技术领域Technical field
本发明属于尿素醇解合成碳酸甘油酯的技术领域，特别涉及一种以尿素和甘油为原料，通过尿素醇解过程合成碳酸甘油酯的方法。The invention belongs to the technical field of synthesizing glyceryl carbonate through the alcoholysis of urea, and in particular relates to a method for synthesizing glyceryl carbonate through the alcoholysis of urea using urea and glycerol as raw materials.
背景技术Background technique
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。As a special biochemical substance, glycerol carbonate (GC) has the characteristics of high boiling point, low volatility, low freezing point, strong polarity, non-toxic, and biodegradable. Widely used in food, medicine, cosmetics, textiles, coatings, plastics, machinery, military, aviation, aerospace, integrated circuits and new energy. The synthesis methods of glycerol carbonate include phosgene method, CO oxidative carbonylation method, transesterification method, glycerol and urea carbonylation method and CO2 conversion method. Among them, glycerol alcoholysis using glycerol and urea as raw materials is considered to be a high molecular efficiency process. Because ammonia is a by-product produced during the alcoholysis of urea, it can also be used as a raw material for the synthesis of urea, and is considered a green process for the synthesis of glycerol carbonate.
在合成过程中，重要的是选择催化剂。During the synthesis process, it is important to select the catalyst.
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)。The catalysts used to synthesize glycerol carbonate from glycerol and urea are mainly the following: zinc-based catalysts (Co3 O4 /ZnO and Co50 Zn50 -350 composite materials, porous ZnO, zinc-aluminum composite materials, etc.), magnesium-based catalysts ( MgO, Au-MgO, Au-Pd-MgO, HT (Mg/Zn/Al) and Mg-Al-Zr), tungsten-based catalyst (SW21 , WO3 /TiO2 , ionic liquid catalyst (MPR[pmim][ Cl]+ZnO, PS-(Im)2 ZnBr2 , Q-MMTs and [PS-(Im)2 MX2 ]) and other catalysts (γ-zirconium phosphate, La2 O3 , La2 Cu0.5 Fe0.5 O4 etc.).
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。These catalysts can be mainly classified into two types: homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts have relatively high catalytic efficiency and fast reaction rates. However, there is a problem of difficulty in separating the product and the catalyst, which greatly increases the production cost. Heterogeneous catalysts can be separated from product and catalyst by simple filtration. However, since the catalyst and reactants belong to a heterogeneous system, its catalytic efficiency is reduced, and the amount of reactants converted per unit time and unit mass of the catalyst is small. In addition, existing catalysts require higher temperatures to convert glycerol into glycerol carbonate.
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，尤其在较低温度下，催化性能较差。In summary, the above-mentioned catalysts that catalyze the reaction of urea and glycerol to synthesize glycerol carbonate have certain defects. Mainly in terms of catalytic efficiency and catalyst separation, especially at lower temperatures, the catalytic performance is poor.
发明内容Contents of the invention
本发明要解决的技术问题是，克服背景技术存在的不足，提供一种尿素醇解法合成碳酸甘油酯的方法，以甘油和尿素为原料，在催化剂存在下，采用釜式反应通过尿素醇解合成碳酸甘油酯。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。The technical problem to be solved by the present invention is to overcome the shortcomings of the background technology and provide a method for synthesizing glyceryl carbonate through urea alcoholysis. Using glycerin and urea as raw materials, in the presence of a catalyst, a kettle reaction is used to synthesize glycerol carbonate through urea alcoholysis. Glyceryl carbonate. Achieve the effects of high yield of glycerol carbonate, short reaction time, low energy consumption (lower reaction temperature), and no pollution.
本发明使用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，高分散于反应液中，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。The catalyst used in the present invention is a solid nitrogen-containing nanocarbon catalyst (carbon quantum dot). The catalyst itself is nanoscale tiny carbon particles, which can form colloids in the reaction system and are highly dispersed in the reaction liquid to achieve ultra-efficient catalytic conversion. The amount of catalyst used is only a few thousandths of the existing reports. In addition, after the reaction, the product and catalyst can be separated by simple centrifugal separation technology.
本发明的具体技术方案如下：The specific technical solutions of the present invention are as follows:
一种合成碳酸甘油酯的方法，以摩尔比为1.5∶1的尿素和甘油为原料；在催化剂存在下进行尿素醇解反应，得到碳酸甘油酯，具体步骤为，在容器中加入原料和催化剂，置于恒温油浴中，在105～125℃下反应6～8h，得到碳酸甘油酯；所述的催化剂是固体含氮纳米碳材料(碳量子点)，催化剂的用量是甘油重量的0.002％～0.006％。A method for synthesizing glyceryl carbonate, using urea and glycerin with a molar ratio of 1.5:1 as raw materials; performing an alcoholysis reaction of urea in the presence of a catalyst to obtain glyceryl carbonate. The specific steps are: adding raw materials and catalyst to a container, Place in a constant temperature oil bath and react for 6 to 8 hours at 105 to 125°C to obtain glycerol carbonate; the catalyst is a solid nitrogen-containing nanocarbon material (carbon quantum dots), and the amount of catalyst is 0.002% to glycerin weight. 0.006%.
