CN105771904B - 一种磁性吸附剂及其制备方法与对硝酸介质中钯的回收 - Google Patents
一种磁性吸附剂及其制备方法与对硝酸介质中钯的回收 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 90
- 239000003463 adsorbent Substances 0.000 title claims abstract description 83
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 62
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 33
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims abstract description 8
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Abstract
本发明涉及一种磁性吸附剂及其制备方法与对硝酸介质中钯的回收。通过EDC•HCl和NHS催化的酰胺化反应,将氮杂大环羧酸衍生物修饰到氨基功能化的磁性微球外表面,制备了以Fe3O4磁性纳米颗粒为核芯,SiO2为保护壳层,氮杂大环羧酸衍生物修饰于壳层外缘的核壳结构吸附剂,制备工艺能耗低、成本低、操作简便。磁性吸附剂在较广的硝酸浓度范围内,对钯吸附容量大、吸附速率快,且在多种高放废液裂片核素的干扰下,对钯表现出极佳的选择性分离能力,而吸附剂表面吸附的钯可以用5%硫脲的硝酸溶液洗脱,利于循环使用。
Description
技术领域
本发明属于资源利用与环境保护技术领域,特别涉及一种磁性吸附剂及其制备方法与对硝酸介质中钯的回收。
背景技术
在能源和环境两大主题的当代,伴随温室效应、雾霾污染等问题的日益严峻,积极发展能量密度高、清洁低碳的核能,不仅能有效改善能源结构,缓解环境压力,更有利于保障国家的能源与经济安全。根据我国核电中长期发展规划(国家发展和改革委员会.核电中长期发展规划2005-2020,2007.),截至到2020年,中国运行核电装机将达到5800万千瓦,在建3000万千瓦。然而,核燃料在循环和后处理的过程中都会产生大量的放射性废液,其中强释热的裂片核素和锕系核素对人类生活和生态环境都构成了潜在的危害。因此,研发绿色环保的新型分离技术实现裂片、锕系核素的选择性分离,对资源的可持续利用和环境保护都具有重要的战略意义。
钯作为铂族金属的一员,地壳中的含量仅约为10-6,但其卓越的理化性质,被广泛应用于择形催化和汽车元件制造等领域。然而,自然界有限的资源供给很难满足人们持续增长的需求。近年来,高放废物中的裂片钯逐渐引起了大家的关注。据文献报道,动力堆的乏燃料在2030年蓄积的裂片钯总量将达到1000t,将在很大程度上缓解目前钯资源供需失调的现状。其次,裂片钯的6种同位素中,仅有含量为17%的Pd107是具有放射性的,且最大的射线能量只有35Kev,是一种较弱的β射线,能在很多工业材料中应用。另外,裂片钯在高放废物最终玻璃固化的过程中易形成单相,这会大大降低玻璃固化体的稳定性,易造成放射性废物的泄露。因此,研究裂片钯的选择性分离在湿法冶金和核燃料后处理等领域都具有重要的指导意义。
目前,硝酸介质中裂片钯的分离方法主要有:离子交换法、溶剂萃取法和吸附法。相较之下,吸附法因其产生的二次废液少、易操作、原料成本低和分离效率高的优点,被逐渐应用于高放废物中低浓度裂片钯的富集与分离。清华大学先后报道了氨基化的二环己基十八冠六醚(Gang Ye,et al.Separation and Purification Technology.2013,106,38-46)和氨基化的杯芳烃冠醚(Gang Ye,et al.Chemical Engineering Journal.2013,232,319-326)修饰的介孔二氧化硅对硝酸介质中裂片钯的分离,并取得了较理想的结果。但是,介孔材料在核燃料后处理强放、高酸条件下的分离则成为了难题。另外,常规固相萃取技术的吸附剂材料,如介孔硅、碳纳米管、有机金属骨架结构在色谱柱填料分离核素的过程中,也会面临因柱压升高而引起的传质阻力过大的问题,这些都限制了其在实际工业中的应用。
