铀酰印迹树脂的合成及其识别性能研究
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摘要
分子印迹技术是近年来才发展起来的新型分离技术，它以其独特的选择性和亲合能力在很多领域引起了人们的重视，离子交换技术是铀提取与分离的主要技术。本文应用印迹技术的基本原理，从合成适于进行离子交换吸附的单体开始，首次合成了用于分离硫酸铀酰的含叔胺基印迹树脂，并进行了树脂识别性能的研究。论文除了对印迹技术及其基本原理、应用领域、前景，以及铀分离技术、离子交换法分离铀存在的问题等作简要介绍外，还包括如下三个主要部分：
首先是单体的合成。本文以烯丙基氯作烷基化试剂，在常压、不加催化剂的情况下合成了二乙基烯丙基胺，并对原料配比、水浴温度、加料方式与时间、以及沸腾反应时间对产率的影响进行了研究。在烯丙基氯与二乙胺摩尔比为1．1：1、水浴温度40℃、总加料时间2h及沸腾反应1h时，二乙基烯丙基胺的产率可达78％。合成反应时间有较大的缩短，产物经重蒸馏提纯后，纯度达98％。
其次，本研究以硫酸铀酰为模板，二乙基烯丙基胺为单体，苯乙烯为树脂基本骨架，二乙烯基苯为交联剂，偶氮二异丁腈为引发剂，在水溶液中进行三元悬浮共聚，进行了硫酸铀酰离子印迹树脂的合成。同时，对树脂合成过程中的单体选择、苯乙烯与二乙烯基苯的用量确定、引发剂的选择与用量、致孔剂选择与影响，以及其他影响因素如搅拌速度、消泡剂选择与用量等进行了研究与讨论。
最后，对合成的硫酸铀酰印迹树脂进行了识别性能研究，以验证印迹树脂的优越性。试验表明：合成树脂对硫酸铀酰的吸附量在一定程度上受pH值的影响，在pH=2时达最大，印迹树脂吸附性能最好。吸附速率随时间变化较大，在最初10min时间内，吸附受离子的外扩散所控制，树脂吸附速度最快，但随后因受内扩散所控制而变慢，并在约3h左右达到平衡。在将印迹树脂与凝胶型树脂201×7、均孔树脂D263进行的比较试验发现，印迹树脂MIPs-4是一种比D263和201×7更好的吸附剂，其吸附等温线是典型的“优吸”等温线，K_d值更大，对于低含量硫酸铀酰有较高的平衡吸附量。柱内吸附试验表明，与D263、201×7树脂相比，MIPs-4树脂的穿透体积更大，达22BV，穿透容量为21.6mg／ml。印迹树脂除了具有较好的吸附性能外，从淋洗试验可以看出，MIPs-4解吸性能也比D263、201×7树脂好，且不易出现淋洗拖尾现象。
Molecular imprinting technology (MIT) with high selectivity and affinity is developed rapidly in recent three decades. Ion exchange technology is widely used in uranium extraction and separation. During the researching, we synthesized a new kind of amine monomer for synthesis imprinted ion exchange resin. Then, a kind of uranyl sulphate imprinted ion exchange resin with amine function group is synthesized using MIT for the first time. Some experiments were also taken to testify the performance of the imprinted ion exchange resins. On basis of a brief introduction about MIT in principle, recent applications and progresses, and about common uranium separation method and it's defects. The following three aspects were studed in this thesis:
First, diethyl allylamine(DEAA) is synthesized at normal pressure and without catalysis, using allyl chloride(AC) as alkylation reagent. The affection of proportion of material, reaction time, method and time of feeding, and time of boiling is discussed. The investigation indicated a yield of 78% in the optimal conditions as follows: mol ratio of allyl chloride: diethyl amine= 1.1:1, reaction temperature=40, feeding time=2h, boiling time =lh. The content of DEAA in redistillate reachs 98%.
Secondly, the uranyl imprinted ion exchange resin for purifying uranium effluent from uranium mining and metallurgy is presented in water by copolymerization of styrene with functional monomer DEAA and crosslinker divinylbenzene, using uranyl sulphate as template and azobisisobutyronitrile as initiator. We also discussed factors influencing polymerization such as ratio of styrene: divinylbenzene, selection of initiator, selection of functional monomer, option of initiatory prerequisite and so on.