所述的催化剂按以下步骤制备：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。The catalyst is prepared according to the following steps: put chitosan, aluminum nitrate nonahydrate, citric acid and water with a molar ratio of 2.0 to 5.0:1.5:1.0:1000 in a round-bottomed flask, stir continuously until completely dissolved, and then add Phosphoric acid, the amount of phosphoric acid used is the same as that of aluminum nitrate nonahydrate, and then use 1:1 ammonia water to adjust the reaction solution to pH=4.5, continue stirring for 3 hours, evaporate on an 80°C water bath for 24 hours to remove the water, and evaporate to dryness The product is carbonized in a muffle furnace at 300°C. After carbonization, it is cooled to room temperature. The obtained carbon material is ground into a powder with a particle size of 40-60 mesh. The ground powder and nitric acid with a concentration of 4mol/L are mixed at the ratio of 1g:10mL. The mixture was stirred under heating conditions at 60°C for 5 hours, then rinsed with water, filtered with suction, and dried at 80°C for 24 hours to obtain the catalyst.
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。Preferably, the molar ratio of chitosan, aluminum nitrate nonahydrate, citric acid and water is: 3.0:1.5:1.0:1000.
有益效果：Beneficial effects:
1、本发明所用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。1. The catalyst used in the present invention is a metal-free catalytic system, which is the first high-efficiency catalyst in this system that does not add metal.
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。2. The reaction efficiency is high. Under the same conditions, the TOF is thousands of times that of the homogeneous catalysts reported in the literature.
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。3. The reaction temperature is low, and the reaction can efficiently synthesize glycerol carbonate at 110-125°C.
4.催化剂循环稳定性好，易于与反应体系分离。4. The catalyst has good cycle stability and is easy to separate from the reaction system.
附图说明Description of the drawings
图1是实施例2制备的Cat2的XPS图。Figure 1 is the XPS pattern of Cat2 prepared in Example 2.
图2是实施例2制备的Cat2的循环反应图。Figure 2 is a cycle reaction diagram of Cat2 prepared in Example 2.
图3是实施例2制备的Cat2的中断反应图。Figure 3 is a diagram of the interruption reaction of Cat2 prepared in Example 2.
具体实施方式Detailed ways
实施例1Example 1
(1)溶胶凝胶法制备含氮纳米碳催化剂(1) Preparation of nitrogen-containing nanocarbon catalysts by sol-gel method
取2.68g壳聚糖、4.8g九水合硝酸铝、1.60g柠檬酸和140ml水(按摩尔比，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％)。Take 2.68g chitosan, 4.8g aluminum nitrate nonahydrate, 1.60g citric acid and 140ml water (molar ratio, chitosan/aluminum nitrate nonahydrate/citric acid/water = 2.0/1.5/1.0/1000) in a circle In the bottom flask, continue stirring until completely dissolved, add 0.9 ml of phosphoric acid, adjust the reaction solution to pH=4.5 with 1:1 ammonia water, continue stirring for 3 hours, pour the reaction solution into the crucible, and evaporate on an 80°C water bath for 24 hours Remove moisture. The evaporated product is carbonized in a muffle furnace at 300°C. After carbonization, it is cooled to room temperature, and the obtained carbon material is ground into powder with a particle size of 40-60 mesh. Add 1g of ground powder and 10ml of nitric acid with a concentration of 4mol/L into a single-mouth bottle with magnetic stirring, stir for 5h under heating conditions at 60°C, then rinse with water and filter, and dry at 80°C for 24h to obtain a solid Nanocarbon material Cat1 (nitrogen content is 6%).
(2)尿素醇解合成碳酸甘油酯反应测试实验(2) Test experiment on reaction of alcoholysis of urea to synthesize glyceryl carbonate
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％。In a three-necked flask, add 45g of urea, 46g of glycerol, and 0.001g of catalyst (less than 1/2000 of the currently reported catalyst dosage). Place it in a constant temperature water bath, heat to 115°C, and perform a decompression reaction at a pressure of 7kPa. The reaction lasts for 6 hours. After sampling, chromatographic analysis was performed, and the yield of glyceryl carbonate was calculated using the internal standard method. The selectivity of glyceryl carbonate is 95%, and the yield of glyceryl carbonate is 62.9%.
