CN107311834A - 配位聚合物多孔材料maf‑23在分离纯化c4烃类混合物和提取丁二烯中的应用 - Google Patents
配位聚合物多孔材料maf‑23在分离纯化c4烃类混合物和提取丁二烯中的应用 Download PDFInfo
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Abstract
本发明提供了配位聚合物多孔材料MAF‑23在分离纯化C4烃类混合物中的新应用,将MAF‑23应用于C4烃类混合物的分离,可通过一步吸附直接得到高纯度的1,3‑丁二烯,同时具有比较高的工作容量。该分离纯化方法在常温常压下即可进行,操作简单,对环境友好,无需进行多次吸附—脱附操作。
Description
技术领域
本发明涉及微孔配位聚合物多孔材料领域,更具体地,涉及配位聚合物多孔材料MAF-23在分离纯化C4烃类混合物和提取丁二烯中的应用。
背景技术
1,3-丁二烯(简称丁二烯)是四大最重要的化工产品之一,通常从生产乙烯的副产物C4烃类混合物中抽提。C4烃类混合物成分复杂,主要的成分为1,3-丁二烯、顺-2-丁烯、反-2-丁烯、正丁烯、异丁烯、异丁烷和正丁烷。C4烃类分子具有非常相似的物理性质,而且丁二烯容易聚合,因此分离难度很大。
在工业上,C4烃类混合物的分离方法是有机溶剂萃取精馏分离,所用到的有机溶剂包括乙腈,N-甲基砒咯烷酮,和N,N-二甲基甲酰胺。这个方法存在比较多的缺点,除了需要大量对环境有害的有机溶剂外,还需要在高温高压条件下操作,而且需要比较高的分离塔板数,特别耗能。此外,为了防止1,3-丁二烯在高温环境中发生聚合,还需要加入阻聚剂。
为了节约能源和保护环境,非常有必要发展新的方法和材料用于在温和条件下分离纯化C4烃类,尤其是纯化丁二烯。通常,将混合气体通过固定吸附床是一种非常简单和有效的分离方法,但前提之一是吸附剂具有足够高的吸附选择性和合适的吸附顺序。已知的吸附剂多数优先吸附丁二烯,但选择性很低;由配位不饱和金属离子修饰的多孔材料可以具有较高选择性,但对丁二烯和丁烯/异丁烯/2-丁烯等的选择性仍然很低;此外,这种优先吸附丁二烯的选择性意味着吸附分离过程后,还需要至少一个脱附过程才能获得所需的丁二烯;而且,残留在吸附床内的其它C4烃类分子会污染脱附出来的丁二烯,降低产品的纯度,因此需要经过多次吸附—脱附过程才能达到所需纯度。如果存在一种吸附剂对丁二烯具有最弱的亲和力,或者优先吸附丁二烯以外的其他C4烃类分子,那么将C4烃类混合物流过这样的吸附剂,就能直接获得高纯度的丁二烯,从而解决以上的问题。虽然疏水型吸附剂具有这种吸附顺序,但其对烃类混合物的选择性极低,导致分离效果可忽略,难以应用。
多孔配位聚合物(PCP),也称金属-有机框架(MOF),是一种由金属离子和有机桥联配体通过配位键连接而成的晶态材料,具有结构丰富可修饰性强等优点,有望实现特殊的吸附选择性。
发明内容
本发明根据现有技术中的不足,提供了配位聚合物多孔材料MAF-23在分离纯化C4烃类混合物尤其是提取丁二烯中的应用。
为了实现上述目的,本发明采用如下技术方案:
配位聚合物多孔材料MAF-23在分离纯化C4烃类混合物中的应用,所述MAF-23的化学式为[Zn2(btm)2],其中,btm2-代表有机配体双(5-甲基-1H-1,2,4-三唑-3-基)甲烷脱去质子后的阴离子,所述MAF-23结晶在单斜晶系,P21/n空间群,a = 10.5783(14) Å,b = 12.3288(17) Å,c = 17.236(2) Å, β= 93.714(2)o,所述MAF-23是通过btm2-配体与四配位的Zn2+离子连接形成的具有一维孔道的三维框架结构。
其中,C4烃类混合物中C4烃类代表碳原子数目为4的饱和或不饱和烃。
优选地,C4烃类混合物为1,3-丁二烯、顺-2-丁烯、反-2-丁烯、正丁烯、异丁烯、异丁烷或正丁烷中的两种或更多种。
