CN112570022B - 一种磁性物质固载有机-无机杂化材料催化剂及其制备和应用 - Google Patents
一种磁性物质固载有机-无机杂化材料催化剂及其制备和应用 Download PDFInfo
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
本申请公开一种磁性物质固载有机‑无机杂化材料催化剂及其制备和应用，制备方法包括：(1)以有机胺、1，3‑丙磺酸内酯为原料在有机溶剂中按有机胺与1,3‑丙磺酸内酯物质的量比0.5‑1.5:1合成离子液体中间体；有机胺为吡啶、2,6‑二甲基吡啶、5‑乙基‑2‑甲基吡啶、喹啉、三乙胺、N,N‑二甲基苯胺、N,N‑二甲基苄胺中的任一种；(2)离子液体中间体与无机酸水溶液于油浴加热反应得酸性离子液体；无机酸为硅钨酸；(3)酸性离子液体与Fe3O4、正硅酸乙酯醇溶液于油浴中反应结束后，经后处理即得。本申请固载后的催化剂基本能够达到游离催化剂的催化性性能，用于月桂酸单甘脂的选择性制备中，催化效率高、选择性好、对环境污染小、重复性能好。
Description
技术领域
本申请涉及酯类制备技术领域，具体涉及一种磁性物质固载有机-无机杂化材料催化剂制备方法以及该催化剂在月桂酸与甘油酯化反应中的应用。
背景技术
月桂酸单甘酯(GML)既是优良的乳化剂，又是安全高效广谱的抗菌剂。GML作为一种安全的食品添加剂已广泛地运用到食品、制药、化妆品等行业。GML的常用制备方法是在质子酸催化剂存在下，通过月桂酸和甘油直接酯化得到，传统的催化法存在后处理繁琐、环境污染大、选择性差及催化效率低等方面的问题。
离子液体是一类新型的绿色化溶剂及催化剂，其无可测蒸气压、可循环使用、无环境污染、可设计性等优点成为研究热点，且在一定程度上解决了液态催化剂再生和废液减量问题，并且作为酯化反应催化剂时具有较好催化效果，但离子液体在使用过程中存在用量大、价格贵、粘度大、回收难等问题。
杂多酸是一种具有强酸性和强氧化性的可设计型固体酸，是一类新型环境友好催化材料。杂多酸催化反应时可调的催化特性及“假液相”反应场使其常显示较好的催化性能。但杂多酸自身存在的比表面积小，使用过程中易溶于极性溶剂而难以分离等问题使其工业应用受到限制。近年来，研究者利用有机物如离子液体特别是磺酸功能化离子液体与杂多酸结合起来制备出新颖有机-无机杂化材料受到广泛关注，该类材料在催化酯化反应、缩醛反应和醇氧化等反应中得到广泛应用，强酸性及“自分离”特性是该类催化剂具有高活性的原因。离子液体改性杂多酸催化反应时虽表现出较好的催化性能，但是该类催化剂仍存在离子液体用量大、成本高、有效活性成分流失及催化剂重复利用性差等缺点。
将离子液体硅钨酸固载于多孔材料上可有效解决上述问题。固载化离子液体不仅具有离子液体催化活性高的优点，同时，载体大的比表面积为催化反应提供更多的活性位点，还能减少催化剂用量，反应后催化剂与反应混合液通过简单过滤就能分离。此外，改变载体性质制备磁性载体，使固体催化剂的分离更加容易和经济。因此，开展磁性物质固载有机-无机杂化材料催化剂制备及催化性能研究具有重要的理论与实际意义。
申请内容
本申请提供了一种磁性物质固载有机-无机杂化材料催化剂的制备方法及其应用，固载后的催化剂基本能够达到游离催化剂的催化性性能，用于月桂酸单甘脂的选择性制备中，催化效率高、选择性好、对环境污染小、重复性能好。
一种磁性物质固载有机-无机杂化材料催化剂的制备方法，包括：
(1)以有机胺、1,3-丙磺酸内酯为原料在有机溶剂中按有机胺与1,3-丙磺酸内酯物质的量比0.5-1.5:1合成离子液体中间体；所述有机胺为吡啶、2,6-二甲基吡啶、5-乙基-2-甲基吡啶、喹啉、三乙胺、N,N-二甲基苯胺、N,N-二甲基苄胺中的任一种；
