CN113214493B - 一种钴基金属有机骨架材料的制备及其低碳烃分离应用 - Google Patents
一种钴基金属有机骨架材料的制备及其低碳烃分离应用 Download PDFInfo
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Abstract
一种钴基金属有机骨架材料的制备及其低碳烃分离应用,属于晶态多孔材料制备和气体分离技术领域。该MOF材料由有机配体5,5'‑双(1H‑吡唑‑4‑基)‑2,2'‑联吡啶(DPBP)与乙酸钴(Co(CH3COO)2)在溶剂热条件下合成。Co‑DPBP具有规则的孔道结构、较高的孔隙率和比表面积。孔道尺寸略大于丙炔/丙烯分子动力学直径,孔道内含有丰富的裸金属位点及氢键作用位点。Co‑DPBP骨架与丙炔分子间的作用力更强,从而实现了丙炔丙烯混合气中优先吸附丙炔的效果,使混合气中丙烯组分得到纯化。
Description
技术领域
本发明属于晶态多孔材料制备和气体分离技术领域,涉及一种新型钴基金属有机骨架材料(Metal organic frameworks,MOF)的制备方法及其应用,该MOF材料具有微孔结构并可以实现丙炔、丙烯气体分离。
背景技术
低碳烃类的分离纯化在石油化工领域具有重要意义。相同碳数的烯烃与炔烃具有相似的结构以及理化性质,使得二者的分离存在挑战性。低温精馏、溶剂吸收等传统的气体分离手段,往往存在耗能较高,耗时较长,设备投资较大等不足之处。采用物理吸附分离的方法则操作简便、分离选择性较高且耗能较低,且不引入新的杂质,是一种备受关注的研究方向(He,Y.;Krishna,R.;Chen,B.,J.Energy&Environmental Science 2012,5(10),9107-9120;Kim,J.;Lin,L.C.;Martin,R.L.;Swisher,J.A.;Haranczyk,M.;Smit,B.,J.Langmuir2012,28(32),11914-9;Ko,D.,J.Industrial&Engineering Chemistry Research 2016,55(33),8967-8978.)。此分离技术的核心要素在于研究开发性能优异的多孔材料,使其具有较高的吸附容量和吸附选择性。MOFs材料是一类由金属离子/金属簇为节点,以具有配位能力的有机配体通过配位键相连接而组成的长程有序的新型多孔晶体材料。MOFs材料的具有高孔隙率、高比表面积、构筑单元多样性以及可修饰性等优点(Furukawa,H.;Cordova,K.E.;O'Keeffe,M.;Yaghi,O.M.,J.Science 2013,341(6149),1230444;Li,J.R.;Sculley,J.;Zhou,H.C.,J.Chemical reviews 2012,112(2),869-932.)。相对于活性炭、分子筛、硅胶等传统吸附材料,MOFs可通过变换金属节点或有机配体达到精确调控其作为多孔吸附材料的孔道环境以及吸附位点,以达到调控MOFs吸附性能(吸附量、吸附选择性)的目的。本发明采用一种具有多个配位位点的有机配体5,5'-双(1H-吡唑-4-基)-2,2'-联吡啶(DPBP)与乙酸钴(Co(CH3COO)2)在溶剂热条件下自组装形成了一例微孔钴基MOF材料。该MOF具有较高的比表面积和孔隙率,为低碳烃的吸附分离提供了结构基础。此材料可以实现丙烯丙炔的有效分离。
发明内容
本发明的目的在于提供一种钴基微孔MOF材料(Co-DPBP)的制备方法,该钴基MOF是由有机配体(DPBP)与钴源(Co(CH3COO)2)通过溶剂热条件反应制备得到块状晶体材料,可用于丙炔、丙烯的分离纯化。