氮杂大环羧酸衍生物是一类含有多个C、N、O原子的饱和大环分子,N原子在环内呈高度对称分布,紧连的羧基臂在环外侧,能同时提供多个O、N原子参与过渡金属、部分重金属和稀有金属的配位模型构建,被广泛应用于核磁显影和放药标记等医学领域中。但至今为止,关于氮杂大环羧酸衍生物对贵金属的配位情况,尤其涉及高放废物中裂片钯的快速分离则尚未报道。另外,氮杂大环羧酸衍生物因羧基和N原子的存在,在硝酸环境中易溶解流失,需要将其修饰于固相材料表面,以实现对金属离子的吸附分离。
发明内容
针对现有技术不足,本发明提供了一种磁性吸附剂及其制备方法与对硝酸介质中钯的回收。
一种磁性吸附剂,其是以Fe3O4磁性纳米颗粒为核芯,SiO2为保护壳层,氮杂大环羧酸衍生物修饰于壳层外缘的核壳结构磁性吸附剂;所述氮杂大环羧酸衍生物的环骨架上含有N原子,环骨架上的N原子与羧基臂相连,且所述羧基臂位于环外。
进一步地,所述氮杂大环羧酸衍生物为1,4,7-三氮杂环壬烷-1,4,7-三乙酸、1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸、1,4,8,11-四氮杂环十四烷-1,4,8,11-四乙酸、1,4,7,10,13-五氮杂环十五烷-1,4,7,10,13-五乙酸或1,4,7,10,13,16-六氮杂环十八烷-1,4,7,10,13,16-六乙酸。
上述一种磁性吸附剂的制备方法,包括以下步骤:
(1)将氮杂大环羧酸衍生物溶解于pH为5.2~5.6的生物缓冲溶液中,氮气保护下,加入催化剂EDC·HCl和NHS,室温下搅拌反应1h,制备氮杂大环羧酸衍生物的活化中间体;
(2)向上述反应液中加入氨基功能化的磁性微球,超声分散后,控制体系的温度和反应时间至酰胺化反应结束,磁铁分离产品后,用0.1mol/L HCl溶液、乙醇和水交替洗涤数次,45℃真空干燥12h,制得核壳结构磁性吸附剂;所述氨基功能化的磁性微球是以Fe3O4磁性纳米颗粒为核芯,SiO2为保护壳层,壳层上含有末端氨基结构。
步骤(1)的反应体系中,每活化1mmol氮杂大环羧酸衍生物,需加入催化剂EDC·HCl的量为9.95~40.05mmol,EDC·HCl和NHS加入量的摩尔比为(2~2.5):1。
步骤(1)的反应体系中,所述生物缓冲溶液为1.0mol/L的吗啉乙磺酸水溶液,加入的量为45~55mL生物缓冲溶液每1.0mmol氮杂大环羧酸衍生物。
步骤(2)的反应体系中,所述氨基功能化的磁性微球加入量为0.45~0.55g每1mmol氮杂大环羧酸衍生物。
步骤(2)的反应体系,控制反应先在25±0.2℃下搅拌反应8h,后调整为4±0.2℃下静置12~16h。
一种磁性吸附剂对硝酸介质中钯的回收,所述磁性吸附剂经真空干燥后,加入到钯的硝酸溶液中,超声5min后,在25±0.2℃的恒温条件下以200r/min振荡至吸附平衡。
所述钯的硝酸溶液,硝酸酸度为0.01~5.0mol/L,钯的浓度为48~52mg/L。
每处理10mL所述钯的硝酸溶液,加入的磁性吸附剂量为0.09~0.11g。
一种磁性吸附剂对硝酸介质中钯的回收,所述磁性吸附剂经真空干燥后,加入到高放废液模拟料液中,超声5min后,在25±0.2℃的恒温条件下以200r/min振荡至吸附平衡;所述高放废液模拟料液中,硝酸酸度为0.9~1.1mol/L,裂片核素包括K,Cs,Sr,Ba,Cd,Ni,Nd,Cr,Ru,Fe,Pd,对应的质量浓度均为48~52mg/L。
每处理10mL所述高放废液模拟料液,加入的磁性吸附剂量为0.1~0.15g。
所述磁性吸附剂表面吸附的钯,在25±0.2℃的恒温条件下采用5%硫脲的硝酸溶液脱附,实现循环使用。
吸附原理:氮杂大环羧酸衍生物环上的多个N原子和羧基臂的O原子,能与钯在硝酸介质中构建稳定的络合物,对其他裂片核素的螯合能力受环空腔大小的限制、N原子和羧基臂O原子质子化效应影响,以及固相材料表面的自由度限制,在硝酸介质中较难形成相应的配合物结构,因此对硝酸介质中的钯具有选择性识别与分离性能。
本发明的有益效果为:
1)本发明通过EDC·HCl和NHS催化的酰胺化反应,将氮杂大环羧酸衍生物修饰到磁性复合微球的SiO2壳层外缘,制备了具有核壳结构的新型磁性吸附剂,且制备工艺能耗低、操作简便,采用低毒、环境污染小的生物缓冲液作为反应溶剂,避免了传统吸附剂制备过程中有机溶剂的耗用,降低运行成本,经济环保,易于实现放大生产。
2)本发明制备的磁性吸附剂表面修饰的氮杂大环羧酸衍生物,在较广的硝酸浓度范围内,对钯吸附容量大、吸附速率快,且在多种高放废液裂片核素的干扰下,对钯表现出极佳的选择性分离能力,而吸附剂表面吸附的钯可以用5%硫脲的硝酸溶液洗脱,利于循环使用。
