disproportionation of turpentine was studied. Meanwhile, the optimal process conditions for preparation of p-cymene from turpentine were searched. After main chemical components of disproportionated products were determined, we discussed the reaction kinetic model of catalytic disproportionation of turpentine. The main contents as follows.CP-3380 gas chromatography of Varian in America was chosen to analyze the components of disproportionated turpentine. The settled conditions of chromatogram used were: BP×5 capeillary column of chromatogram, the flow rate of nitrogen as carrier gas 45mL·min^-1, the flow rate of hydrogen 30mL·min^-1, the flow rate of air 300mL·min^-1, pressure before columniation 0.07MPa, temperature of check machine 523.15K, temperature of boil room 523.15K, split stream ratio 50:1, sample volume 0.01μL, range 10, and raising temperature by five steps programThe results showed that the materials ratio, the amounts of catalyst, stirring rate, reaction temperature and reaction time were the main influencing factors. By uniform design method, the influence of those five factors above on the disproportionation of turpentine were studied further. So the optimal reaction conditions have been determined by uniform design software as follows: materials ratio of turpentine to sulfate 1.0, the amounts of catalyst 0.2%, stirring rate 500r·min^-1, reaction temperature 393.15K, reaction time 10h. Under the best processing condition, optimized result was demonstrated by three parallel experiments. Quantity of the disproportionated products were analyzed by capillary column GC Analyse Method, in which the average yield of pinene was 98.03% （mass percent）, and the average yield of p-cymene was 61.02% （mass percent）.The reaction kinetics of catalytic disproportionation of turpentine over Pd/C catalyst and 20% H₂SO₄ were investigated at temperature 353.15K-393.15K. The kinetic model parameters in Arrhenims equation were also determined, and pre-exponential factors were k₀₁=6.49×10⁹h^-1, k₀₃=3.41×10⁸h^-1, k₀₄=6.35×10¹⁰h^-1, and the activation energies were E_a1=77.86kJ·mol^-1, E_a3=71.33kJ·mol^-1, E_a4=80.18kJ·mor^-1 separately, while the reaction rate constants were confirmed as k₁=6.49×l0⁹exp（-1126.4/T）,k₃=3.41×10⁸exp（-1031.9/T）,k₄=6.35×10¹⁰exp（-1159.9/T） for opening-ring reaction of bicyclic monoterpene, hydrogenation reaction of bicyclic monoterpene, and dehydrogenation reaction of momocyclic monoterpene respectively. The final results demonstrated that kincrease with temperature increasing. In the scope of the above temperatures monoterpene hydrogenation and dehydrogenation can be regarded as the first order reactions（α₁≈α₃≈α₄≈1）. Through proof-tested using the kinetic models and parameters, it was showed that the calculated results were agreed well with the experimental data.更多还原