(2)所得离子液体中间体与无机酸水溶液于油浴加热反应得酸性离子液体；所述无机酸水溶液为硅钨酸水溶液；
(3)所得酸性离子液体与Fe3O4、正硅酸乙酯醇溶液于油浴中反应，经陈化后空气氛围中焙烧即得所述磁性物质固载有机-无机杂化材料催化剂；该步骤的反应体系中Fe3O4物质的量占10％-15％、酸性离子液体物质的量占4％-5％。
步骤(2)和步骤(3)可以分步进行，也可以一步反应。
离子液体不仅在结构和酸性上具有高度的可调性，而且还具备液体酸的高密度反应活性位和固体酸的不挥发性，其重要应用在于它的可设计性，即可与活性物质作用，进而提升反应的活性和选择性。近年来，将离子液体特别是磺酸功能化离子液体与活性物质杂多酸结合起来制备新型有机-无机杂化材料受到广泛关注，强酸性及“自分离”(self-seperation)特性是该类催化剂具有高活性的原因。
离子液体改性杂多酸催化反应时虽表现出较好的催化性能，但是该类催化剂仍存在离子液体用量大、成本高、有效活性成分流失及催化剂重复利用性差等缺点。针对选择性酯化反应过程中存在的一系列反应条件及后处理问题，发展了一种磁性物质固载有机-无机杂化材料催化剂。
本发明采用1,3-丙磺酸内酯、有机胺为原料制备得到有机离子液体中间体，该中间体分别与多种杂多酸结合得酸性离子液体，再利用溶胶凝胶法制备得磁性物质固载有机-无机杂化材料催化剂，催化剂中各组分之间相互协同，强酸性及空间效应使本发明制备得到的催化剂催化活性及稳定性都显著提高，对选择性催化制备月桂酸单甘酯具有良好的活性，3h内月桂酸转化率在90％以上，月桂酸单甘脂的选择性在80％以上，催化剂均可回收利用，在重复实验6次后，测定产率浮动均在6％以内。
磁性载体负载酸性离子液体基催化剂后，便于分离回用，但本申请在实验中发现，磁性载体负载后的催化剂活性不及游离催化剂活性，为解决该问题，本申请经过反复实践探索，发现通过特定的离子液体基催化剂与磁性载体以特定的配比组合，可克服该问题，制备得到的催化剂活性基本达到游离催化剂的活性，且多次重复利用后仍保持较高的催化活性。
以下还提供了若干可选方式，但并不作为对上述总体方案的额外限定，仅仅是进一步的增补或优选，在没有技术或逻辑矛盾的前提下，各可选方式可单独针对上述总体方案进行组合，还可以是多个可选方式之间进行组合。
本申请中所述有机胺为吡啶、2,6-二甲基吡啶、5-乙基-2-甲基吡啶、喹啉、三乙胺、N,N-二甲基苯胺、N,N-二甲基苄胺中的任一种；由此制备得到离子液体中间体吡啶丙基磺酸铵(PPS)、2,6-二甲基吡啶丙基磺酸铵(DMPPS)、5-乙基-2-甲基吡啶丙基磺酸铵(EMPPS)、喹啉丙基磺酸铵(QUPS)、三乙基丙基磺酸铵(TEAPS)、N,N-二甲基苯基丙基磺酸铵(DMAPS)、N,N-二甲基苄基丙基磺酸铵(DMBPS)；所述杂多酸为硅钨酸。
可选的，所述有机胺为N,N-二甲基苄胺和喹啉；所述酸为硅钨酸；更进一步可选的，所述有机胺为喹啉；所述无机酸为硅钨酸。
可选的，N,N-羰基二咪唑也可作为有机胺的选择，磷钨酸、磷钼酸也可作为无机酸的选择，但该选择制备得到的催化剂活性相比游离催化剂活性降低。
所述Fe3O4可采用市购商品，也可采用共沉淀法制备。共沉淀法制备中，使用的原料为FeCl3·6H2O和FeSO4·7H2O，其物质的量之比为2:1，油浴反应温度为40-90℃，时间为2-4h。进一步地，油浴反应温度为50℃，时间为2h。
可选的，步骤(1)中所述有机溶剂为乙酸乙酯或乙腈。
可选的，步骤(1)中所述1,3-丙磺酸内酯与有机胺的物质的量比为1:1。
可选的，步骤(2)中所述离子液体中间体与无机酸水溶液中的无机酸的物质的量比为1:1。