Finally, the adsorption character and selective recognition ability of the MIPs were investigated. The results showed that MIPs-1 resin, MIPs-3 resin, MIPs-4 resin and MIPs-5 resin can be used in a large pH range from 1 to 6, but the adsorption rate is highest when pH=2 for all imprinted or un-imprinted resins. At the same time, compared with 201× 7 strong base type anion ion exchange resin and medium pore resin D263, imprinted ion exchange resin MTPs-4 show better adsorption property and fast adsorption rate. In acid medium, when adsorption reaches equilibrium, the total distribution coefficients of uranium on D263, 201 X 7 and MIPs-4 resin are 0.179, 0.110 and 0.249L/g respectively. When P (U)=1.0mg/ml in effluent, the contact time is 4 minutes, breakthrough point(or breakthrough capacity) of D263, 201×7 and MIPs-4 resin are 20BV(19.6mg/ml), 18BV(17.6mg/ml) and 22BV(21.6mg/ml), and saturated capacity are 39.4, 35.2 and 36.2mg/ml respectively. The MIPs-4 resin's elution property is better than D263 resin an
d 201× 7 resin. Using the 0.05M H2SO4 and 1.0M NaC1 as elution solution, the elution volume is only about 4.0BV. The MTPs-4 resin also shows better operation property in dilute uranium solution among those kind of resins,
首先是单体的合成。本文以烯丙基氯作烷基化试剂，在常压、不加催化剂的情况下合成了二乙基烯丙基胺，并对原料配比、水浴温度、加料方式与时间、以及沸腾反应时间对产率的影响进行了研究。在烯丙基氯与二乙胺摩尔比为1．1：1、水浴温度40℃、总加料时间2h及沸腾反应1h时，二乙基烯丙基胺的产率可达78％。合成反应时间有较大的缩短，产物经重蒸馏提纯后，纯度达98％。
其次，本研究以硫酸铀酰为模板，二乙基烯丙基胺为单体，苯乙烯为树脂基本骨架，二乙烯基苯为交联剂，偶氮二异丁腈为引发剂，在水溶液中进行三元悬浮共聚，进行了硫酸铀酰离子印迹树脂的合成。同时，对树脂合成过程中的单体选择、苯乙烯与二乙烯基苯的用量确定、引发剂的选择与用量、致孔剂选择与影响，以及其他影响因素如搅拌速度、消泡剂选择与用量等进行了研究与讨论。
最后，对合成的硫酸铀酰印迹树脂进行了识别性能研究，以验证印迹树脂的优越性。试验表明：合成树脂对硫酸铀酰的吸附量在一定程度上受pH值的影响，在pH=2时达最大，印迹树脂吸附性能最好。吸附速率随时间变化较大，在最初10min时间内，吸附受离子的外扩散所控制，树脂吸附速度最快，但随后因受内扩散所控制而变慢，并在约3h左右达到平衡。在将印迹树脂与凝胶型树脂201×7、均孔树脂D263进行的比较试验发现，印迹树脂MIPs-4是一种比D263和201×7更好的吸附剂，其吸附等温线是典型的“优吸”等温线，K_d值更大，对于低含量硫酸铀酰有较高的平衡吸附量。柱内吸附试验表明，与D263、201×7树脂相比，MIPs-4树脂的穿透体积更大，达22BV，穿透容量为21.6mg／ml。印迹树脂除了具有较好的吸附性能外，从淋洗试验可以看出，MIPs-4解吸性能也比D263、201×7树脂好，且不易出现淋洗拖尾现象。
Molecular imprinting technology (MIT) with high selectivity and affinity is developed rapidly in recent three decades. Ion exchange technology is widely used in uranium extraction and separation. During the researching, we synthesized a new kind of amine monomer for synthesis imprinted ion exchange resin. Then, a kind of uranyl sulphate imprinted ion exchange resin with amine function group is synthesized using MIT for the first time. Some experiments were also taken to testify the performance of the imprinted ion exchange resins. On basis of a brief introduction about MIT in principle, recent applications and progresses, and about common uranium separation method and it's defects. The following three aspects were studed in this thesis:
First, diethyl allylamine(DEAA) is synthesized at normal pressure and without catalysis, using allyl chloride(AC) as alkylation reagent. The affection of proportion of material, reaction time, method and time of feeding, and time of boiling is discussed. The investigation indicated a yield of 78% in the optimal conditions as follows: mol ratio of allyl chloride: diethyl amine= 1.1:1, reaction temperature=40, feeding time=2h, boiling time =lh. The content of DEAA in redistillate reachs 98%.
Secondly, the uranyl imprinted ion exchange resin for purifying uranium effluent from uranium mining and metallurgy is presented in water by copolymerization of styrene with functional monomer DEAA and crosslinker divinylbenzene, using uranyl sulphate as template and azobisisobutyronitrile as initiator. We also discussed factors influencing polymerization such as ratio of styrene: divinylbenzene, selection of initiator, selection of functional monomer, option of initiatory prerequisite and so on.
Finally, the adsorption character and selective recognition ability of the MIPs were investigated. The results showed that MIPs-1 resin, MIPs-3 resin, MIPs-4 resin and MIPs-5 resin can be used in a large pH range from 1 to 6, but the adsorption rate is highest when pH=2 for all imprinted or un-imprinted resins. At the same time, compared with 201× 7 strong base type anion ion exchange resin and medium pore resin D263, imprinted ion exchange resin MTPs-4 show better adsorption property and fast adsorption rate. In acid medium, when adsorption reaches equilibrium, the total distribution coefficients of uranium on D263, 201 X 7 and MIPs-4 resin are 0.179, 0.110 and 0.249L/g respectively. When P (U)=1.0mg/ml in effluent, the contact time is 4 minutes, breakthrough point(or breakthrough capacity) of D263, 201×7 and MIPs-4 resin are 20BV(19.6mg/ml), 18BV(17.6mg/ml) and 22BV(21.6mg/ml), and saturated capacity are 39.4, 35.2 and 36.2mg/ml respectively. The MIPs-4 resin's elution property is better than D263 resin an
d 201× 7 resin. Using the 0.05M H2SO4 and 1.0M NaC1 as elution solution, the elution volume is only about 4.0BV. The MTPs-4 resin also shows better operation property in dilute uranium solution among those kind of resins,
引文
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