【作者】 毛治博；

【导师】 刘国际；

【作者基本信息】 郑州大学 ， 化学工艺， 2010， 博士

【摘要】 腰果酚是腰果壳液的主要成分,资源丰富,有重要的开发和应用价值。但由于腰果酚主要成分中存在酚羟基的间位长侧链存在1-3个C=C,在深加工过程中易变色、聚合,影响其应用,因此对腰果酚进行系统研究,提高其稳定性和适用性具有非常重要的意义。经过初步实验,对腰果酚进行加氢处理后,可以提高抗氧化能力及抗聚合能力。本文以雷尼镍为催化剂,对腰果酚进行催化加氢进行了深入研究。通过均匀设计和单因素实验系统地考察反应温度、氢气压力、反应时间、催化剂用量等因素对加氢转化率的影响。结果表明,当反应温度为118℃,反应时间4.5 h,催化剂为原料质量的1.38%,氢气压力为3.6 MPa以及搅拌速度为400 r·min-1时,转化率可达到100%,为工业化提供了理论支撑。本文以雷尼镍为催化剂,在消除内、外扩散的条件下,研究了温度在373.15～393.15 K、氢气压力为2.5-4 MPa的范围内腰果酚催化加氢反应本征动力学,选取了适合本体系的动力学模型,并利用实验数据对动力学模型进行回归及检验。实验证明腰果酚催化加氢属于二级不可逆连串平行反应,拟合得到腰果酚催化加氢动力学参数(Ea,K0)及本征动力学方程为：该研究结果完善了加氢反应和连串平行反应动力学理论,为工业化设计提供理论依据。测定了间十五烷基酚的饱和蒸汽压,用所得饱和蒸汽压数据拟合出其安托因方程,由克拉贝隆-克劳修斯方程计算出其平均摩尔汽化热。同时,在常压下采用比重瓶和乌氏粘度计分别测定了间十五烷基酚+乙醇和间十五烷基酚+正庚烷两个体系在283.15 K、288.15 K、293.15 K、298.15 K、303.15 K和308.15 K六个温度下的密度与粘度,利用VTF方程对不同温度下的的密度、粘度与组成数据进行关联,拟合出方程参数,并利用拟合结果对实验数据进行计算,总平均标准偏差小于1.5%。所得结论为分离提纯间十五烷基酚的工业化操作提供了热力学基础数据。溶解度数据是间十五烷基酚的分离和提纯的重要依据。实验采用动态法分别测定了间十五烷基酚在乙醇、丙酮、甲苯、乙酸乙酯、乙醚、四氯化碳、正庚烷和正己烷中的溶解度数据,所测数据均未见相关文献报道。采用A万方程,Apelblat方程、Wilson方程和UNIFAC模型对实验数据进行了关联,计算了各体系的溶解焓和超额焓。由于原型UNIFAC模型对本文各体系溶解度的预测值与实验值总的平均相对误差高达55.87%,本文定义了一个新基团PhOHCH2,利用C++程序寻优得到新基团的表面积参数和体积参数,同时也得到了新基团与其他基团的交互作用参数。修正的UNIFAC模型对本文各体系溶解度预测取得了良好的效果,总的平均相对误差为7.95%。通过溶解度实验数据分析,间十五烷基酚在正庚烷中溶解度随温度变化显著,对间十五烷基酚的结晶分离具有优势。为了更好的确定结晶分离条件,通过超溶解度的测定,确定了间十五烷基酚在正庚烷中介稳区宽度,实验表明,间十五烷基酚在正庚烷中的介稳态宽度随着温度升高而减小,实验条件下介稳态宽度范围为1.6 K-4.33 K。并用正交设计考察了溶剂用量、冷却温度、搅拌速度和结晶次数对重结晶收率和产品纯度的影响。加氢产品的提纯经过减压蒸馏和二次结晶最终得到纯度大于99.5%的产品。分别用红外、质谱和核磁对纯化产物进行了表征,确认为间十五烷基酚。本论文工作为间十五烷基酚的工业化生产奠定了坚实的理论基础。更多还原