实施例2Example 2
(1)溶胶凝胶法制备含氮纳米碳催化剂(1) Preparation of nitrogen-containing nanocarbon catalysts by sol-gel method
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XPS图如图1所示。Take 4.05g chitosan, 4.80g aluminum nitrate nonahydrate, 1.60g citric acid and 140ml water (chitosan/aluminum nitrate nonahydrate/citric acid/water = 3.0/1.5/1.0/1000) in a round-bottomed flask, After continuing to stir until completely dissolved, add 0.9 ml of phosphoric acid, adjust the pH of the reaction solution to 4.5 with 1:1 ammonia water, continue stirring for 3 hours, pour the reaction solution into a crucible, and evaporate on an 80°C water bath for 24 hours to remove water. The evaporated product is carbonized in a muffle furnace at 300°C. After carbonization, it is cooled to room temperature, and the obtained carbon material is ground into powder with a particle size of 40-60 mesh. Add 1g of ground powder and 10ml of nitric acid with a concentration of 4mol/L into a single-mouth bottle with magnetic stirring, stir for 5h under heating conditions at 60°C, then rinse with water and filter, and dry at 80°C for 24h to obtain a solid Nanocarbon material Cat2 (nitrogen content is 12%). The XPS pattern of the prepared solid nanocarbon material Cat2 is shown in Figure 1.
(2)尿素醇解合成碳酸甘油酯反应测试实验(2) Test experiment on reaction of alcoholysis of urea to synthesize glyceryl carbonate
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。具体结果表1和图2所示。另外，对该催化剂进行了多相化测试，将催化剂在反应4h后趁热过滤，得到的滤液继续在相同条件下继续反应，反应结果如图3所示。证明反应过程中并没有活性组分的流失现象产生。In a three-necked flask, add 45g of urea, 46g of glycerin, and 0.002g of Cat2, place it in a constant temperature water bath, heat to 125°C, and perform a pressure reduction reaction at a pressure of 7kPa. Samples were taken at 8 hours of reaction, analyzed by chromatography, and used the internal standard method. , the yield of glycerol carbonate is calculated. The selectivity to glyceryl carbonate was 99%, and the yield of glyceryl carbonate was 93.2%. In addition, the catalyst was recovered through filtration, dried in a vacuum oven at 80°C for 24 hours, and recycled five times. The specific results are shown in Table 1 and Figure 2. In addition, a heterogeneous test was conducted on the catalyst. The catalyst was filtered while hot after reacting for 4 hours, and the obtained filtrate continued to react under the same conditions. The reaction results are shown in Figure 3. It proves that there is no loss of active components during the reaction.
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Table 1 Experimental results of cycle reactions for the synthesis of glycerol carbonate catalyzed by solid catalysts
实施例3：Example 3:
(1)溶胶凝胶法制备含氮纳米碳催化剂(1) Preparation of nitrogen-containing nanocarbon catalysts by sol-gel method
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％)。Take 6.69g chitosan, 4.80g aluminum nitrate nonahydrate, 1.60g citric acid and 140ml water (chitosan/aluminum nitrate nonahydrate/citric acid/water = 5.0/1.5/1.0/1000) in a round-bottomed flask, After continuing to stir until completely dissolved, add 0.9 ml of phosphoric acid, adjust the pH of the reaction solution to 4.5 with 1:1 ammonia water, continue stirring for 3 hours, pour the reaction solution into a crucible, and evaporate on an 80°C water bath for 24 hours to remove water. The evaporated product is carbonized in a muffle furnace at 300°C. After carbonization, it is cooled to room temperature, and the obtained carbon material is ground into powder with a particle size of 40-60 mesh. Add 1g of ground powder and 10ml of nitric acid with a concentration of 4mol/L into a single-mouth bottle with magnetic stirring, stir for 5h under heating conditions at 60°C, then rinse with water and filter, and dry at 80°C for 24h to obtain a solid Nanocarbon material Cat3 (nitrogen content is 15%).
(2)尿素醇解合成碳酸甘油酯反应测试实验(2) Test experiment on reaction of alcoholysis of urea to synthesize glyceryl carbonate
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％。In a three-necked flask, add 45g of urea, 46g of glycerol, and 0.003g of catalyst, place it in a constant temperature water bath, heat to 105°C, and perform a pressure reduction reaction at a pressure of 7kPa. Samples were taken after 7 hours of reaction, and analyzed by chromatography using the internal standard. Method, the yield of glycerol carbonate is calculated. The selectivity to glyceryl carbonate was 98%, and the yield of glyceryl carbonate was 78.4%.
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| CN114957009A (en) | 2022-08-30 |
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