Preparation Of Smart Ruthenium Ion Imprinted Polymer And Study On Its Adsorption And Separation Performance

Ruthenium is the rarest metal with the least content in the earth's crust and it is widely used in high-tech fields such as electronics,chemical industry,aerospace and medicine thanks to excellent properties of high hardness,high strength,good electrical conductivity,and excellent catalytic activity.Due to resource scarcity and uncontrolled exploitation,leading to china's ruthenium resources are severely shorted and a serious imbalance of market supply and demand,which directly impact on the development of science and technology and national strategic security.Ruthenium has been listed as one of key strategic resources for national control and development.At present,the content of ruthenium in the secondary resource waste generated in the application process of ruthenium is higher than that of the primary resource minerals.Therefore,it is necessary to realize the recycling of resources through technology development and integration,which will help alleviate china's resource supply and demand and cost control and national strategies safety is of great significance.Because the secondary resource ruthenium waste has chaotic sources,different shapes,and more complex organizational components,it is difficult to apply the technology of separating ruthenium from primary minerals in secondary resources.Therefore,it is necessary to combine existing research results to develop new materials and new technologies that can directly separate and recover ruthenium from complex environments and achieve high efficiency,short process and low cost of ruthenium from ruthenium-containing waste.In this thesis,a smart ion imprinted polymer capable of accurately separating ruthenium was designed and synthesized,and the following research results were obtained:1.Firstly,the temperature-sensitive block polymer PDEA-b-P(DEA-co-AM)was successfully synthesized by RAFT polymerization and introduced it into the synthesis process of IIP.A smart ruthenium ion-imprinted polymer(Ru-SIIP)with"flexibility"was synthesized.The morphology and structure of Ru-IIP were characterized,and its adsorption performance and process conditions were evaluated.The results showed the optimal conditions were as follows:the molar ratio of n(NMBA)/n(AM),n(AP)/n(AM)and n(TEMED)/n(AM)were 6.25,0.025 and 0.02,respectively,and the reaction temperature,reaction time,and adsorption pH were 35 ?,24 h,and 1.5,respectively.The maximum adsorption capacity and desorption rate of Ru-SIIP were 0.153 mmol/g and 80.32%,and it has a good selectivity and reusability.Secondly,theoretical research results showed that the adsorption process of Ru-SIIP was suitable to be described by a pseudo-first order kinetic model and Langmuir model,indicating that the adsorption of Ru-SIIP was a single-layer adsorption.Finally,Ru-SIIP,recycled for 8 times,could be used as catalyst for the coupling reaction of nitrobenzene and benzyl alcohol to produce imines that were widely used in medicine and agricultural industry.After the catalysis was completed,the residual amount of Ru-SIIP waste would be reduced,which proves that the smart imprinted polymer was a good green material and would not generate waste and cause additional solid waste pollution.2.In order to improve the adsorption and separation performance of Ru-SIIP for Ru,on the basis of the above work,monomer acrylic acid was added to optimize the self-assembly effect of the template ion and the functional monomer by using the synergistic effect between different functional monomers,and Ru-SIIP with better temperature and pH sensitivity was synthesized.The optimized process conditions obtained were as follows:the molar ratios of n(NMBA)/n(AM),n(AA)/n(AM),n(AP)/n(AM),n(TEMED)/n(AM)were 6.5,0.022,1.50 and 0.021,respectively,the polymerization temperature,polymerization time and adsorption pH were 35 ?,28 h and 2 respectively.The maximum adsorption capacity and desorption rate of Ru-SIIP were 0.165 mmol/g and 82.21%,and it has a good selectivity and reusability.Secondly,theoretical research results showed that the adsorption process of Ru-SIIP was suitable to be described by a pseudo-first order kinetic model and Langmuir model,indicating that the adsorption of Ru-SIIP was a single-layer adsorption.Finally,Ru-SIIP,recycled for 8 times,could be used as catalyst for the coupling reaction of nitrobenzene and benzyl alcohol to produce imines that were widely used in medicine and agricultural industry.3.Based on the practical problems of Ru-SIIP obtained by the solution polymerization method,such as small adsorption capacity and slow rate,a new type of porous Ru-SIIP with low density and dispersible in solution with interconnected pores was synthesized by Pickering HIPEs emulsion polymerization technology.The structure and morphology of the Ru-SIIP were characterized,and the adsorption performance was tested.The results showed that the prepared Ru-SIIP had a larger specific surface area,the maximum adsorption capacity of the Ru-SIIP was 0.191mmol/g.The adsorption temperature,adsorption time and adsorption pH were 35 ?,2h and 2,respectively,the desorption temperature and time were 25 ? and 4 h,the desorption rate was 82.99%,and it has good selectivity and reusability.Theoretical research shows that the adsorption process of Ru-SIIP conforms to the mixing model of zero-order and pseudo-first-order kinetic and isotherm adsorption results shown that Ru-SIIP was suitable to be expressed by the Langmuir model,indicating that the adsorption of Ru-SIIP was a single-layer adsorption.