CN114904554A - 一种用于尿素醇解合成碳酸甘油酯的催化剂的制备方法 - Google Patents
一种用于尿素醇解合成碳酸甘油酯的催化剂的制备方法 Download PDFInfo
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Abstract
本发明的一种用于尿素醇解合成碳酸甘油酯的催化剂的制备方法属于催化剂制备的技术领域。将壳聚糖、九水合硝酸铝、柠檬酸和水搅拌至完全溶解后，加入磷酸，再用氨水将反应液调制成pH＝4.5，继续搅拌3h，在80℃水浴上蒸发24h除去水分，将蒸干的产物置于300℃马弗炉中碳化，得到的碳材料研磨并和硝酸在60℃加热条件下搅拌5h，冲洗、抽滤、烘干，得到所述的催化剂。本发明制备的催化剂为无金属催化体系，是该体系中首例不添加金属的高效催化剂，且具有反应效率高、反应温度低、循环稳定性好、易于与反应体系分离等优点。
Description
技术领域
本发明属于催化剂制备的技术领域，特别涉及在一种空间结构为零维的、具有荧光性质、以胶体状态(均匀分散)存在于反应体系中的固体含氮纳米碳催化剂(碳量子点)的制备，以及该催化剂在催化尿素醇解合成碳酸甘油酯方面的应用。
背景技术
碳酸甘油(GC)作为一种特殊的生物化学物质，具有高沸点、低挥发性、低冰点、强极性、无毒、可生物降解等特点。广泛应用于食品、医药、化妆品、纺织品、涂料、塑料、机械、军事、航空、航天、集成电路和新能源等领域。碳酸甘油的合成方法有光气法、CO氧化羰基化法、酯交换法、甘油与尿素羰基化法和CO2转化法。其中，以甘油和尿素为原料的甘油醇解被认为是一种高分子效率的过程。因为氨气是尿素醇解过程中产生的副产物，也可以作为合成尿素的原料，被认为是合成碳酸甘油酯的绿色工艺。
在合成过程中，重要的是选择催化剂。
甘油和尿素合成碳酸甘油酯使用的催化剂主要为以下几种：锌基催化剂(Co3O4/ZnO和Co50Zn50-350复合材料，多孔ZnO，锌铝复合材料等)，镁基催化剂(MgO，Au-MgO，Au-Pd-MgO，HT(Mg/Zn/Al)和Mg-Al-Zr)，钨基催化剂(SW21，WO3/TiO2，离子液体催化剂(MPR[pmim][Cl]+ZnO，PS-(Im)2ZnBr2，Q-MMTs和[PS-(Im)2MX2])和其他催化剂(γ-锆磷酸盐，La2O3，La2Cu0.5Fe0.5O4等)。
这些催化剂主要可以归纳为均相催化剂和非均相催化剂两种类型。均相催化剂催化效率相对较高，反应速率较快。但是存在产物与催化剂分离困难的问题，大大提高了生产成本。非均相催化剂可以通过简单的过滤达到产物和催化剂的分离。但是，由于催化剂与反应物属于非均相体系，从而降低了其催化效率，单位时间单位质量的催化剂转化的反应物的量较少。另外，现有催化剂都需要在较高温度下才能实现甘油向甘油碳酸酯的转化。
综上所述，以上所提到的催化剂，催化尿素与甘油反应合成碳酸甘油酯都存在一定的缺陷。主要是催化效率和催化剂分离两方面不能兼顾，尤其在较低温度下，催化性能较差。
发明内容
本发明要解决的技术问题是，克服背景技术存在的不足，提供一种催化活性高、性质稳定的高效催化剂，用于催化尿素醇解合成碳酸甘油酯，在碳酸甘油酯合成中实现碳酸甘油酯收率高、反应时间短、能耗小(降低反应温度)、无污染的效果。
