CN108484370B - 一种催化制备叶青素的方法 - Google Patents
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- 229960005375 lutein Drugs 0.000 title claims abstract description 34
- ORAKUVXRZWMARG-WZLJTJAWSA-N lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C ORAKUVXRZWMARG-WZLJTJAWSA-N 0.000 title claims abstract description 34
- 235000012680 lutein Nutrition 0.000 title claims abstract description 34
- 239000001656 lutein Substances 0.000 title claims abstract description 34
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 title claims abstract description 34
- FJHBOVDFOQMZRV-XQIHNALSSA-N xanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C=C(C)C(O)CC2(C)C FJHBOVDFOQMZRV-XQIHNALSSA-N 0.000 title claims abstract description 34
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
本发明公开了一种催化制备叶青素的方法，是将苯甲醇、乙缩醛和水的混合溶液在室温下搅拌5~8min后，加入磁性离子液体，继续搅拌反应30~60min，反应完毕后静置30min；下层离子液体直接循环利用；上层含有叶青素的混合液进一步分离纯化，得到叶青素产品和未反应完全的原料。本发明具有具有催化活性高、工艺简单、反应转化率高和叶青素收率高等优点。
Description
技术领域
本发明催化技术领域，具体涉及一种磁性离子液体催化制备叶青素的方法。
背景技术
叶青素又称1-乙氧基-1-苯甲氧基乙烷、乙醛乙醇苯甲醇缩醛，无色液体，具有强烈清新的青叶香气，带有风信子和玫瑰样香韵，主要用于肥皂、洗涤剂、化妆品等日用香精中。目前，国外的一些公司已将其应用于洗衣房的漂白剂和杀虫剂的配方中，使其得到更广泛的应用。
叶青素的传统合成主要有如下5种：1）在酸性催化剂存在下以乙缩醛和苯甲醇为原料进行缩醛交换反应制得；2）苯甲醇与乙烯基乙基醚在钴盐或ATPB作用下催化制得；3）2-苄氧基丙酸与乙醇在氧化汞和碘存在下反应制得；4）以三聚乙醛、乙醇和苯甲醇为原料，在酸催化下制得；5）以α-氯代乙醚与苯甲醇反应制得；上述方法中，方法2）和方法3）需要采用特殊的催化剂，并且催化剂具有剧毒，方法4）副产物多，分离比较困难，方法5）所用到的原料α-氯代乙醚需要自制，无工业化产品；方法1）中所用到的常规酸性催化剂为硫酸，其具有很强的腐蚀性，且产生的废酸不易处理，对环境产生的危害较大。
中国专利201610888733.2公开了一种以液体酸（对甲苯磺酸、三氟化硼、磷酸或氯化铝）为催化剂，将原料苯甲酸和乙烯基乙醚在管式振荡流反应器中连续制备叶青素的方法，其实现了叶青素的连续生产，产品质量稳定、质量高且结构紧凑，但是其仍然使用常规的液体酸作为催化剂，仍存在设备腐蚀、废酸处理、催化剂无法循环利用以及产物颜色也会变黄的缺陷；
近年来，人们发现离子液体具有环境友好、重复利用性好等优点，特别是强酸性离子液体不仅满足了强酸催化反应的需要，而且容易将反应物中的C-H和C-C键活化，促使一些反应在相对较低的温度下进行，从而节省能耗，减少副反应，是一类很有应用潜力的绿色催化材料。
发明内容
针对现有技术存在的工艺复杂、转化率低、叶青素选择性差、催化剂无法回收利用的缺陷，本发明公开了一种以磁性离子液体催化剂反应制备叶青素的方法，其具有催化活性高、工艺简单、反应转化率高、催化剂易于回收利用及叶青素收率高等优点。
本发明是通过如下技术方案实现的：
