CN113578379A - 一种酸催化用双磺酸功能化杂多酸离子液体及其制备方法 - Google Patents
一种酸催化用双磺酸功能化杂多酸离子液体及其制备方法 Download PDFInfo
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Abstract
一种酸催化用双磺酸功能化杂多酸离子液体及其制备方法，属于催化剂技术领域。选用基于咪唑的含有双磺酸官能团的分子与杂多酸分子反应，得到新的催化剂。结构式为
或
Description
技术领域
本发明涉及催化剂材料及精细化工技术领域，具体涉及一种用于酸催化体系的双磺酸功能化的杂多酸离子液体及其制备方法。
背景技术
柠檬酸三丁酯(TBC)是一种新型的柠檬酸酯类增塑剂，其具有低毒性和较好的耐水性的特点，而且TBC对环境友好且对人体的伤害较小，因此柠檬酸三丁酯的制备十分重要。目前，工业上合成TBC使用的传统催化剂是浓H2SO4，但是该催化剂存在腐蚀设备、产物TBC变黄影响色泽、反应结束后催化剂不能重复使用且后处理需要通过碱洗和水洗，污染环境的同时会耗费大量的资源等诸多问题。于是人们新开发了催化剂诸如杂多酸、有机酸、离子交换树脂、表面改性催化剂、负载型催化剂、固体超强酸和离子液体等，其中固体超强酸、负载型催化剂、表面改性催化剂等催化剂虽然基本上解决了对设备的腐蚀等问题，但在催化合成TBC过程中存在催化剂活性组分的流失、工业上实际应用成本高、催化活性不高或重复使用性还有待进一步提高等问题，而且因为催化性能不理想造成原料柠檬酸(CA)的转化率低，未转化的CA在后处理过程中需要大量碱液进行中和处理造成浪费、成本增加。已报道的酸性离子液体的催化活性和重复使用性与上述催化剂相比均具有一定的优势，但是其催化活性、稳定性和重复使用性仍有待进一步提高。
发明内容
针对目前已有催化剂体系的不足，本发明提供了一种能够用于酸催化体系(包括柠檬酸酯的合成)的具有高催化活性、稳定性、易于分离回收、重复使用性能良好的双磺酸功能化杂多酸离子液体及其制备方法。
本发明采用如下技术方案：
选用基于咪唑的含有双磺酸官能团的分子与杂多酸分子反应，得到新的催化剂。结构式为
D为杂多酸的阴离子，m≤y，y为杂多酸的阴离子的核电荷数。进一步，上述催化剂的制备方法为：
1)基于咪唑的含有双磺酸官能团的分子为1，3-二(3-磺酸基丙基)咪唑(简记为PS2IM)或1，3-二(4-磺酸基丁基)咪唑(简记为BS2IM)。
2)杂多酸分子其特征在于，所述杂多酸的阳离子为质子，阴离子结构为Keggin结构类型，包括：[XM’xM12-xO40]y-(X＝P,Si，B，H,Zn，Co，Ge，Fe，As，Al，M’＝V，Mo,W；M＝Mo,W，x＝0-6)；Dawson结构类型，包括[X2M’xM18-xO62]y-(X＝P,Si，As；M’＝Mo,W,V；M＝Mo,W，x＝0-6)中的一种。
3)基于咪唑的含有双磺酸官能团的分子与杂多酸反应，反应条件是：咪唑的含有双磺酸官能团的分子溶解在溶剂中，浓度为0.05～1.2mol/L；杂多酸溶解于溶剂中，浓度为0.07～2.00mol/L。二者混合后搅拌，转速100～900转/分钟，反应时间1～72h。之后通过旋转蒸发方法出去溶剂，得到固体产物。
4)用于溶解含有双磺酸官能团的分子和杂多酸分子的溶剂是水、乙醇、甲醇、丙酮、甲酰胺、乙酰胺、N’N-二甲基甲酰胺，二甲亚砜中的一种或者它们的混合物。
5)将4)中所得产物置于50～150℃真空条件下进行干燥，除去所有水分，即得到双磺酸杂多酸离子液体催化剂。
步骤(3)反应时基于咪唑的含有双磺酸官能团的分子与杂多酸的摩尔比为9:1～1:9。
本发明所得双磺酸功能化多杂酸离子液体的应用，用于酸与醇的酯化反应，尤其用于柠檬酸与丁醇制备柠檬酸三丁酯：将离子液体催化剂、柠檬酸、正丁醇加入到装有回流冷凝管及分水器的反应装置中，在回流温度下加热搅拌回流反应，使反应产生的水从分水器分出，然后静置冷却到室温，反应液经减压蒸馏除去剩余的正丁醇，过滤。
本发明的有益效果：
本发明采用的反应原料1，3-二(3-磺酸基丙基)咪唑(简称PS2IM)和1，3-二(4-磺酸基丁基)咪唑(简称BS2IM)中含有两个磺酸官能团，相同物质的量的催化剂的催化活性中心比含有单个磺酸官能团的催化剂的催化活性中心增加了一倍，进而提高了催化活性。杂多酸和其它酸相比，PS2IM、BS2IM和杂多酸结合在一起生成的催化剂熔点更高，在常温下为固体。如此，常温下、反应前催化剂为固体，反应过程中为液体，反应后体系降至常温后催化剂又成固体状态，这样非常有利于催化剂与反应物、产物的分离，减少催化剂的损失，提高催化剂的重复使用性。
附图说明
图1为(HPS2IM)3PW12O40和(HBS2IM)3PW12O40离子液体的结构示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