3)本方明制备的磁性吸附剂具有良好的超顺磁性能,在外部磁场作用下易于分离,缩短了固相萃取中固液分离的周期,适于强放、低酸极端条件下的操作,成本低、分离效率高。
附图说明
图1(a)为实施例1中氨基功能化的磁性微球透射电子显微镜照片;
图1(b)为实施例1中磁性吸附剂的透射电子显微镜照片;
图2(a)为Fe3O4磁性纳米颗粒的X射线衍生谱图;图2(b)为实施例1中氨基功能化的磁性微球的X射线衍生谱图;图2(c)为实施例1中磁性吸附剂的X射线衍生谱图;
图3为磁性吸附剂对钯的吸附率与硝酸浓度的曲线图。
具体实施方式
下面结合附图和具体实施方式对本发明做进一步说明。应该强调的是,下述说明仅仅是示例性的,而不是为了限制本发明的范围及其应用。
实施例1:一种磁性吸附剂的制备方法,包括以下步骤:
(1)将1.0mmol氮杂大环羧酸衍生物1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸(DOTA)溶解于50mL吗啉乙磺酸生物缓冲溶液中,调节pH缓冲区间为5.4~5.5,氮气保护下,加入催化剂25.0mmol EDC·HCl和10mmol NHS,室温下搅拌反应1h,制备氮杂大环羧酸衍生物DOTA的活化中间体。
(2)向上述反应液中加入0.5g氨基功能化的磁性微球(氨基功能化的磁性微球的制备参考有关文献Wang Xiangke,et al.Chemical Engineering Journal.2014,235,275-283),超声分散后,首先在25±0.2℃温度下,机械搅拌的作用下反应8h,再冷却至4±0.2℃静置12h。磁铁分离产品后,用0.1mol/L HCl、乙醇和水交替洗涤数次,45℃下真空干燥12h,制得所需的核壳结构磁性吸附剂。
图1(a)为氨基功能化的磁性微球的透射电子显微镜照片,可以明显观察到核芯Fe3O4(颜色较深的黑色部分)粒径为300nm左右,SiO2壳层(颜色较浅的灰色部分)厚度为20nm左右。图1(b)为磁性吸附剂的透射电子显微镜照片,其原有的壳层形貌和厚度没有明显变化,说明氮杂大环羧酸衍生物主要修饰在SiO2壳层的边缘。
图2(a)为Fe3O4磁性纳米颗粒的X射线衍生谱图,对应的晶面分别为(111),(220),(311),(400),(422),(511),(440),属于标准Fe3O4卡片的面心立方晶系;图2(b)为氨基功能化的磁性微球的X射线衍生谱图,图2(c)为磁性吸附剂的X射线衍生谱图,可以看出氨基的功能化和有机分子氮杂大环羧酸衍生物的修饰,都没有改变原有的Fe3O4晶型结构。
实施例2:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为0.01mol/L的50mg/L钯溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.1g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出上层清液,用原子吸收光谱测定其中钯的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率E=99.8%。
实施例3:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为0.1mol/L的50mg/L钯溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.1g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出上层清液,用原子吸收光谱测定其中钯的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率E=98.2%。
