CN110078092A - 一种制备ts-2分子筛膜的方法 - Google Patents
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Abstract
本发明提供了一种制备纯相TS‑2分子筛膜的方法。采用纯相的TS‑2分子筛晶体为晶种,通过二次水热生长法在支撑体的外表面制备高催化活性TS‑2分子筛膜。本发明首次在多孔陶瓷支撑体上制备出生长连续致密的TS‑2分子筛膜,可解决TS‑2分子筛的分离回收困难和重复利用率低等问题,为钛硅分子筛膜在双氧水的催化氧化反应体系中的工业应用奠定了理论和技术基础。
Description
技术领域
本发明涉及制备TS-2分子筛膜的方法,属于无机膜材料制备和应用领域。
背景技术
1983年,Taramasso等以硅酸四乙酯(TEOS)为硅源合成了具有MFI结构的TS-1分子筛。Reddy等在1990年将模板剂TPAOH换成TBAOH,成功合成出钛硅分子筛家族的第二个成员,具有MEL结构的TS-2分子筛。TS-2分子筛是含Ti(Ⅳ)的MEL结构分子筛材料。MEL型分子筛具有三维平行于a轴方向和b轴方向的十元环直型交叉孔道,孔道尺寸为0.54×0.53nm,且有两种不同类型的孔道交叉点。由于a轴和b轴的两个直通道,使得TS-2结构较TS-1的一个直通道能容纳更大的有机分子,分子筛在催化烷烃的部分氧化、烯烃的环氧化、醇类的氧化、苯酚及苯的羟基化以及环己酮的氨氧化反应具有十分优异的催化选择氧化活性,因而引起了广泛的重视。
目前研究表明较小尺寸钛硅分子筛颗粒(0.1~0.3μm)具有较好的催化活性,但分子筛在实际应用于催化反应的过程时,有两个方面的缺点。一方面,当分子筛表面进行催化反应时,反应物和反应产物不能一次性达到全部分离;如果反应产物不能及时的从分子筛表面离开,将会发生副反应,导致反应的选择性和回收率下降。另一方面,分子筛颗粒的尺寸很小,生产成本高而且分离与回收的困难。例如采用传统的负载技术浸渍法,分子筛孔道不仅会被反应产物堵塞而且稳定性也很差,分子筛在溶剂冲刷等作用下容易脱离载体,导致催化效率下降、成本上升。为解决上述问题,很多研究者尝试采用水热合成或者自组装等技术将钛硅分子筛晶体负载到基板上制成分子筛膜,这不仅可以克服分子筛催化剂与产物分离的困难,而且有利于提高分子筛颗粒的分布面积和分散程度。通过控制反应物流经膜的速率来控制反应物与催化剂的接触时间,促进目标反应在接近理想的条件下进行,从而可极大地提高化学反应速率和产品的收率。
由于钛硅分子筛及其膜的制备条件极其刻,目前尚未有关于在制备TS-2分子筛膜的报道。
发明内容
针对钛硅分子筛需求量大、制备成本高、分离和回收困难等问题,本发明提供一种新的制备TS-2分子筛膜的方法。
本发明的一种制备TS-2分子筛膜的方法,包括如下步骤:
(1)合成溶胶制备:以硅源、钛源、有机胺、有机醇和水为原料,配制成摩尔组成为1SiO2:0.01~0.05 TiO2:0.30~0.50 TBA+:2~10 IPA:60~180 H2O的合成溶胶,其中TBA+表示有机胺,IPA表示有机醇;
(2)晶种化支撑体:将纯相的TS-2分子筛晶体涂覆在支撑体上,并干燥;
(3)二次水热合成:将步骤(1)的合成溶胶和步骤(2)的干燥后的支撑体一并转移到反应釜中,在100~200℃下水热晶化2~10天,得到分子筛膜前驱体;
(4)干燥处理:将分子筛膜前驱体表面用蒸馏水洗涤至中性,并干燥;
(5)煅烧去除模板剂:经干燥处理后的分子筛膜前驱体在400~600℃下煅烧4~20h,得到TS-2分子筛膜。
优选的,所述的硅源可以为沉淀二氧化硅、硅溶胶或正硅酸四乙酯;钛源可以为四异丙基钛酸酯、四氯化钛或钛酸四丁酯;有机胺可以为四丁基氢氧化铵或四丁基溴化铵;有机醇可以为甲醇、乙醇、丙醇或异丙醇。
优选的,所述的支撑体为莫来石支撑体或管状多孔陶瓷支撑体。
优选的,所述的水热晶化的温度为160~200℃,时间为2~4天。
优选的,所述的煅烧在马弗炉中进行,煅烧温度为450~550℃,煅烧时间为6~15h,其中升温速率为0.1~1℃/min。
本发明的有益效果:采用二次水热生长法,将负载纯相TS-2分子筛晶种的支撑体置入含有机胺模板剂的合成溶胶中,在钛硅溶胶中水热合成,在支撑体表面形成一层致密且连续的TS-2分子筛晶体层。该方法操作简单,有利于解决钛硅分子筛在工业应用上分离回收困难和重复利用率低等问题。该方法制备的TS-2分子筛膜层生长致密、具有一定的催化活性,这为实现TS-2分子筛膜在催化氧化反应中的应用提供了基础。该方法制备的TS-2分子筛膜可广泛应用于催化氧化的反应领域,如各类直链以及环状烯烃的环氧化反应、芳烃的羟基化、酮类的氨肟化、烷烃的选择氧化以及醇和胺的选择氧化等等。
附图说明
