【作者】 张楠；

【导师】 高瑞昶； 萧泛舟；

【作者基本信息】 天津大学 ， 制药工程（专业学位）， 2016， 硕士

【摘要】 本文以7-氨基头孢烷酸(以下简称7-ACA)生产中的工业废水为研究对象,探索性地研究了采用中空纤维支撑液膜(HFSLM)技术进一步回收7-ACA的工艺可行性。在对7-ACA络合-解络传质机理分析的基础上,提出了HFSLM技术回收7-ACA过程的数学模型,并进行了模型验证。最后,对中空纤维支撑液膜技术回收废水中7-ACA的过程进行了技术经济评价,为该技术在制药废水处理领域的工业化应用提供了可靠的理论与实验依据。首先,以国内某制药企业的模拟7-ACA废水为研究对象,选取甲基三辛基氯化铵(TOMAC)-乙酸丁酯作为络合萃取体系,研究了萃取、反萃的主要影响因子,通过工艺优化得到较优操作参数。结果表明:反应温度25℃,7-ACA浓度0.2 g/L,TOMAC浓度5 mmol/L,萃取pH=7,反萃相pH=2,萃取相比0.5,反萃相比0.4是较优的工艺参数。四级萃取后萃取率、反萃率可达96.3%、95.9%。萃取剂重复使用5次后,分配系数无明显降低,该反应是放热反应。其次,在络合萃取的基础上,考察反萃相预分散支撑液膜(HFSLM-SD)技术对7-ACA稀溶液的处理效果,选取聚丙烯膜组件,确定适宜操作条件。结果表明:当膜浸润时间2 h、搅拌速度300 rpm、跨膜压差0.04 MPa、管程流速0.0177m/s和壳程流速0.007695 m/s时,萃取率可达85%。连续三次萃取率无明显减小,液膜稳定性较好。在上述试验研究基础上,本文提出了HFSLM-SD技术回收低浓度7-ACA的数学模型,并进行模型求解、验证及传质性能的分析。结果表明:K模型与K实验数量级相同,相对误差为14.6%,说明模型具有一定的可靠性。主要传质阻力分布在液膜相及壳程。HTU=0.453 m,NTU=0.283,总传质阻力较小。不同管程流速、壳程流速下的总传质系数计算值与传质阻力分析的结果、实验值吻合,进一步验证了模型的正确性。最后,通过对液膜技术回收7-ACA进行初步的技术经济分析,为该技术在处理制药废水方面的工业化应用奠定了基础。更多还原

【Abstract】 The paper focused on 7-amino-cephalosporanic acid(7-ACA)in industrial wastewater and exploringly studied the possibility in the recovering process of7-ACA by using hollow fiber supported liquid membrane(HFSLM).Based on the mass transfer mechanism analysis of complexing–decomplexing of 7-ACA,a mathematical model of HFSLM process was proposed and verified.Finally,a reliable theoretical and experimental basis was provided for the industrial application in the field of pharmaceutical wastewater treatment by the techno-economic evaluation of the HFSLM technology.Firstly,the complexation extraction system consisted of methyl trioctyl ammonium chloride(TOMAC)and butyl acetate was selected based on the simulate7-ACA wastewater from a certain domestic pharmaceutical enterprise.The main effect factors of extraction and back-extraction were studied and the optimal operating conditions were obtained by optimization.The results showed that the single-stage extraction and back-extraction partition coefficient had a maximum value when the reaction temperature was 25 ℃,the concentraction of 7-ACA was 0.2 g/L,the concentration of complexing agent was 5 mmol/L,the extraction pH was 7,the back-extraction pH was 2,the extraction phase ratio was 0.5,the back-extraction phase ratio was 0.4.The extraction rate and back-extraction rate after fourstage extraction were 96.3% and 95.9% respectively.The extraction and back-extraction partition coefficient had no significant decrease after reusing complexing agent five times,and the reaction was exothermic.Secondly,the hollow fiber supported liquid membrane with stripping dispersion(HFSLM-SD)was studied in the process of recovering 7-ACA.The polypropylene membrane module was employed to determine the appropriate operation conditions.The results showed that the extraction rate was 85% when the dipping time of membrane was 2 h,the stirring time was 300 rpm,the transmembrane pressure was0.04 MPa,the flow rate of tube side and shell side were 0.0177 m/s and 0.007695 m/s respectively.The extraction rate had no significant decrease after reusing of complexing agent three times,the liquid membrane had a good stability.Based on the abovementioned experimental results,a mass transfer mathematical model was proposed,and the model was solved,verified and applied to analyze the mass transfer performance.The results showed that the order of magnitudes of the model value and the experiment value were the same and the error was 14.6%,which verified the model was reliable.The mass transfer resistance mainly existed in the liquid membrane and the shell side.HTU = 0.453 m,NTU = 0.283,the total mass transfer resistance was small.The calculation value was consistent with the analysis results of mass transfer resistance under different flow rates of the tube side and the shell side,which further verified the accuracy of the model.Finally,a foundation was layed for its industrial application in the field of pharmaceutical wastewater treatment by a preliminary techno-economic evaluation of HFSLM-SD.更多还原