本发明公开了一种催化制备叶青素的方法，将苯甲醇、乙缩醛和水的混合溶液在室温下搅拌5~8min后，加入磁性离子液体，继续搅拌反应30~60min，反应完毕后静置30min；下层离子液体催化剂经磁场分离后直接循环利用；上层含有叶青素的混合液进一步分离纯化，得到叶青素产品和未反应完全的原料；其搅拌速度均为500~800r/min；
作为一种优选实施方式，所述苯甲醇、乙缩醛和水的摩尔比为1:5~10:10~30；所述磁性离子液体的加入量为混合溶液重量的5~12%。
其中，所述磁性离子液体的制备方法为：
1）磁核ZnFe2O4的制备
将FeCl3·6H2O 和Zn(Ac)2·2H2O溶于乙二醇溶液中，然后向其中加入醋酸钠和CTAB超声处理30min使之充分分散得到混合物；然后将混合物在220℃的水浴条件下反应24h得到悬浊液，将悬浊液自然冷却至室温后，经离心、洗涤、干燥后得到ZnFe2O4磁性纳米晶；
2）ZnFe2O4的表面TiO2包覆
将步骤1）得到的ZnFe2O4磁性纳米晶分散在由乙二醇和去离子水混合而成的分散相中，然后添加氨水在功率为200W的条件下超声处理30min，再在剧烈搅拌的条件下滴加钛酸四丁酯，继续在室温下搅拌3h后进行离心分离，离心分离后的固体产物在105℃处理12h得到ZnFe2O4@TiO2载体；此步骤一方面可以显著提高催化剂的比表面积，另一方面可以与离子液体上的SO4 2-作用形成固体超强酸，进而强化催化剂的反应活性；
3）磁性离子液体的负载
将ZnFe2O4@TiO2载体置于水溶液中，然后加入离子液体Y在300w的超声条件下分散处理2h，然后将其置于70℃真空干燥箱中处理12h得到磁性离子液体；
其中，所述离子液体Y的结构式为：
作为一种优选实施方式，步骤1）中，FeCl3·6H2O、Zn(Ac)2·2H2O、醋酸钠和CTAB的物质的量之比为6:3:40:12，混合物中醋酸钠物质的量浓度为0.5mol/L。
作为一种优选实施方式，步骤2）中，乙二醇、去离子水、氨水、钛酸四丁酯的体积比为100:25:5:1，ZnFe2O4磁性纳米晶与乙二醇的质量体积比为5g/L。
作为一种优选实施方式，步骤3）中，离子液体Y与ZnFe2O4@TiO2载体的质量比为15wt%~30wt%，ZnFe2O4@TiO2载体与水的质量体积比为1/20 g/mL。
与现有技术相比，本发明的优点在于：
1）本发明采用的多酸性离子液体与常规酸性离子液体相比具有酸密度高、热稳定性和反应稳定性高、反应活性高、易于回收利用等优点，同时在反应过程中得到的苯甲醇转化率高、叶青素的选择性也得到了明显提升；
2）本发明采用的多酸基离子液体具有催化剂使用量少、重复利用过程中反应活性未见明显下降、反应产物分离方便以及反应条件比较温和等优点；
3）ZnFe2O4的表面包覆TiO2一方面可以显著提高催化剂的比表面积，另一方面可以与离子液体上的SO4 2-作用形成固体超强酸，进而强化催化剂的反应活性。
4）在催化剂中加入适量的水能够解离出质子，从而增加催化剂的酸性，并且能够降低催化体系的黏度，有利于反应物的充分接触以及叶青素与催化剂的分离，从而增强催化性能。
具体实施方式
以下结合实施例对本发明作进一步详细描述，其中所用催化剂的制备步骤如下：
（1）磁核ZnFe2O4的制备
将3.0 mmol FeCl3·6H2O 和1.5mmol Zn(Ac)2·2H2O溶于40.0mL的乙二醇溶液中，然后加入20.0 mmol的醋酸钠和6.0mmolCTAB，在功率为200W的条件下超声处理30min，使之充分分散，得到混合物；然后将混合物在220℃的水浴条件下反应24h得到悬浊液，将悬浊液自然冷却至室温后，经离心、洗涤、干燥后得到ZnFe2O4磁性纳米晶；
（2）ZnFe2O4的表面TiO2包覆
将0.1g步骤1）得到的ZnFe2O4磁性纳米晶分散在由20mL乙二醇和5mL去离子水混合而成的分散相中，然后添加1.0mL氨水在功率为200W的条件下超声处理30min，再在剧烈搅拌的条件下滴加钛酸四丁酯，继续在室温下搅拌3h后进行离心分离，离心分离后的固体产物在105℃处理12h得到ZnFe2O4@TiO2载体；
（3）离子液体的负载
实验过程中所用的离子液体种类如下所示，记为离子液体Y
将ZnFe2O4@TiO2载体置于水溶液中，然后向其中加入磁性离子液体在300w的超声条件下分散处理2h，然后将其置于70℃真空干燥箱中处理12h得到磁性离子液体，离子液体Y与ZnFe2O4@TiO2载体的质量比为15wt%~30wt%，ZnFe2O4@TiO2载体与水的质量体积比为1/20g/mL。
实施例1
