制备生物柴油的过程中会副产甘油，每生产10 吨生物柴油会副产约1 吨的甘油。近年来生物柴油产量快速增长，如何充分地、合理地利用甘油这种可再生的绿色化工基础原料成为当前的一个研究热点。目前，甘油转化可以得到一系列的化工产品，其中，碳酸甘油酯由于其独特的物理性质和活泼的反应性质而具有重要的应用价值，因此，本文对甘油转化为碳酸甘油酯进行了研究。甘油转化为碳酸甘油酯的生产路线主要有二氧化碳法、尿素法、碳酸乙烯酯法、碳酸二甲酯法等，各个生产路线的化学平衡常数尚未有文献报道。本文首次通过计算化学平衡常数，对各种反应路线及其适宜的操作条件进行比较和分析，结果表明甘油和碳酸二甲酯反应制备碳酸甘油酯是较好的生产路线。固体碱催化剂是碳酸二甲酯和甘油反应制备碳酸甘油酯的较好选择，已经报道的催化剂只有氧化钙和水滑石及其衍生物，这些催化剂存在严重的失活问题，并且其失活机理尚不清楚。本文比较了不同的固体碱催化剂，结果表明氧化锶、甲醇钙等固体碱也是催化活性较好的催化剂，但是，类似于氧化钙，其他固体碱催化剂均存在失活问题。针对固体碱催化剂在碳酸二甲酯和甘油反应中的失活问题，本文首次进行了系统研究，结果表明催化剂本身与甘油以及碳酸甘油酯的化学反应，以及催化剂在体系中的溶解损失是造成其失活的原因。在失活机理的基础上，发现甘油钙的抗失活性能较好，不过仍存在溶解损失问题。碳酸二甲酯和甘油反应制备碳酸甘油酯的传统工艺是一个先反应、后分离的过程，并且在反应阶段使用过量碳酸二甲酯。过量碳酸二甲酯和碳酸甘油酯的副反应降低了碳酸甘油酯产率，降低了产品纯度；同时，过量碳酸二甲酯的回收循环也会增加能量消耗。本文创新性地采用反应恒沸精馏耦合工艺来生产碳酸甘油酯，使碳酸二甲酯和甘油按照化学反应方程式计量系数比例完全反应，避免了过量碳酸二甲酯的使用，减少了碳酸甘油酯和碳酸二甲酯的副反应，提高了产品纯度，碳酸甘油酯产率大于94%，经过精制后的产品纯度大于97%。反应恒沸精馏耦合工艺也避免了过量碳酸二甲酯的回收，可以降低能耗。最后，采用Aspen Plus软件对反应恒沸精馏耦合新工艺进行了模拟，模拟结果与实验结果吻合；同时，通过与传统工艺比较，计算表明反应恒沸精馏耦合工艺的能耗是传统工艺能耗的29.9%。

In the biodiesel preparation, glycerol (G) is produced as a by-product with the amount as one tenth of biodiesel. With the development of biodiesel, much attention has been focused on the utilization of glycerol which is a renewable raw material in chemical industry. Now, a number of fine chemicals could be derived from glycerol. Glycerol carbonate(GC), as a new high value-added product, can be widely used for many applications due to its unique physical properties and active chemical properties. In this thesis, the conversion of glycerol to glycerol carbonate was studied.Glycerol can be converted to glycerol carbonate by the reaction of glycerol with carbon dioxide, the reaction of glycerol with urea, the transesterification of glycerol with ethylene carbonate or dimethyl carbonate(DMC). Chemical equilibrium constants of these reactions have not been reported. In this thesis, the chemical equilibrium of the reaction route was calculated in order to compare the reaction routes of glycerol to glycerol carbonate according to the theoretical conversion extent and to explore the optimal operation conditions. The results show that the reaction of glycerol with dimethyl carbonate is the most thermodynamically favorable and is the best choice for the preparation of glycerol carbonate from glycerol.Using hetergeneous alkali solid catalyst is a good choice for the preparation of glycerol carbonate from glycerol and dimethyl carbonate. The reported catalysts include calcium oxide and hydrotalcite. The catalyst deactivation was all observed in the recycle experiments. The deactivation mechanism of the alkali solid catalyst has not been investigated clearly. In this thesis, the different alkali solid catalysts were firstly compared. Alkali solid catalysts, such as calcium methoxide and strontium oxide also show good activity, but the catalyst deactivation was also observed in the recycle. Catalyst deactivation was then studied systematically.The results show that the chemical interactions of glyceol and glycerol carbonate with the alkali solid catalyst lead to the formation of basic calcium carbonate. The formation of basic calcium carbante and the catalyst dissolution in the reaction medium deactivated the catalysts. Based on the deactivation mechanism, calcium diglyceroxide was verified to have the excellent reusability for the transesterification of glycerol with dimethyl carbonate, but its dissolution in the reaction medium was also observed.The conventional production of glycerol carbonate from glycerol and dimethyl carbonate is a two steps process with the reaction of excess dimethyl carbonate with glycerol followed by the separation process. Excess dimethyl carbonate is used in the reaction step, which easily leads to the side reaction of glycerol carbonate with dimethyl carbonate and decreases the yield and purity of glycerol carbonate. The excess dimethyl carbonate should be recovered for recycling, which increased the energy consumption. In this thesis, the method of coupling reaction and azeotropic distillation was developed for the preparation of glycerol carbonate. The mole ratio of dimethyl carbonate to glycerol can be lowered to 1 according to the stoichiometric coefficient. The yield of glycerol carbonate can be above 94%. After the purification process, the concentration of glycerol carbonate can reach 97wt%. The new method avoids the use and recovery of excess dimethyl carbonate, which also lowers the energy consumption. Simulation of the conventional production method and method of coupling reaction and azeotropic distillation was conducted with Aspen Plus software. The simulation results are in agreement with the experiment results. The energy consumption of producing glycerol carbonate by the method of coupling reaction and azeotropic distillation is 29.9% of that by the conventional production method.