更优选地,C4烃类混合物为1,3-丁二烯、正丁烯、异丁烯或正丁烷中的两种或更多种。
最优选地,所述MAF-23用于分离纯化C4烃类混合物中的丁二烯,得到高纯度的丁二烯。
即在所述C4烃类混合物中至少包括丁二烯,用于实现丁二烯的高纯度分离。
本申请人研究了多个具有代表性的MOF材料在分离纯化C4烃类混合物中的性能,尤其是在纯化丁二烯的性能,其中发现了一例先前我们报道过的多孔配位聚合物(MAF-23),由于其具有非常独特的孔道形状和孔表面结构,其对C4烃类分子的亲和力具有独特的强弱顺序,而且对丁二烯的亲和力最弱。这个顺序使得MAF-23能够在温和条件下通过一步吸附直接得到纯度>99.5%的丁二烯。
作为一种简便的应用方式,可以将MAF-23作为吸附剂,将其通过固定吸附床进行吸附分离C4烃类混合物,简单高效,单次低能耗实现高产品纯度的分离。
本发明使用的MAF-23可以温和条件下,将丁二烯/正丁烯/异丁烯/正丁烷混合气体进行高效的分离,并且获得高纯度的1,3-丁二烯。
与现有技术相比,本发明具有如下优点及有益效果:
本发明提供了MAF-23材料在分离纯化C4烃类混合物中的新应用。将MAF-23作为吸附剂,将C4烃类混合物流过吸附剂,因为丁二烯的亲和力最弱,最先流出,可以直接得到高纯度的丁二烯,其纯度达到>99.5%的聚合纯度要求,同时具有比较高的工作容量。该分离提纯方法在常温常压下即可进行,且操作简单,对环境友好,无需进行多次吸附—脱附操作。
附图说明
图1为本发明多孔材料MAF-23的结构。
图2为本发明MAF-23的X射线粉末衍射图,包括原合成和模拟的粉末。
图3为本发明MAF-23在298K条件下1,3-丁二烯、正丁烯、正丁烷和异丁烯吸附等温线。
图4为本发明MAF-23所制备的吸附固定床在298 K和一个大气压条件下对体积比1:1:1:1的丁二烯/正丁烯/异丁烯/正丁烷混合气体分离穿透实验曲线。
图5为本发明MAF-23所制备的吸附固定床在298 K和一个大气压条件下对体积比5:2:2:1的丁二烯/正丁烯/异丁烯/正丁烷混合气体分离穿透实验曲线。
具体实施方式
以下结合具体实施例和附图进一步说明本发明,其实施例在附图中图示并在后面加以说明,给出了部分详细的实施方式和具体的操作过程。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
其中,以下实施例中提及的MAF-23粉末样品的合成制备及相应的表征请参见:Liao, P.-Q.; Zhou, D.-D.; Zhu, A.-X.; Jiang, L.; Lin, R.-B.; Zhang, J.-P.*;Chen, X.-M. Strong and Dynamic CO2 Sorption in a Flexible Porous FrameworkPossessing Guest Chelating Claws. J. Am. Chem. Soc. 2012, 134, 17380-17383。
图1和图2为MAF-23粉末样品的结构及X射线粉末衍射图。其中,MAF-23粉末样品化学式为[Zn2(btm)2], 其中btm2-代表有机配体双(5-甲基-1H-1,2,4-三唑-3-基)甲烷(H2btm) 脱去质子后的阴离子。本发明使用的多孔材料MAF-23结晶在单斜晶系,P21/n空间群,a = 10.5783(14) Å,b = 12.3288(17) Å,c = 17.236(2) Å,β = 93.714(2)o,是通过btm2-配体与三个四配位的Zn2+离子连接形成的具有一维孔道(最窄处为3.6 Å)的三维框架结构。
实施例1多孔配位聚合物MAF-23的气体吸附性质表征
将多孔材料MAF-23放入石英样品管中,然后在BELSORP-max吸附仪在298 K条件下分别测定其丁二烯(C4H6),正丁烯(n-C4H8),正丁烷(C4H10) 和异丁烯(i-C4H8)气体吸附等温线,其吸附等温线图见图3。从图3中可知,MAF-23对几种C4烃类物质的吸附强弱顺序为:异丁烯>正丁烯>正丁烷>丁二烯。