实施例4:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为0.5mol/L的50mg/L钯溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.1g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出上层清液,用原子吸收光谱测定其中钯的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率E=90.3%。实施例5:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为1.0mol/L的50mg/L钯溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.1g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出上层清液,用原子吸收光谱测定其中钯的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率E=76.7%。实施例6:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为2.0mol/L的50mg/L钯溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.1g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出上层清液,用原子吸收光谱测定其中钯的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率E=66.1%。实施例7:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为3.0mol/L的50mg/L钯溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.1g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出上层清液,用原子吸收光谱测定其中钯的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率E=60.7%。实施例8:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为4.0mol/L的50mg/L钯溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.1g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出上层清液,用原子吸收光谱测定其中钯的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率E=53.1%。实施例9:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为5.0mol/L的50mg/L钯溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.1g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出上层清液,用原子吸收光谱测定其中钯的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率E=50.3%。
图3为硝酸介质中,磁性吸附剂对钯的吸附率E与硝酸浓度C(HNO3)的曲线图,磁性吸附剂对钯在0.01~5.0mol/L的硝酸浓度范围内都有较强的吸附性能,吸附率为50%以上,且吸附率随硝酸浓度的升高而较低,硝酸浓度低于1.0mol/L,磁性吸附剂对钯的吸附率为76%以上;硝酸浓度低于0.5mol/L,磁性吸附剂对钯的吸附率为90%以上;硝酸浓度低于0.1mol/L,磁性吸附剂对钯的吸附率为98%以上;硝酸浓度为0.01mol/L,磁性吸附剂对钯的吸附率达99.8%;这主要是因为高硝酸浓度下,环内的N原子和羧基臂的O原子会质子化作用,从而导致H+与钯竞争吸附剂表面的吸附位点。
实施例10:磁性吸附剂的循环利用
选择5%硫脲的硝酸溶液作为钯的解析剂,其中硝酸浓度为0.5mol/L。将实施例4中达到吸附平衡后的磁性吸附剂,磁铁分离后,用去离子水洗涤4-5次,以去除残余未吸附的钯的硝酸溶液,真空60℃干燥12h后,转入到锥形瓶中,并加入5%硫脲的硝酸溶液,在25±0.2℃的恒温空气浴内以200r/min振荡2h,离心分离固体后,取出清液样品,用原子吸收光谱测定钯的质量浓度。根据吸附平衡公式计算此时钯累计的洗脱率为92%。如表1所示,磁性吸附剂循环复用4次后,对钯的吸附性能无明显降低。