本发明的钴基微孔MOF材料Co-DPBP,其化学式为Co8C70N24O15H58(Co-DPBP),分子结构式为Co8(DPBP)4(COO)2(H2O)5(OH)2O2,DPBP为5,5'-双(1H-吡唑-4-基)-2,2'-联吡啶。
在Co-DPBP中,存在两种由Co构筑的金属簇。第一种为由八个钴离子、四个氢氧根与两个水组成的12连接钴八核次级构筑单元(SBU)Co8(OH)4(H2O)2。每个钴八核SBU与十二个DPBP配体通过吡唑基相连接;第二种为由两个钴离子通过氧原子桥联成的钴双核次级构筑单元(SBU),一个甲酸根和一个吡唑基与钴双核配位,此外,两个钴离子分别与两个水配位。
本发明上述Co-DPBP的合成方法,主要包括以下步骤方法:
(1)将有机配体DPBP与Co(CH3COO)2在溶解于N,N-二甲基甲酰胺(DMF)、四氢呋喃(THF)、乙酸(AcOH)和水的混合溶液中;
(2)将步骤(1)中的混合溶液超声波震荡、搅拌后,进行溶剂热反应,获得块状单晶,先后用DMF和甲醇洗涤;
进一步上述Co-DPBP技术方案中DPBP和Co(CH3COO)2的摩尔比为1:2.5~1:3.5;混合溶剂中DMF与THF、AcOH、水的体积比例为15:10:1:5;每毫摩尔有机配体DPBP对应溶剂用量体积(mL)比例为1:200。溶剂热反应温度为155℃~165℃,反应时间为48h~56h。
上述得到的Co-DPBP材料经过DMF洗涤以及甲醇或二氯甲烷溶剂交换并真空脱出溶剂分子以后用于选择性分离丙炔、丙烯混合气的最终分离材料。
本发明基于一种具有多配位点的有机配体5,5'-双(1H-吡唑-4-基)-2,2'-联吡啶与金属钴源制备了一种新型钴基微孔MOF材料。热分析实验表明此配位聚合物的配位骨架具有较高的热稳定性。气体吸附实验表明它在室温条件下可以较大量地吸附丙炔气体,但同样条件下吸附较少的丙烯。穿透实验进一步验证了该材料可以有效地选择性吸附丙炔,从而达到纯化丙烯气体的目的。因此,该配位聚合物可作为气体分离剂,在低碳烃类的分离纯化方面具有良好的应用前景。
附图说明
图1为本发明中Co-DPBP的三维晶体结构示意图(沿b轴方向)
图2为本发明中Co-DPBP的三维晶体结构示意图(沿c轴方向)
图3为本发明中Co-DPBP新鲜合成样品及吸附测试后样品粉末衍射图
图4为本发明中Co-DPBP在298K条件下丙炔和丙烯单组分吸附曲线图
图5为本发明中Co-DPBP的热分析图
图6为本发明中Co-DPBP的298K条件下丙炔/丙烯(50:50)混合气的穿透曲线图
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。
实例1:(Co-DPBP)
第一步:称取5.76mgDPBP有机配体,10.62mg乙酸钴,溶解于3mL N,N-二甲基甲酰胺(DMF)、2mL四氢呋喃(THF)以及1mL去离子水中,加入0.2mL的乙酸后装入20mL玻璃反应瓶中,将玻璃瓶放进聚四氟乙烯内胆中,用不锈钢反应釜密封。在160℃烘箱下反应48h,得到Co-DPBP晶体样品。
第二步:挑选一颗大小合适、结晶度良好的单晶样品,在298K条件下利用单晶衍射仪收集衍射数据,再利用结构解析软件Olex2精修得到晶体结构。具体结构见说明书附图。样品纯度通过X射线粉末衍射技术确认。
第三步:为了去除材料孔道中的溶剂分子,上述得到的晶态样品经过DMF溶剂洗涤之后浸泡于甲醇溶剂中,溶剂交换持续3-5次。将交换完的样品在90℃,真空条件下脱气10h制备得到用于测试气体吸附的材料。
第四步:在单组分静态吸附测试前,将上述材料装入吸附管中在90℃下再次脱气3h,收集在298K下丙炔丙烯的吸附曲线数据。