可选的，步骤(3)中，反应体系中Fe3O4物质的量占10％-15％、酸性离子液体物质的量占4％-5％。进一步可选的，反应体系中Fe3O4物质的量占10％、酸性离子液体物质的量占4％。
Fe3O4物质的量占10％-15％可以理解为Fe3O4物质的量占反应体系中三种原料物质量的总和的百分比，例如正硅酸乙酯、酸性离子液体和Fe3O4的物质的量的总和为100M，Fe3O4物质的量为10-15M。更进一步可选的，正硅酸乙酯与离子液体、Fe3O4的物质的量比为86:4:10。
可选的，步骤(1)在油浴中进行，油浴温度为40-80℃，时间为2-24h；步骤(2)中油浴温度为70-110℃，时间为18-30h；步骤(3)中油浴温度为50-100℃，搅拌时间为12-24h。
进一步可选的，步骤(1)中油浴反应的温度为60℃，时间为18h；步骤(2)中油浴反应的温度为90℃，时间为18h；步骤(3)反应的温度为60℃，时间为12h。
可选的，焙烧温度为200-220℃。
进一步可选的，将反应液置于培养皿挥发至干，110℃下过夜烘干，收集剩余物放置马弗炉中200℃煅烧5h，最终得所述的产物。
本申请还提供一种如所述制备方法制备得到的磁性载体固载有机-无机杂化材料催化剂。
本申请还提供一种如所述磁性载体固载有机-无机杂化材料催化剂在催化制备高级脂肪酸中的应用。
本申请还提供一种催化制备高级脂肪酸酯的方法，包括：
(1)以醇和羧酸为原料、权利要求6所述的磁性载体固载有机-无机杂化材料为催化剂，80-170℃油浴中反应0.5-5h；
(2)反应结束后冷却，催化剂与反应体系分层，通过磁分离回收固体催化剂，固体催化剂经乙醚洗涤、干燥后直接重复用于下一次反应。
可选的，所述羧酸为C8-C20的饱和或不饱和脂肪酸中的一种；所述醇为甲醇、乙醇、丙醇、乙二醇和丙三醇中的一种。进一步地，所述羧酸为月桂酸，所述醇为丙三醇。
可选的，所述羧酸与醇的物质的量比为1:2-14，所述催化剂的用量为羧酸质量的1％-8％。
进一步可选的，所述羧酸与醇的物质的量比为1:6，所述催化剂的用量为羧酸质量的4％-8％。
可选的，制备月桂酸单甘酯最优选在150℃油浴中反应3h。在上述优选条件组合下催化制备月桂酸单甘脂的产率和纯度都能达到一个较高值。
与现有技术相比，本申请至少具有如下有益效果之一：
本申请以1,3-丙磺酸内酯、有机胺与多种强酸为原料制备离子液体催化剂，并利用磁性载体将其固载化，得到的固载化催化剂应用于月桂酸单甘脂选择性酯化反应，反应操作简便、不同酸效应的协同作用使催化剂催化活性优良、产物选择性高、回收便利、循环使用性能良好。
本申请突出优点是离子液体使用量低、催化活性好、选择性高、催化剂分离回收简单、后处理简单、循环使用性能良好，属于绿色化学；更重要的是，本申请通过选择特定的离子液体基催化剂种类与磁性载体负载以及通过控制催化剂中相对含量来获得催化性能最优、稳定性最佳的催化剂，从而克服磁性物质负载类催化剂在酯化反应中催化活性的局限性。
具体实施方式
下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，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，都属于本申请保护的范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。
以下实施例中所用原料均为市售商品。
实施例1
以10％磁性物质负载4％喹啉基丙基磺酸基硅钨酸氢铵离子液体为例，催化剂的制备方法如下：
