【作者】 邱挺；

【导师】 马沛生； 王良恩；

【作者基本信息】 天津大学 ， 化学工艺， 2003， 博士

【摘要】 本文在催化精馏水解工艺工业化成功的基础上，进行了醋酸甲酯和甲醇共沸物催化精馏水解新工艺及其相关基础研究，以进一步改进工艺，达到简化流程及节能降耗的目的，同时建立起催化精馏过程模拟和设计的理论体系，为中试及将来的工业化打下了坚实的基础。主要研究内容如下：1．在直径为25mm的小试塔中进行了实验，获得了丰富的实验数据和满意的实验结果。结果表明，最佳工艺条件为：醋酸甲酯和甲醇从塔顶进料，空速为0.356，水酯比为5.0，回流进料比为2.15，此时酯水解率可达80.38%,回收系统的能耗比传统的固定床工艺降低39.99%，比催化精馏工艺降低23.5%，以年产3.3万吨PVA规模计，可获得经济效益达942.5万元/年。因此，该新工艺的工业化将可获得很高的经济效益和社会效益。2．在间歇搅拌釜式反应器中测定了SK-1A型阳离子交换树脂催化的醋酸甲酯水解反应动力学，得到了以单位质量干催化剂为基准的醋酸甲酯催化水解动力学方程为：其中： 这为醋酸甲酯催化精馏水解过程的模拟计算提供必要的基础数据。3．利用液液平衡釜测定了常压下醋酸甲酯－水二元系（20.0～50.0℃）的部分互溶度数据、醋酸甲酯－甲醇－水和醋酸甲酯－水－醋酸三元体系（20.0～50.0℃）以及醋酸甲酯－甲醇－水－醋酸四元体系（20.0～50.0℃）的液液平衡数据，为工业生产提供了设计依据，也充实了液液平衡数据库。同时，采用NRTL和UNIQUAC模型，利用单纯形优化方法对上述体系的液液平衡数据进行了关联，得到相应的模型参数。根据回归的模型参数进行了计算,所得计算值与实测值的平均误差较小。另外，采用面向对象的VB6.0开发出液液相平衡关联及预测通用软件，可以方便地运用于液液相平衡计算。4．建立了非平衡级速率模型，采用收敛性能很好的Newton同伦连续算法，在计算中合理地引入阻尼因子，建立了可稳定收敛的计算方法。应用该方法结<WP=4>合实验测定的醋酸甲酯催化水解动力学数据对醋酸甲酯与甲醇共沸物催化精馏水解小试过程进行了模拟计算，得到了满意的结果。该计算方法对初值的选取范围几乎没有限制，收敛性能很好，解决了以往对初值要求高的缺点。通过模拟计算得出了增大回流进料比不能有效强化醋酸甲酯水解的催化精馏过程的结论，为中试过程提供了有效的指导，也给工业化提供了依据。更多还原

【Abstract】 Based on the success of the industrialization of the process of catalytic distillation of methyl acetate hydrolysis, the new process of catalytic distillation of methyl acetate and methanol azeotrope hydrolysis and related fundamental research were studied. These can make further improvement on the process in order to simplify the process and reduce the energy-consumed of the recovery system. In addition, theoretical system of the simulation and design the catalytic distillation process were established, which can provide the basis of the pilot plant and industrialization in the future. The main works were as follows:1. The experiments were carried out in a column of 25mm in diameter, and the large quantity of experimental data and satisfactory results were obtained. The results demonstrate that optimal technological conditions are as follows: methyl acetate and methanol azeotrope fed from the top of reactive section, space velocity was 0.356, molar ratio of water-methyl acetate was 5.0 and ratio of reflux to feed was 2.15. Under the optimal operational conditions, the conversion of ester could reach 80.38% and the energy consumption of recovery system was lower by 39.99% than conventional fixed bed reactor technology, by 23.5% than catalytic distillation technology. Based on the scale of 33 thousands ton of PVA per year, the economic benefit could reach 9.425 million yuan per year. Therefore, the industrialization of new technology will obtain greater economic and social benefit. 2. The kinetics of the hydrolysis of methyl acetate was measured in a batch stirred reactor with SK-1A cation exchange resin as catalyst, and the kinetic equation based on the per catalyst quality for describing the hydrolysis of methyl acetate could be expressed aswhere <WP=6>These can provide necessary data for the simulation and calculation of the process of catalytic distillation hydrolysis of methyl acetate.3. LLE(liquid-liquid equilibrium) data have been determined in the LLE still for the quaternary system of methyl acetate-methanol-water-acetic acid, the related ternary system of methyl acetate-methanol-water and methyl acetate-water-acetic acid, and the related methyl acetate-water binary system at 20℃,30℃,40℃ and 50℃ under atmospheric pressure. These works can provide sufficient data support for industry design and add new LLE data into the data bank. The experimental data have been correlated by the activity coefficient models including NRTL and UNIQUAC. And the model parameters were gained by simplex optimization and the comparison between calculated and experimental data shows good agreement. In addition, the software of LLE correlation and prediction was developed by Visual Basic 6.0, which can correlate and calculate LLE data conveniently.4. A stable convergence calculation method using Newton homotopy continuation method based on the non-equilibrium rate model was established. It was used to simulate the catalytic distillation column of methyl acetate and methanol azeotrope hydrolysis combined with the macro-dynamic equation of methyl acetate hydrolysis. The facts of rapid convergence from any one starting point show that the algorithm is more robust. It was concluded from the calculation that the results were satisfactory and the ratio of reflux to methyl acetate feed had less influence on the conversion of methyl acetate. It is good guide to the pilot experiment, and can provide the basis for the industrial design.更多还原