CN104876886B - 十三吗啉季铵碱的制备方法 - Google Patents

十三吗啉季铵碱的制备方法 Download PDF

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CN104876886B
CN104876886B CN201510179832.9A CN201510179832A CN104876886B CN 104876886 B CN104876886 B CN 104876886B CN 201510179832 A CN201510179832 A CN 201510179832A CN 104876886 B CN104876886 B CN 104876886B
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quaternary ammonium
tridemorph
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沈爱宝
吴锦明
华宇杰
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Shandong Yatai Medical Instrument Co ltd
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    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract

本发明公开了十三吗啉季铵碱的制备方法，十三吗啉季铵碱通过十三吗啉烷基化、阴离子交换和碱化三步反应制备得到；该化合物作为催化剂在油脂与甲醇酯交换反应制备生物柴油中的应用。本发明的优点是十三吗啉季铵碱作为制备生物柴油的催化剂不但具有优异的催化活性，且反应结束后易分离，能够循环使用多次后仍保持较高的活性。

Description

十三吗啉季铵碱的制备方法
本申请是申请号：201410069592.2、申请日：2014.2.27、名称“十三吗啉季铵碱及其制备方法和用途”的分案申请。
技术领域
本发明涉及一种十三吗啉季铵碱及其制备方法和用途。
背景技术
季铵碱的应用广泛，可作为分子筛合成的模板剂、相转移催化剂、碱催化剂等。常见的季铵碱有氢氧化四甲基铵、氢氧化四丁基铵等，它们可作为催化剂用于生物柴油的生产，但它们在反应结束后，无法直接回收和循环使用，因此需要设计合成一种催化活性优良、能够循环使用的季铵碱，同时能简化生物柴油的生产工艺，降低生产成本。
发明内容
本发明的目的在于提供一种催化性能优异、容易回收和重复使用的十三吗啉季铵碱及其制备方法和用途。
本发明的技术解决方案是：
一种十三吗啉季铵碱，其特征是：结构式为：
R为正丁基、正辛基、苄基或2-吡啶甲基，C13H27为十三烷基。
一种十三吗啉季铵碱的制备方法，其特征是：包括以下步骤：
1)卤化十三吗啉季铵盐的制备：十三吗啉与等摩尔的卤代烃在100～120℃反应24～72h，经重结晶，得淡黄色固体或粘稠物，即为卤化十三吗啉季铵盐；
2)硫酸氢十三吗啉季铵盐的制备：第1)步反应得到的卤化十三吗啉季铵盐与等摩尔的硫酸氢钠于90℃反应3～6h，抽滤除去反应生成的卤化钠固体，得黄色油状的硫酸氢十三吗啉季铵盐；
3)十三吗啉季铵碱的制备：第2)步反应得到的硫酸氢十三吗啉季铵盐溶于水后与等摩尔的氢氧化钡溶液反应2～4h，抽滤除去反应生成的硫酸钡固体，滤液分去水层，即得黄色粘稠状的十三吗啉季铵碱(低温时呈半凝固状)。
十三吗啉季铵碱的合成路线如下：
所述的十三吗啉季铵碱的制备方法，其特征是：所述卤代烃为正丁基溴、正辛基溴、苄基氯或2-氯甲基吡啶。
一种十三吗啉季铵碱作为酯交换反应催化剂的应用，其特征是：包括以下步骤：
油脂、甲醇按摩尔比1∶6～10投料，再投入油脂质量1～5％的催化剂十三吗啉季铵碱，回流2～4h，将反应液冷却、静置，催化剂呈半凝固状析出(简单过滤，即可回收，可直接用于下一轮反应)，其余分成两层，上层为生物柴油，经蒸馏得到成品，下层为甲醇和甘油混合物，通过蒸馏分离。