(1)将PS2IM溶于去离子水配置得到浓度为0.22mol/L的PS2IM溶液；
(2)将H3PW12O40用去离子水溶解，配置得到浓度为0.07mol/L的H3PW12O40溶液；
(3)搅拌条件下将H3PW12O40水溶液逐滴加入PS2IM水溶液中，其中H3PW12O40与PS2IM的物质的量比为1:3。滴加完毕后将反应体系升温至80℃反应9h。通过旋蒸得到产物；
将所得产物然后将所产物置于100℃的真空环境下进行干燥，除去所有水分，即得双磺酸磷钨酸离子液体，记为[HPS2IM]3PW12O40。其结构示意图示于图1。
实施例2
(1)将BS2IM溶于离子水得到浓度为0.22mol/L的BS2IM溶液；
(2)将H3PW12O40用去离子水溶解，配置得到浓度为0.07mol/L的H3PW12O40溶液；
(3)搅拌条件下H3PW12O40水溶液逐滴加入BS2IM水溶液中，其中H3PW12O40与BS2IM的物质的量比为1:3。滴加完毕后将反应体系升温至80℃反应9h。通过旋蒸得到产物；
将产物然后将所产物置于100℃的真空环境下进行干燥，除去所有水分，即得双磺酸磷钨酸离子液体，记为[HBS2IM]3PW12O40。其结构示意图示于图1。
实验例1
将离子液体[HPS2IM]3PW12O40(0.8g)、柠檬酸(11.5284g)，正丁醇(22.2360g)，加入到装有回流冷凝管及分水器的100ml圆底烧瓶中，在回流温度下加热搅拌回流反应3.5小时，使反应产生的水从分水器分出，然后静置冷却到室温，反应液经减压蒸馏除去剩余的正丁醇，柠檬酸的转化率为98.81％。
完成一次催化后，将柠檬酸三丁酯从烧瓶中倒出，离子液体不进行任何处理，进行下一次反应，探究其循环利用性能。循环使用4次后，[HPS2IM]3PW12O40对柠檬酸的转化率仍能保持在91％以上，如表1所示。
实验例2
将离子液体[HBS2IM]3PW12O40(0.8g)、柠檬酸(11.5284g)，正丁醇(22.2360g)，加入到装有回流冷凝管及分水器的100ml圆底烧瓶中，在回流温度下加热搅拌回流反应3.5小时，使反应产生的水从分水器分出，然后静置冷却到室温，反应液经减压蒸馏除去剩余的正丁醇，柠檬酸的转化率为96.17％。
完成一次催化后，将柠檬酸三丁酯从烧瓶中倒出，离子液体不进行任何处理，进行下一次反应，探究其循环利用性能。循环使用3次后，[HBS2IM]3PW12O40对柠檬酸的转化率仍能保持在90％以上，如表1所示。
表1。[HPS2IM]3PW12O40，[HBS2IM]3PW12O40催化TBC合成循环四次对柠檬酸的转化率
Claims (7)
1.一种酸催化用双磺酸功能化杂多酸离子液体，其特征在于，选用基于咪唑的含有双磺酸官能团的分子与杂多酸分子反应得到；结构式为
D为杂多酸的阴离子，m≤y，y为杂多酸的阴离子的核电荷数。
2.按照权利要求1所述的一种酸催化用双磺酸功能化杂多酸离子液体，其特征在于，基于咪唑的含有双磺酸官能团的分子为1，3-二(3-磺酸基丙基)咪唑(简记为PS2IM)或1，3-二(4-磺酸基丁基)咪唑(简记为BS2IM)。
3.按照权利要求1所述的一种酸催化用双磺酸功能化杂多酸离子液体，其特征在于，所述杂多酸的阳离子为质子，阴离子结构为Keggin结构类型，包括：[XM’xM12-xO40]y-，X＝P,Si，B，H,Zn，Co，Ge，Fe，As，Al，；M’＝V，Mo,W；M＝Mo,W，x＝0-6；或阴离子结构为Dawson结构类型，包括[X2M’xM18-xO62]y-，X＝P,Si，As；M’＝Mo,W,V；M＝Mo,W，x＝0-6。
4.权利要求1-3任一项所述的一种酸催化用双磺酸功能化杂多酸离子液体的制备方法，其特征在于，包括以下步骤：将基于咪唑的含有双磺酸官能团的分子溶解在溶剂中，浓度为0.05～1.2mol/L；杂多酸溶解于溶剂中，浓度为0.07～2.00mol/L；二者混合后搅拌，转速100～900转/分钟，反应时间1～72h；之后通过旋转蒸发方法出去溶剂，得到固体产物，干燥即可；
用于溶解基于咪唑的含有双磺酸官能团的分子和杂多酸分子的溶剂是水、乙醇、甲醇、丙酮、甲酰胺、乙酰胺、N’N-二甲基甲酰胺、二甲亚砜中的一种或者几种的混合物。
5.权利要求1-3任一项所述的一种酸催化用双磺酸功能化杂多酸离子液体的应用，作为催化剂，用于催化酸与醇的酯化反应。
6.按照权利要求5的应用，用于柠檬酸与丁醇制备柠檬酸三丁酯。
7.按照权利要求6的应用，将离子液体催化剂、柠檬酸、正丁醇加入到装有回流冷凝管及分水器的反应装置中，在回流温度下加热搅拌回流反应，使反应产生的水从分水器分出，然后静置冷却到室温，反应液经减压蒸馏除去剩余的正丁醇，过滤。
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