(1)磁性物质(Fe3O4)的合成：采用共沉淀法制备磁性材料Fe3O4，具体过程为：一定量FeCl3·6H2O和FeSO4·7H2O混合后溶于蒸馏水中，搅拌至完全溶解，然后缓慢滴加的NaOH溶液，油浴条件下反应，磁力沉降，将所得黑色沉淀分别用蒸馏水和无水乙醇洗涤，减压抽滤，真空干燥，自然冷却后得到Fe3O4样品。FeCl3·6H2O与FeSO4·7H2O物质的量之比为2:1；油浴反应温度为50℃，反应时间为2h。
(2)QUPS的制备：将1,3-丙磺酸内酯溶于乙腈中，然后向其中加入喹啉，将反应体系放置于油浴中，搅拌反应结束后，将产物用乙腈洗涤后，抽滤，真空干燥，可得到白色固体喹啉基丙烷磺酸盐(QUPS)。乙腈的量约为1,3-丙磺酸内酯的3-4倍，加入的喹啉与1,3-丙磺酸内酯同等摩尔量，油浴反应温度为60℃，反应时间为18h。
(3)适量磁性材料(Fe3O4)与一定量无水乙醇超声处理后，加入正硅酸乙酯混合物搅拌，然后向三颈瓶中加入适量离子液体前驱体(QUPS)及硅钨酸溶液，升温搅拌过夜。
离子液体前驱体与硅钨酸溶液中硅钨酸的物质的量之比为1:1；乙醇的量约为正硅酸乙酯的4-5倍，正硅酸乙酯与酸性离子液体、Fe3O4的物质的量比为86:4:10；油浴反应温度为60℃，反应时间为24h。
该步骤中也可分步进行，QUPS先与硅钨酸溶液反应得酸性离子液体，酸性离子液体再与磁性材料(Fe3O4)和正硅酸乙酯通过溶胶凝胶发制备固载催化剂。
(4)反应结束后，将胶状物移入培养皿中挥发至干，然后在110℃条件下干燥过夜，最后将所得固体物质在200℃条件下干燥5h，即得磁性材料负载不同量离子液体硅钨酸催化剂[QUPSH]1H3SiW12O40/SG-Fe3O4。
分别以磷钨酸(H3PW12O40)、磷钼酸(H3PMo12O40)替换以上步骤(2)中硅钨酸，以吡啶、2,6-二甲基吡啶、5-乙基-2-甲基吡啶、三乙胺、N,N-二甲基苯胺、N,N-二甲基苄胺、N,N-羰基二咪唑替换步骤(1)中的喹啉，得离子前驱体吡啶丙基磺酸铵(PPS)、2,6-二甲基吡啶丙基磺酸铵(DMPPS)、5-乙基-2-甲基吡啶丙基磺酸铵(EMPPS)、三乙基丙基磺酸铵(TEAPS)、N,N-二甲基苯基丙基磺酸铵(DMAPS)、N,N-二甲基苄基丙基磺酸铵(DMBPS)、N,N-羰基二咪唑丙基磺酸铵盐(CDIPS)，进而与磁性载体负载制备得到磁性材料负载的不同离子液体催化剂：[QUPSH]1H3SiW12O40/SG-Fe3O4、[QUPSH]1H2PW12O40/SG-Fe3O4[QUPSH]1H2PMo12O40/SG-Fe3O4、[PPSH]1H3SiW12O40/SG-Fe3O4、[DMPPSH]1H3SiW12O40/SG-Fe3O4、[EMPPSH]1H3SiW12O40/SG-Fe3O4、[TEAPSH]1H3SiW12O40/SG-Fe3O4、[DMAPSH]1H3SiW12O40/SG-Fe3O4、[DMBPSH]1H3SiW12O40/SG-Fe3O4、[CDIPSH]1/2H3SiW12O40/SG-Fe3O4。
同时在相同条件下制备游离的离子液体基催化剂，用作对照：
[QUPSH]1H3SiW12O40、[QUPSH]1H2PW12O40、[QUPSH]1H2PMo12O40、[PPSH]1H3SiW12O40、[DMPPSH]1H3SiW12O40、[EMPPSH]1H3SiW12O40、[TEAPSH]1H3SiW12O40、[DMAPSH]1H3SiW12O40、[DMBPSH]1H3SiW12O40、[CDIPSH]1/2H3SiW12O40。
将上述制备得到的不同离子液体催化剂用于以下实施例中催化合成月桂酸单甘脂。
实施例2-29
向装有恒压滴液漏斗和回流冷凝管的100mL的三口瓶中，依次加入月桂酸10.0g，丙三醇23.0g，负载催化剂(实施例1制备)或非负载催化剂(实施例1制备)0.60g，将其置于150℃油浴中加热反应3.0h。反应结束后冷却，催化剂与反应体系分层，通过磁铁简单处理分离固体催化剂，经乙醚洗涤、干燥后可直接用于下一次反应。蒸除过量的丙三醇，减压蒸馏得月桂酸单甘脂，气相色谱进行纯度检测。