本发明制备的催化剂是固体含氮纳米碳催化剂(碳量子点)。该催化剂本身就是纳米级的微小碳颗粒，可以在反应体系中形成胶体，使其高分散在反应液中，达到超高效催化转化的目的，催化剂用量仅为现有报道的千分之几。另外，反应后可以通过简单的离心分离技术实现产物和催化剂的分离。该固体含氮纳米碳催化剂(碳量子点)以壳聚糖，硝酸铝，柠檬酸，蒸馏水等为原料采用凝胶溶胶法制备。通过调节壳聚糖和柠檬酸的比例，制备出氮的质量百分含量为6-15％，粒径为1-2nm的零维的碳量子点材料。
本发明的具体技术方案如下：
一种用于尿素醇解合成碳酸甘油酯的催化剂的制备方法，步骤如下：将摩尔比为2.0～5.0:1.5:1.0:1000的壳聚糖、九水合硝酸铝、柠檬酸和水于圆底烧瓶中，持续搅拌至完全溶解后，加入磷酸，磷酸的用量与九水合硝酸铝的物质的量相同，再用1:1的氨水将反应液调制成pH＝4.5，继续搅拌3h，在80℃水浴上蒸发24h除去水分，将蒸干的产物置于300℃马弗炉中碳化，碳化后冷却至室温，将得到的碳材料研磨为粒径40～60目的粉末；将研磨后的粉末和浓度为4mol/L的硝酸按1g:10mL的比例在60℃加热条件下搅拌5h，然后用水冲洗抽滤，在80℃条件下烘干24h，得到所述的催化剂。
作为优选，壳聚糖、九水合硝酸铝、柠檬酸和水的摩尔比为：3.0:1.5:1.0:1000。
有益效果：
1、本发明制备的催化剂为无金属催化体系，是该体系中首例不添加金属的高效催化剂。
2、反应效率高，相同条件下，TOF是文献报道的均相催化剂的几千倍。
3、反应温度低，反应可以在110-125℃条件下高效合成碳酸甘油酯。
4.催化剂循环稳定性好，易于与反应体系分离。
附图说明
图1是实施例2制备的Cat2的TEM图。
图2是实施例2制备的Cat2的荧光图。
图3是实施例2制备的Cat2的固体紫外图。
具体实施方式
实施例1
(1)溶胶凝胶法制备含氮纳米碳催化剂
取2.68g壳聚糖、4.8g九水合硝酸铝、1.60g柠檬酸和140ml水(壳聚糖/九水合硝酸铝/柠檬酸/水＝2.0/1.5/1.0/1000)于圆底烧瓶中，持续搅拌至完全溶解后，加入0.9ml磷酸，用1:1的氨水将反应液调制成pH＝4.5，继续搅拌3h，将反应液倒入坩埚中，在80℃水浴上蒸发24h除去水分。将蒸干的产物置于300℃马弗炉中碳化，碳化后冷却至室温，将得到的碳材料研磨为粒径40-60目的粉末。将1g研磨后的粉末和10ml浓度为4mol/L的硝酸加入到带磁力搅拌的单口瓶中，60℃加热条件下搅拌5h，然后用水冲洗抽滤，在80℃条件下烘干24h，得到固体纳米碳材料Cat1(含氮量为6％)。
(2)尿素醇解合成碳酸甘油酯反应测试实验
在三颈烧瓶中，加入尿素45g，甘油46g，催化剂0.001g(小于现有报道催化剂用量的1/2000)，置于恒温水浴中，加热至115℃，压力为7kPa进行减压反应，反应6h后取样，经色谱分析，利用内标法，经过计算得到碳酸甘油酯的收率。碳酸甘油酯选择性为95％，碳酸甘油酯收率为62.9％。
实施例2
(1)溶胶凝胶法制备含氮纳米碳催化剂
