CN103896772A - 一种催化酯化甘油制备甘油酯的方法 - Google Patents
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Abstract
本发明涉及一种催化酯化甘油制备甘油酯的方法，即甘油和小分子有机酸在磺化石墨烯催化剂的催化作用下反应生成甘油酯。该方法所用的催化剂的载体为具有二维平面结构的石墨烯，活性组分为具有酸催化活性的有机官能团。在同比条件下采用磺化石墨烯催化剂所获得的甘油二酯和甘油三酯的选择性是HY、HBeta等沸石分子筛催化剂的3~5倍。本发明所说的方法中采用的催化剂以呈现二维平面结构、空间位阻小的石墨烯为载体，能够为大分子反应提供开阔的空间，因此能够获得较高的二、三酯选择性。
Description
技术领域
本发明涉及一种酯化反应方法，特别涉及一种催化酯化甘油制备甘油酯的方法。
背景技术
甘油酯是甘油和乙酸在酸催化剂作用下反应生成的，又分为一乙酸甘油酯、二乙酸甘油酯和三乙酸甘油酯。
一乙酸甘油酯可以用来制造鞣剂、溶剂染料、炸药。二乙酸甘油酯，可以用作增塑剂、溶剂和软化剂。三乙酸甘油酯，俗称作三醋精，它是一种无色透明的油状液体，无毒、无刺激性，略有一点酸味，是一种很好的增塑剂和溶剂，还可用于香料、印染和食品工业，它对硝基纤维素、乙酸纤维素、乙基纤维素的混溶性好，并且有着良好的胶凝作用，常用作做香烟过滤嘴中的胶凝剂，在香料生产中可用作溶剂和定香剂，还可以作为油墨的组分用于塑料和其它不易吸收表面上的印刷。在我国甘油多酯（二、三乙酸甘油酯）年消耗量很大，是一种非常有前景的化工原料。
工业生产甘油酯经常采用硫酸为催化剂,但是硫酸具有强腐蚀性和氧化性，因此会生成许多副产物，还出现较大程度的聚合现象，而且对设备有严重的腐蚀性。反应结束后，反应产物难与催化剂硫酸分离，产物需经过中和、水洗、干燥等处理，工艺较为复杂，且对环境存在严重污染。还有以氨基磺酸、离子液体、对甲苯磺酸等作为催化剂，试图提高酯化收率。但这些催化剂的催化效果尚未达到工业化水平。
目前业内正在研制能够用于酯化反应的固体酸催化剂，反应结束后，产物和催化剂分为两相，催化剂容易回收和循环使用。但是很多具有三维立体结构的固体酸催化剂，由于孔道限制，多酯的选择性较低。 Lauriol-Garbey P, Postole G, Loridant S, et al. Acid– base properties of nio bium–zirconium mixed oxide catalysts for glycerol dehydration by calorimetric and catalytic investigation. Appl Catal B: Environ [J], 2011, 106:94–102用大孔Amberlyst - 15催化剂在高压（20 KPa），乙酸甘油比为24:1的高摩尔比条件下取得较高的二三酯收率，但是，这么高的摩尔比在工业生产中是很不实际的，不仅浪费资源，而且树脂类催化剂热稳定性不好。
发明内容
本发明的目的是提供一种采用多相催化反应，具有反应活性高、反应条件温和稳定的催化酯化甘油制备甘油酯的方法。
磺化石墨烯是具有二维平面结构的催化剂，对二三酯大分子形成无位阻效应，对提高甘油的转化率和甘油多酯的选择性有着良好的促进作用。本发明即采用磺化石墨烯为催化剂合成甘油酯。
本发明通过以下技术方案予以实现：
甘油和乙酸在磺化石墨烯催化剂作用下反应生成甘油酯，反应温度为70~140℃，甘油与乙酸的摩尔比为1:1 ~1:50，反应压力为0 ~2MPa。
其中磺化石墨烯催化剂包括载体和催化活性组分，载体为还原石墨烯，催化活性组分为与还原石墨烯呈化学键结合的含有-SO3H基团的酸催化活性官能团。
还原石墨烯采用以下方法制备：
(1)通过氧化插层法结合超声分离或热膨胀法将鳞片石墨制备成氧化石墨烯；
(2)再将氧化石墨烯通过还原法制成还原石墨烯。
所述酸催化活性官能团包括苯磺酸官能团（-Ar-SO3H）、烷基磺酸官能团（-CnH2n-SO3H）、与石墨烯直接相连的磺酸官能团(-SO3H)中的一种或几种。
本发明的有益效果是：以往研究表明，硫酸作为催化剂有腐蚀性严重、反应后处理繁琐等缺点，具有三维立体孔道结构的中微孔酸性沸石位阻效应明显，二三酯收率低。大孔酸性树脂的热稳定性不理想。石墨烯呈现二维平面结构，空间位阻小，能够为大分子反应提供开阔的空间。将苯磺酸官能团化学嫁接到还原石墨烯表面，制备成磺化石墨烯催化剂，既具有酸催化活性，又无空间位阻作用，且为多相催化反应，为甘油和乙酸的酯化反应提供了一条高效绿色的合成路线。