非负载型催化剂得到酯化反应结果如表1所示。
表1游离催化剂酯化反应结果
| 催化剂种类 | 月桂酸转化率/％ | 单酯产率/％ |
| [QUPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub> | 95.0 | 80.2 |
| [QUPSH]<sub>1</sub>H<sub>2</sub>PW<sub>12</sub>O<sub>40</sub> | 94.3 | 76.3 |
| [QUPSH]<sub>1</sub>H<sub>2</sub>PMo<sub>12</sub>O<sub>40</sub> | 90.8 | 69.1 |
| [PPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub> | 91.7 | 69.8 |
| [DMPPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub> | 90.5 | 76.6 |
| [EMPPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub> | 92.5 | 76.8 |
| [TEAPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub> | 91.2 | 75.8 |
| [DMAPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub> | 93.5 | 76.8 |
| [DMBPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub> | 92.9 | 78.8 |
| [CDIPSH]<sub>1/2</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub> | 92.5 | 73.2 |
选用实施例1中制备的不同种类负载催化剂，按上述实例操作，得到酯化反应结果如表2和表3所示。
表2磁性物质负载不同量喹啉基丙基磺酸基硅钨酸氢铵离子液体催化剂催化活性
表3不同量磁性物质负载喹啉基丙基磺酸基硅钨酸氢铵离子液体催化剂催化活性
| 催化剂种类 | 月桂酸转化率/％ | 单酯产率/％ |
| 4％[QUPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub>/SG-Fe<sub>3</sub>O<sub>4</sub>(1％) | 77.3 | 56.4 |
| 4％[QUPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub>/SG-Fe<sub>3</sub>O<sub>4</sub>(5％) | 82.8 | 64.9 |
| 4％[QUPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub>/SG-Fe<sub>3</sub>O<sub>4</sub>(10％) | 94.0 | 79.1 |
| 4％[QUPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub>/SG-Fe<sub>3</sub>O<sub>4</sub>(15％) | 92.7 | 76.1 |