图1是本发明实施例中例1~4制备的TS-2分子筛膜的X射线衍射图。
图2是本发明实施例1中制备的TS-2分子筛膜的EDX图。
图3是本发明实施例1中制备的TS-2分子筛膜的表面和断面电镜图。
图4是本发明实施例2中制备的TS-2分子筛膜的表面和断面电镜图。
图5是本发明实施例3中制备的TS-2分子筛膜的表面和断面电镜图。
图6是本发明实施例4中制备的TS-2分子筛膜的表面和断面电镜图。
具体实施方式
下面将结合附图和具体实施例来详细说明本发明所具有的有益效果,旨在帮助阅读者更好地理解本发明的实质,但不能对本发明的实施和保护范围构成任何限定。
实施例1
将正硅酸四乙酯、钛酸四丁酯、异丙醇与水混合均匀,制备摩尔比1 SiO2:0.035TiO2:0.25TBAOH:2.75 IPA:120 H2O的分子筛膜合成溶胶。采用纯相的棒状TS-2分子筛为晶种涂覆在10cm长的莫来石管状支撑体的外表面上,然后将分子筛膜合成溶胶和预涂晶种的莫来石管状支撑体转移至不锈钢反应釜中,反应釜放入170℃的烘箱中晶化2天。晶化后的样品放入沸水中清洗至中性后并烘干,样品在80℃的烘箱干燥后被放入马弗炉中煅烧去除模板剂,其中煅烧温度和煅烧时间分别为500℃和10h,升温和降温速率都为0.3℃/min。
将煅烧之后的TS-2分子筛膜应用于异丙醇的催化氧化反应,异丙醇氧化反应的渗透汽化成分和渗透侧混合物使用气相色谱分析(岛津,GC-2014C/GC-14C)进行分析,反应原理如下所示:
TS-2分子筛膜的渗透汽化性能由渗透通量Q(单位为kg·m-2·h-1)和催化性能两个参数表示,具体计算公式如下:
Q=W/(A×t)
CIPA=Macetone/(MIPA+Macetone)×100%
其中,W是渗透测收集产物总质量(kg),A是TS-2分子筛膜的有效膜面积(m2),t是收集时间(h),Macetone和MIPA分别为丙酮和异丙醇在渗透侧的摩尔含量。在反应温度为70℃,异丙醇和双氧水的摩尔比为0.5时,转化率别为6.53%和100%,本分子筛膜的渗透通量为4.00kg·m-2·h-1。图1和图3分别为制备的TS-2分子筛膜的XRD谱图和SEM照片。图1和图3显示制备的分子筛膜具有纯相的MEL型分子筛结构,支撑体表面被一层致密的棒状MEL型分子筛晶体覆盖,晶体层的厚度约为10μm。
实施例2
将实施例1中的摩尔配比调整为1 SiO2:0.035 TiO2:0.25 TBAOH:2.75 IPA:100H2O,其他合成条件与实施例1一致。
实施例3
将实施例1中的摩尔配比调整为1 SiO2:0.035 TiO2:0.20 TBAOH:2.75 IPA:120H2O,其他合成条件与实施例1一致。
实施例4
将实施例1中的摩尔配比调整为1 SiO2:0.040 TiO2:0.25 TBAOH:2.75 IPA:120H2O,其他合成条件与实施例1一致。
表1是本发明实施例中例1~4制备的TS-2分子筛膜的催化性能结果。
表1
Claims (8)
1.一种制备TS-2分子筛膜的方法,包括如下步骤:
(1)以硅源、钛源、有机胺、有机醇和水为原料,配制成摩尔组成为1 SiO2:0.01~0.05TiO2:0.30~0.50 TBA+:2~10 IPA:60~180H2O的合成溶胶,其中TBA+表示有机胺,IPA表示有机醇;
(2)将纯相的TS-2分子筛晶体涂覆在支撑体上,并干燥;
(3)将步骤(1)的合成溶胶和步骤(2)的干燥后的支撑体一并转移到反应釜中,在100~200℃下水热晶化2~10天,得到分子筛膜前驱体;
(4)将分子筛膜前驱体表面用蒸馏水洗涤至中性,并干燥;
(5)经干燥处理后的分子筛膜前驱体在400~600℃下煅烧4~20h,得到TS-2分子筛膜。
2.根据权利要求1所述的方法,其特征在于:所述的硅源为沉淀二氧化硅、硅溶胶或正硅酸四乙酯;钛源为四异丙基钛酸酯、四氯化钛或钛酸四丁酯;有机胺为四丁基氢氧化铵或四丁基溴化铵;有机醇为甲醇、乙醇、丙醇或异丙醇。
3.根据权利要求1所述的方法,其特征在于:所述的支撑体为莫来石支撑体或管状多孔陶瓷支撑体。
4.根据权利要求1所述的方法,其特征在于:所述的水热晶化的温度为160~200℃,时间为2~4天。
5.根据权利要求1所述的方法,其特征在于:所述的煅烧在马弗炉中进行,煅烧温度为450~550℃,煅烧时间为6~15h,其中升温速率为0.1~1℃/min。
6.根据权利要求1~5任一权利要求所述的方法得到的TS-2分子筛膜。
7.根据权利要求6所述的TS-2分子筛膜的应用。
8.根据权利要求7所述的应用,其特征在于:所述的TS-2分子筛膜用作催化氧化的反应的催化剂。
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