取4.05g壳聚糖、4.80g九水合硝酸铝、1.60g柠檬酸和140ml水(壳聚糖/九水合硝酸铝/柠檬酸/水＝3.0/1.5/1.0/1000)于圆底烧瓶中，持续搅拌至完全溶解后，加入0.9ml磷酸，用1:1的氨水将反应液调制pH＝4.5，继续搅拌3h，将反应液倒入坩埚中，在80℃水浴上蒸发24h除去水分。将蒸干的产物置于300℃马弗炉中碳化，碳化后冷却至室温，将得到的碳材料研磨为粒径40-60目的粉末。将1g研磨后的粉末和10ml浓度为4mol/L的硝酸加入到带磁力搅拌的单口瓶中，60℃加热条件下搅拌5h，然后用水冲洗抽滤，在80℃条件下烘干24h，得到固体纳米碳材料Cat2(含氮量为12％)。制得的固体纳米碳材料Cat2的TEM图如图1所示，荧光图如图2所示，固体紫外图如图3所示。
(2)尿素醇解合成碳酸甘油酯反应测试实验
在三颈烧瓶中，加入尿素45g，甘油46g，Cat2 0.002g，置于恒温水浴中，加热至125℃，压力为7kPa进行减压反应，分别在反应8h取样，经色谱分析，利用内标法，经过计算得到碳酸甘油酯的收率。碳酸甘油酯选择性为99％，碳酸甘油酯收率为93.2％。另外，通过过滤方法回收催化剂，在真空烘箱中80℃烘干24h，循环使用5次。具体结果如下：
表1固体催化剂催化合成碳酸甘油酯的循环反应实验结果
| 反应次数 | 碳酸甘油酯选择性 | 碳酸甘油酯收率 |
| 1 | 99％ | 93.2％ |
| 2 | 99％ | 91.8％ |
| 3 | 98％ | 91.6％ |
| 4 | 98％ | 90.9％ |
| 5 | 99％ | 90.1％ |
实施例3：
(1)溶胶凝胶法制备含氮纳米碳催化剂
取6.69g壳聚糖、4.80g九水合硝酸铝、1.60g柠檬酸和140ml水(壳聚糖/九水合硝酸铝/柠檬酸/水＝5.0/1.5/1.0/1000)于圆底烧瓶中，持续搅拌至完全溶解后，加入0.9ml磷酸，用1:1的氨水将反应液调制pH＝4.5，继续搅拌3h，将反应液倒入坩埚中，在80℃水浴上蒸发24h除去水分。将蒸干的产物置于300℃马弗炉中碳化，碳化后冷却至室温，将得到的碳材料研磨为粒径40-60目的粉末。将1g研磨后的粉末和10ml浓度为4mol/L的硝酸加入到带磁力搅拌的单口瓶中，60℃加热条件下搅拌5h，然后用水冲洗抽滤，在80℃条件下烘干24h，得到固体纳米碳材料Cat3(含氮量为15％)。
(2)尿素醇解合成碳酸甘油酯反应测试实验
在三颈烧瓶中，加入尿素45g，甘油46g，催化剂0.003g，置于恒温水浴中，加热至105℃，压力为7kPa进行减压反应，分别在反应7h后取样，经色谱分析，利用内标法，经过计算得到碳酸甘油酯的收率。碳酸甘油酯选择性为98％，碳酸甘油酯收率为78.4％。
Claims (2)
1.一种用于尿素醇解合成碳酸甘油酯的催化剂的制备方法，步骤如下：将摩尔比为2.0～5.0:1.5:1.0:1000的壳聚糖、九水合硝酸铝、柠檬酸和水于圆底烧瓶中，持续搅拌至完全溶解后，加入磷酸，磷酸的用量与九水合硝酸铝的物质的量相同，再用1:1的氨水将反应液调制成pH＝4.5，继续搅拌3h，在80℃水浴上蒸发24h除去水分，将蒸干的产物置于300℃马弗炉中碳化，碳化后冷却至室温，将得到的碳材料研磨为粒径40～60目的粉末；将研磨后的粉末和浓度为4mol/L的硝酸按1g:10mL的比例在60℃加热条件下搅拌5h，然后用水冲洗抽滤，在80℃条件下烘干24h，得到所述催化剂。
2.根据权利要求1所述一种用于尿素醇解合成碳酸甘油酯的催化剂的制备方法，其特征在于，壳聚糖、九水合硝酸铝、柠檬酸和水的摩尔比为：3.0:1.5:1.0:1000。
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