| 4％[QUPSH]<sub>1</sub>H<sub>3</sub>SiW<sub>12</sub>O<sub>40</sub>/SG-Fe<sub>3</sub>O<sub>4</sub>(20％) | 88.7 | 72.7 |
由表1和表2结果可知，4～5％[QUPSH]1H3SiW12O40/SG-Fe3O4(10％)、4％[PPSH]1H3SiW12O40/SG-Fe3O4(10％)、4％[DMPPSH]1H3SiW12O40/SG-Fe3O4(10％)、4％[EMPPSH]1H3SiW12O40/SG-Fe3O4(10％)、4％[TEAPSH]1H3SiW12O40/SG-Fe3O4(10％)、4％[DMAPSH]1H3SiW12O40/SG-Fe3O4(10％)和4％[DMBPSH]1H3SiW12O40/SG-Fe3O4(10％)的催化活性均能达到游离催化剂的催化活性。
由表3的结果可知，当磁性载体的相对含量在10-15％范围内时，负载催化剂活性基本达到游离催化剂活性。
实施例30-32
采用不同的方式制备催化剂4％[QUPSH]1H3SiW12O40/SG-Fe3O4(10％)，按上述实例2-19操作，得到酯化反应结果如表4所示。
表4不同方式制备的4％[QUPSH]1H3SiW12O40/SG-Fe3O4(10％)催化剂催化活性
| 催化剂制备方式 | 月桂酸转化率/％ | 单酯产率/％ |
| 浸渍法 | 78.1 | 63.4 |
| 共沉淀法 | 82.8 | 66.9 |
| 溶胶-凝胶法 | 94.0 | 79.1 |
| 交联法 | 93.4 | 77.2 |
由表4的结果可知，制备方法对磁性负载催化剂的活性也有一定影响。
实施例33-37
向装有回流冷凝管的100mL的三口瓶中，依次加入月桂酸10.0g，丙三醇23.0g，催化剂0.6g，将其置于150℃油浴中加热反应3.0h，反应结束后冷却，催化剂与反应体系分层，通过磁铁简单处理分离固体催化剂，经乙醚洗涤、干燥后可直接用于下一次反应。气相色谱对月桂酸转化率及月桂酸单甘酯收率进行分析。改变丙三醇与月桂酸物质的量比得到酯化反应结果如表5所示。
表5
| 醇酸物质的量比 | 月桂酸转化率/％ | 单酯产率/％ |
| 3 | 89.4 | 73.3 |
| 4 | 93.1 | 76.7 |
| 5 | 94.0 | 79.1 |
| 6 | 95.4 | 80.8 |
| 7 | 96.7 | 79.6 |
| 8 | 97.2 | 79.1 |
实施例38-47
向装有回流冷凝管的100mL的三口瓶中，依次加入月桂酸10.0g，丙三醇27.6g，催化剂0.6g，将其置于油浴中加热反应3.0h，反应结束后冷却，催化剂与反应体系分层，产物抽滤分离固体催化剂,经乙醚洗涤、干燥后可直接用于下一次反应。气相色谱对反应转化率及月桂酸单甘酯收率进行分析。改变不同反应温度得到酯化反应结果如表6所示。
表6
| 反应温度/℃ | 月桂酸转化率/％ | 单酯产率/％ |
| 130 | 81.3 | 70.5 |
| 140 | 88.6 | 76.9 |
| 150 | 95.4 | 80.8 |
| 160 | 98.0 | 77.7 |
| 170 | 99.1 | 72.7 |
以上反应结束后，催化剂均可回收利用，在重复实验六次后，测定产率浮动均在6％以内，重复实验数据见表7。
表7
| 重复使用次数 | 月桂酸转化率/％ | 单酯产率/％ |
| 1 | 95.0 | 79.5 |
| 2 | 93.7 | 78.8 |
| 3 | 90.9 | 77.9 |
| 4 | 88.8 | 76.8 |
| 5 | 86.9 | 75.9 |
| 6 | 84.9 | 75.1 |