实施例2 以MAF-23为填料吸附固定床的制作和四组分混合气体分离
将MAF-23粉末样品填充进内径为0.46 cm,长度为10 cm的不锈钢管,尽量压实填密。柱子在He气氛,423 K加热恒温10小时,冷却至298 K,一个大气压下,向柱子通入总流速为2.0mL min-1,体积比为1:1:1:1 的丁二烯/正丁烯/异丁烯/正丁烷混合气体,气体的绝对浓度用热导检测器(TCD, 7890A, HP-AL/S毛细管柱)检测。得到的穿透曲线实验数据图见图4,从图4中可以得出,上述四种混合气体分子被一一分开,先流出为丁二烯,具有非常好的分离效果。
实施例3 以MAF-23为填料吸附固定床的制作和体积比为5:2:2:1的丁二烯/正丁烯/异丁烯/正丁烷分混合气体分离
将MAF-49粉末样品填充进内径为0.46 cm,长度为10 cm的不锈钢管,尽量压实填密。柱子在He气氛,423 K加热恒温10小时,冷却至313 K,一个大气压下,向柱子通入总流速为2mL min-1,体积比为5:2:2:1 的丁二烯/正丁烯/异丁烯/正丁烷混合气体,气体的绝对浓度用热导检测器(TCD, 7890A, HP-AL/S毛细管柱)检测,相对浓度用MS (5975C)检测。得到的穿透曲线实验数据图见图5,四种气体分子被一一分开,先流出的丁二烯,经测定,其纯度达到聚合级要求99.5%。
Claims (8)
1.配位聚合物多孔材料MAF-23在分离纯化C4烃类混合物中的应用,其特征在于,所述MAF-23的化学式为[Zn2(btm)2],其中,btm2-代表有机配体双(5-甲基-1H-1,2,4-三唑-3-基)甲烷脱去质子后的阴离子,所述MAF-23结晶在单斜晶系,P21/n空间群,a = 10.5783(14) Å,b = 12.3288(17) Å,c = 17.236(2) Å,β = 93.714(2)o ,所述MAF-23是通过btm2-配体与四配位的Zn2+离子连接形成的具有一维孔道的三维框架结构;
其中,C4烃类混合物中C4烃类代表碳原子数目为4的饱和或不饱和烃。
2.根据权利要求1所述的应用,其特征在于,C4烃类混合物为丁二烯、顺-2-丁烯、反-2-丁烯、正丁烯、异丁烯、异丁烷或正丁烷中的两种或更多种。
3.根据权利要求1或2所述的应用,其特征在于,C4烃类混合物中为丁二烯、正丁烯、异丁烯、异丁烷或正丁烷中的两种或更多种。
4.根据权利要求1或3所述的应用,其特征在于,所述MAF-23用于分离纯化C4烃类混合物中的丁二烯。
5.一种分离纯化C4烃类混合物的方法,其特征在于,将配位聚合物多孔材料MAF-23作为吸附剂吸附C4烃类混合物,MAF-23的化学式为[Zn2(btm)2],其中,btm2-代表有机配体双(5-甲基-1H-1,2,4-三唑-3-基)甲烷脱去质子后的阴离子,所述MAF-23结晶在单斜晶系,P21/n空间群,a = 10.5783(14) Å,b = 12.3288(17) Å,c = 17.236(2) Å, β= 93.714(2)o,所述MAF-23是通过btm2-配体与三个四配位的Zn2+离子连接形成的具有一维孔道的三维框架结构;
其中,C4烃类混合物中C4烃类代表碳原子数目为4的饱和或不饱和烃。
6.根据权利要求5所述的方法,其特征在于,C4烃类混合物为丁二烯、顺-2-丁烯、反-2-丁烯、正丁烯、异丁烯、异丁烷或正丁烷中的两种或更多种。
7.根据权利要求5或6所述的方法,其特征在于,C4烃类混合物中为丁二烯、正丁烯、异丁烯、异丁烷或正丁烷中的两种或更多种。
8.根据权利要求7所述的方法,其特征在于,所述MAF-23用于分离纯化C4烃类混合物中的丁二烯。
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