中药废水资源化膜材料表面改性—微结构调变的专属膜反应器精准构筑机理研究

In our country, shortage of water resources has become a heavy constraint on social and economic development. According to the basic principle of zero discharge of pharmaceutical wastewater and our team’s preliminary studies, this project focused on the design of membrane materials and the selectively assemble of the basic unit which was conforming to the characteristics of traditional Chinese Medicine wastewater. Because it was an effective way to realize the utilization of traditional Chinese Medicine wastewater, the following proposal was taken as: based on the basic principle and research pattern of material genomics, precise construction mechanism of the specific membrane reactor was formed via theoretical prediction and experimental verification. Firstly, according to our preliminary studies, the common characteristics of blockage resistance and surface deposition resistance were elucidated by date mining from 218 kinds of water extract of Chinese medicines. Then, 40-50 kinds of representative herb components, including alkaloids, phenolic acids, flavonoids were screened to establishing original wastewater simulation system and the experimental data were obtained by several means, such as MD analysis, SEM, XPS technology, etc. At the same time, the common law of "surface modification - microstructural adjustment" was revealed and the basic unit design mechanism of anti-pollution membrane material was formed by using XDLVO theory to predict and analyze the interface interaction of these components in membrane process. Finally, the correlation between reaction kinetics equation and membrane microstructure was accurately characterized and the mechanism of selective assembly was clarified simultaneously. The project is designed to solve the problem of pollution and damage to water environment with traditional Chinese medicine wastewater. Our studies would provide strong support for the sustainable development of traditional Chinese medicine industry.

水资源匮乏已成为制约我国社会经济发展的瓶颈问题。基于制药废水零排放基本原理与项目组前期研究发现：设计符合中药废水特征的膜反应器材料并进行选择性组装，是实现中药废水资源化的有效途径；提出：引入材料基因组学基本原理和研究模式，通过理论预测、实验验证，形成专属膜反应器精准构筑机理。因此，拟开展工作：1、从项目组前期建立的218种中药水提液的数万个数据中挖掘出形成膜堵塞阻力和表面沉积阻力的共性特征；2、筛选40~50种代表性中药组分—生物碱、酚酸、黄酮等建立原水模拟体系，通过MD分析与SEM、XPS等实验测定，运用XDLVO理论预测、分析上述组分在膜运行过程中的界面相互作用，揭示膜材料“表面改性—微结构调变”共性规律，形成抗污染膜基本单元设计机理；3、准确表征“反应动力学方程—膜微结构”相关性，揭示基本单元选择性组装机理。解决中药废水对水环境的污染和破坏问题，为我国中药产业可持续发展提供有力支撑。

中药废水中含有常规生化处理无法识别的中药特征性成分，该类成分既是中药中未充分利用的活性药效成分，也是新型药物POPs污染物，长期蓄积会对水体造成不可逆污染，但是，相关研究尚处于起步阶段。本项目构筑绿色、节能、对中药成分专属性处置的膜反应器，研究中以废水中各类成分与膜材料之间“构效关系”阐明为基础，形成膜材料改性与膜反应器规模化应用的设计机理。研究初期提出和建立中药废水模拟体系，阐明膜技术应用的适宜性和可行性；研究过程以中药大品种脉络宁注射液、蒲地蓝消炎口服液生产废水为研究模型，在对其中的中药特征性POPs污染物进行识别基础上，采用膜反应器消解原水中各类成分，同时最大限度地采用膜技术对活性药效成分进行回收利用，实现废水达标排放和中药资源性成分高效利用的双重研究目标。“构效关系”研究基于课题组长期在膜材料设计和膜技术应用研究基础上，通过MD分析与SEM、XPS等实验测定膜材料与中药废水中各类成分的“trade-off”效应；运用XDLVO理论预测、分析废水中各类成分在膜运行过程中的界面相互作用，揭示膜材料“表面改性—微结构调变”共性规律；针对困扰膜技术规模化应用的“膜污染严重导致膜过程无法运行”瓶颈问题，通过预处理和“双膜法”废水消解工艺研究，揭示抗污染膜单元设计和组装机理。通过四年的研究，形成了膜反应器构筑原理，对中药脉络宁注射液、蒲地蓝消炎口服液的生产废水进行了示范性消解和活性药效成分回收研究，其中，自组装的两种小型膜生物反应器均可实现蒲地蓝消炎口服液生产废水中黄芩苷回收率>80%、纯度>95%，二级出水达到直接排放标准。本项目填补了中药废水研究的空白，研究结果为中药废水处置指导原则和技术规范的建立提供支持，并为中药生产过程资源利用率不足30%的窘迫现状提供解决策略。本项目解决中药生产过程存在的环境污染、资源浪费等问题，对于推进资源生态保护和中药行业可持续发展具有重要意义。