荷电膜分离过程中的卷式组件和相关设备研究

发布时间：2019-04-26 20:24

【摘要】：荷电膜技术作为一种新型的分离技术,由于其独特的荷电特性,可以进行离子物系的分离分级,在绿色化学和清洁化工方面具有十分广泛的应用前景。本论文围绕荷电膜分离过程设备开发和应用方面进行了相关的研究与讨论。第一部分,针对现有板式扩散渗析器装填密度小、传质效率低的缺点,设计了一种全新的扩散渗析组器——螺旋卷式扩散渗析膜组件,并对其进行结构优化和工业化应用研究,实现了该膜组件的批量制备。第二部分,研制了一种实验用集成式双极膜电渗析器,并应用于烟酸的清洁化生产实验研究。主要结果如下:1)发明了一种螺旋卷式扩散渗析膜组件,将膜组件用于H2SO4/FeSO4料液和HCl/FeCl2料液的酸回收过程,结果显示,两种体系的回收率都可达85%以上,同时Fe2+的泄漏率都小于20%,采用螺旋卷式扩散渗析膜组件的单位膜面积废酸处理量大于小型实验用板框式扩散渗析器的单位膜面积废酸处理量,说明本螺旋卷式扩散渗析膜组件的传质效率优于现有技术的板框式扩散渗析器,而对于HCl/FeCl2体系,这种优势更加明显。2)基于阿基米德螺线,建立了螺旋卷式扩散渗析膜组件的几何模型,并对其进行了模型验证,误差小于1%;对螺旋卷式扩散渗析膜组件的传质模型进行了讨论分析,提出总传质系数的表达式。3)作为螺旋卷式扩散渗析膜组件的结构优化,研制了一种双程螺旋卷式扩散渗析膜组件,该新型膜组件省略了侧流管,有比单程式膜组件更大的装填密度,单位膜面积料液处理量更大。4)设计加工了SWDD-01型预紧式卷膜机,可实现11 m2、5 m2、10 m2三个规格的膜组件的同线生产;提出了螺旋卷式扩散渗析膜组件产品的质量控制指标和控制方法;长期稳定性试验显示膜组件在30%硫酸介质连续运行6个月,膜组件不串漏;第三方性能测试结果显示:对于HCl/AlCl3料液样品(含Al3+ 0.995 mol/L,H+ 2.96 mol/L),10平方米组件在回收酸流量达7.4 mL/m2.min时H+回收率达96.9%,而Al3+截留率达99.5%;提出了螺旋卷式扩散渗析膜组件作为废酸回收工程应用的工艺流程和实现方法。5)设计加工了一种集成式双极膜电渗析器,可以满足各种膜堆构型的双极膜电渗析实验的需要;进行了双极膜电渗析法由烟酸钠清洁生产烟酸的实验,使用BP-C-BP膜堆构型,考察了料液浓度、电流效率等操作参数对双极膜电渗析效果(诸如能量消耗、电流效率、膜堆电压和转化率等)的影响,在经济可行的条件下烟酸钠转化效率可达73%,电流效率最高可达95%,产生每千克烟酸(0.1 mol/L)的能耗最低可达4.1 kWh。所得烟酸可通过冷却结晶法简易地从溶液中析出,所得烟酸纯度达99%,实现了烟酸的清洁化生产。
[Abstract]:As a new separation technology, charged membrane technology can be used in separation and classification of ion system because of its unique charged characteristics. It has a wide application prospect in green chemistry and clean chemical industry. In this paper, the development and application of charged membrane separation equipment are studied and discussed. In the first part, aiming at the shortcomings of low loading density and low mass transfer efficiency of the existing plate diffusivity dialyzers, a new diffusing dialyzer, spiral coil diffused dialysate membrane assembly, is designed, and its structure optimization and industrial application are studied. The batch preparation of the membrane module was realized. In the second part, an integrated bipolar membrane electrodialysis device is developed and applied to the clean production of nicotinic acid. The main results are as follows: 1) A spiral coil diffusion dialysis membrane module was invented, which was used in the acid recovery process of H2SO4/FeSO4 and HCl/FeCl2 feed solution. The results show that the recovery rate of both systems can reach more than 85%. At the same time, the leakage rate of Fe2 is less than 20%, and the waste acid treatment capacity per unit membrane area using spiral coil diffusion dialyzer module is larger than that of small-scale plate-frame diffusing dialyzer. It is shown that the mass transfer efficiency of the spiral coil diffusion dialyzer module is better than that of the frame diffusion dialyzer with the prior art, and this advantage is more obvious for the HCl/FeCl2 system. 2) based on Archimedes solenoid, The geometric model of the diffuser-dialyzed membrane module with spiral coil is established and verified. The error is less than 1%. The mass transfer model of the diffusion dialysis membrane module with spiral coil is discussed and analyzed, and the expression of the total mass transfer coefficient is put forward. 3) as the structural optimization of the diffusion dialysis membrane module with spiral coil, a kind of two-way spiral coil diffusion dialysis membrane module is developed. The new membrane assembly omits the sideflow tube, has a higher loading density than the single-pass membrane module, and a larger liquid handling capacity per unit membrane area. 4) the SWDD- 01 pre-tight film coiling machine is designed and processed. Can achieve 11 m ~ 2, 5 m ~ 2, 10 m ~ 2 three specifications of membrane assembly of the same line production; The quality control index and control method of the product of spiral coil diffusion dialysis membrane module were put forward, the long-term stability test showed that the membrane module operated continuously in 30% sulfuric acid medium for 6 months, and the membrane module did not leak in series. The results of the third-party performance test showed that for the HCl/AlCl3 sample (including Al3 0.995 mol/L,H 2.96 mol/L), the H recovery rate of 10 square meter components reached 96.9% when the recovery rate of acid reached 7.4 mL/m2.min. The rejection rate of Al3 was 99.5%. The technological process and realization method for the application of spiral coil diffusion dialysate module as waste acid recovery engineering are put forward. 5) an integrated bipolar membrane electrodialysis device is designed and manufactured. It can meet the needs of bipolar membrane electrodialysis experiments of various membrane stack configurations. The experiment of clean production of nicotinic acid from sodium nicotinate by bipolar membrane electrodialysis was carried out. The BP-C-BP membrane stack configuration was used to investigate the effects of operating parameters such as liquid concentration and current efficiency on electrodialysis of bipolar membrane, such as energy consumption, current efficiency, and so on. Under the economical and feasible conditions, the conversion efficiency of sodium nicotinate can reach 73%, the current efficiency can be up to 95%, and the energy consumption per kilogram of nicotinic acid (0.1 mol/L) can be as low as 4.1 kWh.. The obtained nicotinic acid can be easily precipitated from the solution by cooling crystallization. The purity of niacin can reach 99% and the clean production of nicotinic acid can be realized.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TQ051.893

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