由以上实施例证表明，该方式制备的催化剂，较低离子液体使用量时就显示较好的催化活性和高的单甘酯选择性，且后处理简便、催化剂重复利用性高、污染少，属于绿色化工技术。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。
Claims (9)
1.磁性物质固载有机-无机杂化材料催化剂在催化制备高级脂肪酸酯中的应用，其特征在于，所述磁性物质固载有机-无机杂化材料催化剂的制备方法包括：
(1)以有机胺、1,3-丙磺酸内酯为原料在有机溶剂中按有机胺与1,3-丙磺酸内酯物质的量比0.5-1.5:1合成离子液体中间体；所述有机胺为吡啶、2,6-二甲基吡啶、5-乙基-2-甲基吡啶、喹啉、三乙胺、N,N-二甲基苯胺、N,N-二甲基苄胺中的任一种；
(2)所得离子液体中间体与无机酸水溶液于油浴加热反应得酸性离子液体；所述无机酸水溶液为硅钨酸水溶液；
(3)所得酸性离子液体与Fe3O4、正硅酸乙酯醇溶液于油浴中反应，油浴温度为50-100℃，搅拌时间为12-24h；经陈化后空气氛围中200-220℃焙烧即得所述磁性物质固载有机-无机杂化材料催化剂；该步骤的反应体系中Fe3O4物质的量占10％-15％、酸性离子液体物质的量占4％-5％。
2.根据权利要求1所述的应用，其特征在于，步骤(1)中所述有机溶剂为乙酸乙酯或乙腈。
3.根据权利要求1所述的应用，其特征在于，步骤(2)中所述离子液体中间体与无机酸水溶液中的无机酸的物质的量比为1:1。
4.根据权利要求1所述的应用，其特征在于，步骤(1)在油浴中进行，油浴温度为40-80℃，时间为2-24h；步骤(2)中油浴温度为70-110℃，时间为18-30h。
5.一种催化制备高级脂肪酸酯的方法，其特征在于，包括：
(1)以醇和羧酸为原料、磁性物质固载有机-无机杂化材料为催化剂，80-170℃油浴中反应0.5-5h；所述羧酸与醇的物质的量比为1:2-14，所述催化剂的用量为羧酸质量的1％-8％；
所述磁性物质固载有机-无机杂化材料催化剂的制备方法包括：
1)以有机胺、1,3-丙磺酸内酯为原料在有机溶剂中按有机胺与1,3-丙磺酸内酯物质的量比0.5-1.5:1合成离子液体中间体；所述有机胺为吡啶、2,6-二甲基吡啶、5-乙基-2-甲基吡啶、喹啉、三乙胺、N,N-二甲基苯胺、N,N-二甲基苄胺中的任一种；
2)所得离子液体中间体与无机酸水溶液于油浴加热反应得酸性离子液体；所述无机酸水溶液为硅钨酸水溶液；
3)所得酸性离子液体与Fe3O4、正硅酸乙酯醇溶液于油浴中反应，油浴温度为50-100℃，搅拌时间为12-24h；经陈化后空气氛围中200-220℃焙烧即得所述磁性物质固载有机-无机杂化材料催化剂；该步骤的反应体系中Fe3O4物质的量占10％-15％、酸性离子液体物质的量占4％-5％；
(2)反应结束后冷却，催化剂与反应体系分层，通过磁分离回收固体催化剂，固体催化剂经乙醚洗涤、干燥后直接重复用于下一次反应。
6.根据权利要求5所述催化制备高级脂肪酸酯的方法，其特征在于，所述羧酸为C8-C20的饱和或不饱和脂肪酸中的一种；所述醇为甲醇、乙醇、丙醇、乙二醇和丙三醇中的一种。
7.根据权利要求5所述的方法，其特征在于，步骤1)中所述有机溶剂为乙酸乙酯或乙腈。
8.根据权利要求5所述的方法，其特征在于，步骤2)中所述离子液体中间体与无机酸水溶液中的无机酸的物质的量比为1:1。
9.根据权利要求5所述的方法，其特征在于，步骤1)在油浴中进行，油浴温度为40-80℃，时间为2-24h；步骤2)中油浴温度为70-110℃，时间为18-30h。
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