将苯甲醇、乙缩醛和水按照摩尔比为1:10:30的比例混合得到的混合溶液在室温下以800r/min的搅拌速率搅拌5min后，加入占混合溶液总质量为12%的磁性离子液体催化剂，继续搅拌反应60min，反应完毕后静置30min，下层的磁性离子液体催化剂经磁场分离后无需经过任何处理直接循环利用，上层含有叶青素的混合液进一步分离纯化，得到叶青素产品和未反应完全的原料；其中，磁性离子液体中离子液体Y与ZnFe2O4@TiO2载体的质量比为15wt%。
经分析后得出苯甲醇的转化率为99.7%，叶青素的产率为98.6%。
实施例2
将苯甲醇、乙缩醛和水按照摩尔比为1:5:10的比例混合得到的混合溶液在室温下以500r/min的搅拌速率搅拌8min后，加入占混合溶液总质量为5%的磁性离子液体催化剂，继续搅拌反应30min，反应完毕后静置30min，下层的磁性离子液体催化剂经磁场分离后无需经过任何处理直接循环利用，上层含有叶青素的混合液进一步分离纯化，得到叶青素产品和未反应完全的原料；其中，磁性离子液体中离子液体Y与ZnFe2O4@TiO2载体的质量比为30wt%。
经分析后得出苯甲醇的转化率为97.8%，叶青素的产率为96.5%。
实施例3
将苯甲醇、乙缩醛和水按照摩尔比为1:8:20的比例混合得到的混合溶液在室温下以650r/min的搅拌速率搅拌6min后，加入占混合溶液总质量为8%的磁性离子液体催化剂，继续搅拌反应45min，反应完毕后静置30min，下层的磁性离子液体催化剂经磁场分离后无需经过任何处理直接循环利用，上层含有叶青素的混合液进一步分离纯化，得到叶青素产品和未反应完全的原料；其中，磁性离子液体中离子液体Y与ZnFe2O4@TiO2载体的质量比为23wt%。
经分析后得出苯甲醇的转化率为99.4%，叶青素的产率为97.9%。
实施例4：
将实施例1中回收得到的磁性离子液体催化剂在同样的反应条件下进行循环利用，其相应的测试结果如下表1所示：
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是本发明的原理，在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。
Claims (5)
1.一种催化制备叶青素的方法，其特征是：将苯甲醇、乙缩醛和水的混合溶液在室温下搅拌5~8min后，加入磁性离子液体，继续搅拌反应30~60min，反应完毕后静置30min；下层离子液体催化剂经磁场分离后直接循环利用；上层含有叶青素的混合液进一步分离纯化，得到叶青素产品和未反应完全的原料；
其中，所述磁性离子液体的制备方法为：
1）磁核ZnFe2O4的制备
将FeCl3·6H2O 和Zn(Ac)2·2H2O溶于乙二醇溶液中，然后向其中加入醋酸钠和CTAB超声处理30min，得到混合物；然后将混合物在220℃的水浴条件下反应24h得到悬浊液，将悬浊液自然冷却至室温后，经离心、洗涤、干燥后得到ZnFe2O4磁性纳米晶；
2）ZnFe2O4的表面TiO2包覆
将步骤1）得到的ZnFe2O4磁性纳米晶分散在由乙二醇和去离子水混合而成的分散相中，然后添加氨水并超声30min，再在剧烈搅拌的条件下滴加钛酸四丁酯，继续在室温下搅拌3h后进行离心分离，离心分离后的固体产物在105℃处理12h得到ZnFe2O4@TiO2载体；
3）磁性离子液体的负载
将ZnFe2O4@TiO2载体置于水溶液中，然后加入离子液体Y在300w的超声条件下分散处理2h，然后将其置于70℃真空干燥箱中处理12h得到磁性离子液体；其中，离子液体Y与ZnFe2O4@TiO2载体的质量比为15wt%~30wt%，ZnFe2O4@TiO2载体与水的质量体积比为1/20 g/mL；
其中，所述离子液体Y的结构式为：
2.如权利要求1所述催化制备叶青素的方法，其特征在于：步骤1）中，FeCl3·6H2O、Zn(Ac)2·2H2O、醋酸钠和CTAB的物质的量之比为6:3:40:12，混合物中醋酸钠物质的量浓度为0.5mol/L。
3.如权利要求1所述催化制备叶青素的方法，其特征在于：步骤2）中，乙二醇、去离子水、氨水、钛酸四丁酯的体积比为100:25:5:1，ZnFe2O4磁性纳米晶与乙二醇的质量体积比为5g/L。
4.如权利要求1-3中任一所述催化制备叶青素的方法，其特征在于：所述苯甲醇、乙缩醛和水的摩尔比为1:5~10:10~30。
5.如权利要求4所述催化制备叶青素的方法，其特征在于：所述磁性离子液体的加入量为混合溶液重量的5~12%。
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