其中DPBP合成步骤参考以下文献:(He,T.;Zhang,Y.-Z.;Wang,B.;Lv,X.-L.;Xie,L.-H.;Li,J.-R.ChemPlusChem 2016,81(8),864-871;Taylor,M.K.;Runcevski,T.;Oktawiec,J.;Bachman,J.E.;Siegelman,R.L.;Jiang,H.;Mason,J.A.;Tarver,J.D.;Long,J.R.J.Am.Chem.Soc.2018,140(32),10324-10331;Taylor,M.K.;Runcevski,T.;Oktawiec,J.;Gonzalez,M.I.;Siegelman,R.L.;Mason,J.A.;Ye,J.;Brown,C.M.;Long,J.R.J.Am.Chem.Soc.2016,138(45),15019-15026.)。
其中晶体数据如下:
图1和图2中的晶体结构表明:该配合物结构具有三维贯通的孔道结构。
图3中的粉末衍射谱图表明:新鲜制备的Co-DPBP样品结晶良好,纯度良好。同时吸附测试后的样品结构未发生坍塌。
图4中的丙炔丙烯单组分吸附曲线表明:Co-DPBP对两种低碳烃气体具有较好的吸附容量和分离选择性,框架与丙炔的作用力更强,表现为低压区同等压力下吸附量更大。
图5中的热分析图证明Co-DPBP具有较高的热稳定性,在275℃之前,未见框架结构的明显坍塌。(200℃之前的质量损失推测为孔道中以及配位的溶剂分子的移除。)
图6中Co-DPBP的298K条件下丙炔丙烯混合气穿透曲线图表明:Co-DPBP对丙烯丙炔混合气具有良好的分离能力,在一定时间里,丙炔被吸附在分离柱中,从而可以直接获得纯的丙烯产品。这一现象证实Co-DPBP具有良好的丙炔/丙烯分离能力。
上述结果表明该Co-DPBP材料具有较高的稳定性,同时对丙炔丙烯表现出良好的分离性能。该发明为金属有机骨架材料在结构设计与气体分离性能关联上提供了有益的参考,推进了该类材料在低碳烃分离领域中的应用。
以上内容为本发明的较佳实例而已,但本发明不应局限于该实例所公开内容。所以凡不脱离本发明所公开的精神下完成的等效或修改,都落入本发明保护的范围。
Claims (8)
1.一种钴基微孔MOF材料,其特征在于,有机配体和钴源通过溶剂热反应制备得到块状晶体材料,其化学式为Co8C70N24O15H58(Co-DPBP),分子结构式为Co8(DPBP)4(COO)2(H2O)5(OH)2O2,DPBP为5,5'-双(1H-吡唑-4-基)-2,2'-联吡啶。
3.制备权利要求1所述的钴基微孔MOF材料的方法,其特征在于,包括以下步骤:
(1)将有机配体DPBP与乙酸钴(Co(CH3COO)2)溶解于在N,N-二甲基甲酰胺(DMF)、四氢呋喃(THF)、乙酸(AcOH)和水的混合溶液中;
(2)将步骤(1)中的混合溶液超声波震荡、搅拌后,进行溶剂热反应,获得块状单晶,先后用DMF和甲醇洗涤。
4.按照权利要求3所述的方法,其特征在于步骤(1)中,有机配体DPBP和Co(CH3COO)2的摩尔比为1:2.5~1:3.5。
5.按照权利要求3所述的方法,其特征在于步骤(1)中,每毫摩尔有机配体DPBP对应溶剂用量体积mL比例为1:200。
6.按照权利要求3所述的方法,其特征在于步骤(1)中,混合溶剂中DMF与THF、AcOH、水的体积比例为15:10:1:5。
7.按照权利要求3所述的方法,其特征在于步骤(2)中,溶剂热反应条件155℃~165℃,反应时间为48h~56h。
8.权利要求1所述的钴基微孔MOF材料的应用,作为吸附材料用于丙炔、丙烯气体的高效吸附分离。
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