Preparation And Adsorption Separation Properities Research Of Thermosensitive Porous ReO₄^- Imprinted Polymer

Rhenium,as a kind of strategic material,the demand is very related to the new high-tech fields.Due to the scarcity of rhenium resources,the development of new recycling technology of rhenium resources from industrial waste containing rhenium as secondary resource has attracted worldwide attentions.However,due to the complex components in waste,the traditional enrichment of separation methods and technologies with the disadvantages of low separation and purification efficiency,long period are difficult to meet the require of industrial application.Therefore,it is urgent to develop a new technology and material to accurately and efficiently separate and recovery rhenium from waste.In this paper,the thermosensitive porous imprinted polymer was studied to precisely separate Re,and the following research results were obtained:1)The thermosensitive-sensitive block polymer PDEA-b-P(DEA-co-AM)was synthesized by RAFT(Reversible Breakage Chain Transfer)polymerization.PDEA-b-P(DEA-co-AM)as a"flexible"segment was introduced into preparation process of IIP(Ion Imprinted Polymer)to prepared Thermosensitive Porous ReO₄^-Imprinted Polymer(ReO₄^--TPIP,Thermosensitive Porous ReO₄^-Imprinted Polymer)via Pickering-like polymerization,and the process conditions of synthesis were optimized.Results shown that the Q,R and D of ReO₄^--TPIP were 0.1568 mmol/g,3.41 and 85.22%and reduced to 0.1212 mmol/g,1.23 and 70.01%after reuse for 11 times,respectively when polymerization temperature of 33 ? and n(AM)/n(AA),n(EGDMA)/n(AA),n(H₂O₂)/n(AA),n(Vc)/n(AA),n(NH₄ReO₄)/n(AA)of 1.01,1.82,0.042,0.011 and0.046,showing good adsorption performance and reusability.Results of adsorption study shown that the adsorption equilibrium of ReO₄^--TPIP was achieved within 120min,the adsorption kinetics conforms to the zero-order kinetics in the early stage and the quasi-first-order kinetics in the late stage.Langmuir model was more suitable to describe isothermal adsorption indicating that the adsorption was monolayer adsorption.The purity of rhenium increased from 35.4119%to 53.4812%after one adsorption/desorption cycle in the simulation solution of secondary leaching of superalloy containing rhenium.2)In order to improve the mass transfer rate of ReO₄^--TPIP,further improve the separation efficiency of ReO₄^--TPIP.Based on above work,ReO₄^--TPIP with highly perforated pore structure was prepared via Pickering HIPE-like polymerization,and the process conditions of synthesis were optimized.Results shown that the Q,R and D of ReO₄^--TPIP were 0.1650 mmol/g,3.26 and 82.21%,respectively when the ReO₄^--TPIP was prepared with n(AM)/n(AA),n(EGDMA)/n(AA),n(APS)/n(AA),n(TEMED)/n(AA),n(NH₄ReO₄)/n(AA)as 0.812,1.82,0.032,0.062 and 0.052,respectively.Q,R and D decreased to 0.1290 mmol/g,1.40 and 71.01%after reuse for11 times,which shown good reusability.Results of adsorption study shown that the adsorption equilibrium of ReO₄^--TPIP was reached within 80 min.The adsorption kinetics in the early stage was in accordance with the zero-order kinetics model,in the late stage was in accordance with the quasi-first-order kinetics model.Langmuir model was more conformed the isotherm adsorption.In simulation solution for secondary leaching of superalloy containing rhenium,the purity of rhenium increased from35.4119%to 62.8233%after an adsorption/desorption cycle.3)Due to the difficulty of recovery of the above synthesized ReO₄^--TPIP after adsorption,a thermosensitive/magnetic solid particle was designed,and a Thermosensitive/Magnetic Porous Imprinted Polymer(ReO₄^--TMPIP,Thermosensitive and Magnetic Porous ReO₄^-Imprinted Polymer)was prepared by Pickering HIPE polymerization.Results showed that the ReO₄^--TMPIP could be separated and recovered quickly under the action of external magnetic field after adsorption.After reusing for 11 times,the Q,R and D of ReO₄^--TMPIP decreased from 0.1408 mmol/g,3.26 and 86.21%,respectively,to 0.1112 mmol/g,1.203 and 74.08%,indicating good adsorption performance and reusability.Results of adsorption showed that the adsorption equilibrium of ReO₄^--TMPIP was reached within 90 minutes.The adsorption kinetics of ReO₄^--TMPIP was more fitting with the zero-order kinetics model in the early stage and the quasi-first-order kinetics model in the late stage.Langmuir model was more suitable to describe the adsorption process of ReO₄^--TMPIP.In simulation solution for secondary leaching of superalloy containing rhenium,the purity of rhenium increased from 35.4119%to 60.3571%after an adsorption/desorption cycle,proving the ReO₄^--TMPIP has great potential in industrial application.