所述油脂为植物油或经过处理的地沟油。
本发明具有以下优点：
因独特的氧氮杂环及长链的十三烷基结构，使其具有独特的理化性质，尤其是它的粘度受温度变化显著，在高于60℃时，粘度小，经搅拌，与油脂、甲醇混合性能好，保证了高的催化活性，在低于20℃时，成高粘度的半固体析出，易于与其他物质(如生物柴油、甘油、甲醇)分离。作为催化剂能循环使用多次，仍保持较高的活性。制备方法简便，生产成本相对低廉，适合规模生产。作为生产生物柴油的催化剂，简化了生物柴油的生产流程，并且生产过程基本无废水、绿色环保。
下面结合实施例对本发明作进一步说明。
具体实施方式
实施例1：溴化十三吗啉正丁基铵的制备
44.6g(0.150mol)十三吗啉与20.6g(0.150mol)正丁基溴120℃下搅拌反应48h，得黄色半固体粗品，经乙酸乙酯重结晶，得淡黄色固体的溴化十三吗啉正丁基铵63.2g，产率96.9％。
实施例2：N-正丁基十三吗啉硫酸氢盐的制备
43.4g(0.100mol)溴化十三吗啉正丁基铵与12.0g(0.100mol)硫酸氢钠，90℃搅拌反应4h，过滤除去反应生成的溴化钠固体，得黄色油状的N-正丁基十三吗啉硫酸氢盐43.5g，产率96.2％。
实施例3：N-正丁基十三吗啉季铵碱的制备
22.6g(0.0500mol)N-正丁基十三吗啉硫酸氢盐溶解于100mL水与含8.6g(0.050mol)氢氧化钡的水溶液搅拌反应3h，过滤除去反应生成的硫酸钡固体，滤液分去水层，得到黄色粘稠状的N-正丁基十三吗啉季铵碱18.1g，收率97.3％。
所得N-正丁基十三吗啉季铵碱的测定结果：
核磁共振氢谱(1H NMR,300MHz,D2O)δ3.66-3.62(m,2H)，3.51-3.48(m，4H)，3.24-3.22(m,4H)，1.34-1.32(m,22H)，1.73(m,4H)，1.21(d，J＝7.2Hz，6H)，0.97(t，J＝7.2Hz，3H)，0.96(t，J＝7.2Hz，3H)。
傅里叶变换红外光谱(溴化钾压片)：3415cm-1(宽大峰)为H-O-键的伸缩振动峰；2962cm-1、2873cm-1为甲基C-H键的伸缩振动峰；2929cm-1为亚甲基的C-H键的伸缩振动峰；1458cm-1、1378cm-1为甲基的C-H键的弯曲振动峰；1333cm-1为吗啉环上C-H键的弯曲振动峰；1179cm-1、1146cm-1为C-N+键的伸缩振动峰；1082cm-1、1046cm-1为C-O键的伸缩振动峰。
实施例4：N-正丁基十三吗啉季铵碱催化制备生物柴油
250mL三颈瓶上安装电动搅拌机、回流冷凝管，加入100g大豆油、35mL甲醇、5g N-正丁基十三吗啉季铵碱，回流反应3h，将反应液冷却、静置分层，过滤回收催化剂，其余分成两层，下层为甘油与甲醇混合物(可通过蒸馏分别回收)，上层为生物柴油粗品，经蒸馏，得纯品96.4g，产率96.4％(以大豆油质量计)。
实施例5：催化剂重复使用性能
将前一轮分离所得催化剂用于下一轮试验，步骤同实例4，五轮试验所得的生物柴油产率分别为96.4％、96.0％、95.4％、94.6％、93.6％(如适当补充催化剂，可使收率提高)。

Claims (1)

1.一种十三吗啉季铵碱的制备方法，其特征是：包括以下步骤：
1)卤化十三吗啉季铵盐的制备：十三吗啉与等摩尔的卤代烃在100～120℃反应24～72h，经重结晶，得淡黄色固体或粘稠物，即为卤化十三吗啉季铵盐；
2)硫酸氢十三吗啉季铵盐的制备：第1)步反应得到的卤化十三吗啉季铵盐与等摩尔的硫酸氢钠于90℃反应3～6h，抽滤除去反应生成的卤化钠固体，得黄色油状的硫酸氢十三吗啉季铵盐；
3)十三吗啉季铵碱的制备：第2)步反应得到的硫酸氢十三吗啉季铵盐溶于水后与等摩尔的氢氧化钡溶液反应2～4h，抽滤除去反应生成的硫酸钡固体，滤液分去水层，即得黄色粘稠状的十三吗啉季铵碱；
所述卤代烃为正丁基溴；
所述十三吗啉季铵碱，结构式为：
R为正丁基。
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