具体实施方式
以下是通过实施例和对比例子进一步说明本发明实施方式和所产生的效果，但本发明的保护范围并不限于实施例所列的内容。
实验条件
1. 催化剂制备：参考文献J. Ji, G. Zhang, H. Chen, S. Wang, G. Zhang, F. Zhang, X. Fan, Chem. Sci. 2 (2011) 484 -487采用化学嫁接法制备磺化石墨烯催化剂。
本实施例中所用磺化石墨烯具体合成步骤为：将1g石墨烯在室温下超声分散在480ml乙醇中，之后冰浴控温2~5℃并在300r/min搅拌，再加入480ml质量百分含量为50%的次磷酸（分析纯，事先在冰箱里冷藏至2~5℃）和11克对重氮基苯磺酸湿饼（由对氨基苯磺酸制成的重氮产物，详细制备过程请见《有机化学实验》（第二版），兰州大学，复旦大学，王清廉编著，P203。由于干燥后的对氨基苯磺酸容易燃烧爆炸，所以过滤后形成的湿饼状产物不经干燥直接使用），40分钟后再加入480ml质量百分含量为50%的次磷酸，继续冰浴下搅拌1小时后停止反应，接着进行过滤分离，得到嫁接改性后的磺化石墨烯滤饼，之后用200ml的乙醇洗涤滤饼，再用去离子水洗涤至中性，将滤饼冷冻后放入真空冷冻干燥机中干燥24小时，得到黑色蓬松的磺化石墨烯催化剂。
为了对照说明本专利中的磺化石墨烯的效益，在对比实施例中采用了商业的酸性HY， HBeta和HZSM-5沸石分子筛作催化剂。沸石分子筛在反应前于马弗炉中500℃干燥3小时。
2. 反应测试：采用间歇反应进行甘油醚化反应。具体步骤为：
取一定量磺化石墨烯催化剂放入5ml容量的后壁耐压玻璃反应釜种中，往反应釜中加入276.27mg（3mmol)甘油和一定量乙酸，密封后放入事先预热好的磁力搅拌反应器中，开始计时在500转/分钟磁力搅拌下反应一段时间。反应后产物加入乙二醇内标物，用乙醇稀释后用气相色谱分析。色谱分析条件为：采用氢火焰检测器（FID），氢气作为载气。甘油转化率和甘油一酯(MAG)、甘油二酯(DAG)和甘油三酯（TAG）选择性作为评价指标，转化率为反应所消耗的甘油的物质量与最初投入甘油的物质量之比值；转化率为目标产物的物质量与转化掉的甘油物质量的比值。
3. 实施例
实施例1~4，不同反应温度的结果
反应条件：276.27mg（3mmol)甘油与1080.9mg(18mmol)乙酸，13.8mg 磺化石墨烯催化剂，应时间4h。
实施例5~8, 不同乙酸用量的结果
反应条件：276.27mg（3mmol)甘油，13.8mg 磺化石墨烯催化剂，应时间4h，反应温度100℃。
对比实施例1~4， 其他催化剂的反应性能
反应条件：276.27mg（3mmol)甘油与1080.9mg(18mmol)乙酸，13.8mg催化剂，应时间4h，反应温度100℃。
从实施例和对比实施例的实验结果来看，同比条件下磺化石墨烯和其它四个催化剂在催化甘油与乙酸酯化反应时均能获得较高的转化率，但是磺化石墨烯催化的二三酯的选择性要明显高于其它催化剂。
Claims (4)
1.一种催化酯化甘油制备甘油酯的方法，其特征在于，甘油和乙酸在磺化石墨烯催化剂作用下反应生成甘油酯，反应温度为70~140℃，甘油与乙酸的摩尔比为1:1 ~1:50，反应压力为0 ~2MPa。
2.根据权利要求1所述的催化酯化甘油制备甘油酯的方法，其特征在于，所述的磺化石墨烯催化剂包括载体和催化活性组分，载体为还原石墨烯，催化活性组分为与还原石墨烯呈化学键结合的含有-SO3H基团的酸催化活性官能团。
3.根据权利要求2所述的催化酯化甘油制备甘油酯的方法，其特征在于，所述还原石墨烯采用以下方法制备：
(1)通过氧化插层法结合超声分离或热膨胀法将鳞片石墨制备成氧化石墨烯；
(2)再将氧化石墨烯通过还原法制成还原石墨烯。
4.根据权利要求2所述的催化酯化甘油制备甘油酯的方法，其特征在于，所述酸催化活性官能团包括苯磺酸官能团（-Ar-SO3H）、烷基磺酸官能团（-CnH2n-SO3H）、与石墨烯直接相连的磺酸官能团(-SO3H)中的一种或几种。
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