表1
实施例11:实施例1所得的磁性吸附剂对硝酸介质中钯的回收
移取硝酸酸度为1.0mol/L的高放废液裂片核素溶液10mL于锥形瓶中,加入实施例1所得的磁性吸附剂0.15g,超声5min后,在25±0.2℃的恒温空气浴内以200r/min振荡24h。磁铁分离吸附剂后,取出剩余清液,用电感耦合等离子体光谱仪(ICP-OES)测定各裂片核素K,Cs,Sr,Ba,Cd,Ni,Nd,Cr,Ru,Fe,Pd的质量浓度,根据吸附平衡公式计算出该吸附剂此时对钯的吸附率为93.1%,而其他裂片核素的吸附率均在5%以下,具体结果见表2所示。
表2
Claims (11)
1.一种磁性吸附剂在回收硝酸介质中钯的应用,其特征在于,所述磁性吸附剂是以Fe3O4磁性纳米颗粒为核芯,SiO2为保护壳层,氮杂大环羧酸衍生物修饰于壳层外缘的核壳结构磁性吸附剂;所述氮杂大环羧酸衍生物的环骨架上含有N原子,环骨架上的N原子与羧基臂相连,且所述羧基臂位于环外;
所述氮杂大环羧酸衍生物为1,4,7-三氮杂环壬烷-1,4,7-三乙酸、1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸、1,4,8,11-四氮杂环十四烷-1,4,8,11-四乙酸、1,4,7,10,13-五氮杂环十五烷-1,4,7,10,13-五乙酸或1,4,7,10,13,16-六氮杂环十八烷-1,4,7,10,13,16-六乙酸;
所述磁性吸附剂对硝酸介质中的钯具有选择性识别与分离性能,用于回收钯的硝酸溶液中的钯,其中硝酸浓度为0.01~5.0 mol/L,钯的浓度为48~52 mg/L;还能用于回收高放废液模拟料液中钯,其中硝酸浓度为0.9~1.1 mol/L,裂片核素包括K、Cs、Sr、Ba、Cd、Ni、Nd、Cr、Ru、Fe、Pd,对应的质量浓度均为48~52 mg/L。
2.根据权利要求1所述的应用,其特征在于,所述磁性吸附剂的制备方法包括以下步骤:
(1) 将氮杂大环羧酸衍生物溶解于pH为5.2~5.6的生物缓冲溶液中,氮气保护下,加入催化剂EDC ▪ HCl和NHS,室温下搅拌反应1 h,制备氮杂大环羧酸衍生物的活化中间体;
(2) 向上述反应液中加入氨基功能化的磁性微球,超声分散后,控制体系的温度和反应时间至酰胺化反应结束,磁铁分离产品后,用0.1 mol/L HCl溶液、乙醇和水交替洗涤数次,45℃真空干燥12 h,制得核壳结构磁性吸附剂;所述氨基功能化的磁性微球是以Fe3O4磁性纳米颗粒为核芯,SiO2为保护壳层,壳层上含有末端氨基结构。
3.根据权利要求2所述的应用,其特征在于,步骤(1)的反应体系中,每活化1 mmol氮杂大环羧酸衍生物,需加入催化剂EDC ▪ HCl的量为9.95~40.05 mmol,EDC ▪ HCl和NHS加入量的摩尔比为(2~2.5): 1。
4.根据权利要求2所述的应用,其特征在于,步骤(1)的反应体系中,所述生物缓冲溶液为1.0 mol/L的吗啉乙磺酸水溶液,加入的量为45~55 mL生物缓冲溶液每1.0 mmol氮杂大环羧酸衍生物。
5.根据权利要求2所述的应用,其特征在于,步骤(2)的反应体系中,所述氨基功能化的磁性微球加入量为0.45~0.55 g每1 mmol氮杂大环羧酸衍生物。
6.根据权利要求2所述的应用,其特征在于,步骤(2)的反应体系,控制反应先在25±0.2 ℃下搅拌反应8 h,后调整为4±0.2 ℃下静置12~16 h。
7.根据权利要求1所述的应用,其特征在于,所述磁性吸附剂经真空干燥后,加入到钯的硝酸溶液中,超声5 min后,在25±0.2℃的恒温条件下以200 r/min振荡至吸附平衡。
8.根据权利要求7所述的应用,其特征在于,每处理10 mL所述钯的硝酸溶液,加入的磁性吸附剂量为0.09~0.11 g。
9.根据权利要求1所述的应用,其特征在于,所述磁性吸附剂经真空干燥后,加入到高放废液模拟料液中,超声5 min后,在25±0.2℃的恒温条件下以200 r/min振荡至吸附平衡。
10.根据权利要求9所述的应用,其特征在于,每处理10 mL所述高放废液模拟料液,加入的磁性吸附剂量为0.1~0.15 g。
11.根据权利要求7-10任一权利要求所述的应用,其特征在于,所述磁性吸附剂表面吸附的钯,在25±0.2℃的恒温条件下采用5 %硫脲的硝酸溶液脱附,实现循环使用。
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