【Abstract】 Cardanol, the major components of cashew nut shell liquid, is abundant and has high values of development and application.But cardanol will darken and polymerize because there are 1～3 C=C in the unsaturated side chain of the chief constituents of cardanol.Consequently, it is very important to systematically investigate cardanol, and improve its stability and applicability.It was proved by preliminary experiment that hydrogenation could improve the antioxidizability and anti-polymerizality of cardanol.In this work, the catalytic hydrogenation reaction of cardanol was carried out by using Raney nickel as catalyst. Then the effects of the reaction temperature, pressure of hydrogen, reaction time, the amount of catalyst and stirred speed on the conversion were systematically studied by the method of homogeneous design and One-factor experimental design. As the results showed us,when the temperature is 118℃,reaction time is 4.5 h, the amount of catalyst is 1.38% of the material quantity, the pressure of hydrogen is 3.6 MPa, ard the stirred speed is 400 r·min-1,the conversion can reach 100%. The result affords theoretical support for industrialization.The experiment of catalytic hydrogenation of cardanol was carried out on Raney nickel catalyst at the condition of eliminating internal and external diffusion. The kinetics data have been collected experimentally from 2.5 to 4 MPa and 373.15 to 393.15 K, respectively. Then the intrinsic kinetics of catalytic hydrogenation reaction of cardanol was studied, and the appropriate intrinsic kinetics model was selected to be regressed and tested reliable by experimental data. It was proved that the catalytic hydrogenation of cardanol is second order irreversible series-parallel reaction. The kinetic parameters (Ea, K0) and kinetic equation were obtained through fitting, the equations are as follows: These results improve the hydrogenation reaction consecutive parallel reaction kinetics theory, and provide a theoretical basis for industrial design.The data of saturation vapor pressure was determinated and used to fit Antoine equation, and the average molar heat of vaporization was calculated by Benoit Pierre Emile Clapeyron-Rudolph Clausius equation.Densities and viscosities of the binary mixtures of 3-pentadecylphenol with ethanol and n-heptane were determined by using Ostwald-Sprengel-type picnometers and Ubbelohde capillary viscometer under atmospheric pressure. The temperature was range from 283.15 K-308.15 K. The experimental values of densities and viscosities were correlated by the VTF equation, and then parameters were fitted and used to obtain calculated values.The total average standard deviations between the measured and fitted values were less than 1.5%.The results provide thermodynamic data for the separation and purification of 3-pentadecylphenol in industrialized operation.Solid-liquid equilibrium data is important foundation of the separation and purification. In this wok, dynamic method was used to determine the solubilities of 3-pentadecylphenol in ethanol, acetone, toluene, ethyl acetate chloroform, ethoxyethane, tetrachloromethane, n-heptane, and n-hexane, which didn’t appear in related literatures.The results are correlated withλh equation, Apelblat equation, Wilson equation, and UNIFAC model, then enthalpy of solution and enthalpy of excess were calculated. Because the average deviation of the values predicted by separate original UNIFAC model from the experimental valves is 55.87%, one new group was defined as PhOHCH2 in this article. With the method of procedural seeking optimum, the volume parameters and surface-area parameters of new groups were obtained, and the new interaction parameters were also obtained. Conseqently, the modified UNIFAC can perfectly predict the solubilities of the systems in this work, and the total average relative error is 7.95%.Through analysing the experimental data of solubilities, the solubility of 3-pentadecylphenol in n-heptane changes significantly by temperature, this is good for the crystallization of 3-pentadecylphenol.In order to determine better crystallization conditions, the metastable zone width of the 3-pentadecylphenol was determined by mensurating super-solubility in n-heptane. The results show that the metastable state in n-heptane decreases when the temperature increasing. The range of metastable width is 1.6K～4.33 K. Under experimental conditions, the effects of the amount of solvent, chilling temperature, stirred speed and crystal frequency on the conversion were systematically studied by the method of homogeneous design.3-pentadecylphenol can be obtained through vacuum distillation and two-step crystallization, and its purity can reach more than 99.5%.The product was characterized by MS,IR and H-NMR, and identified as 3-pentadecylphenol.This work established solid theoretical foundation of the industrial production of 3-pentadecylphenol.更多还原