顶空-色谱法研究松节油倍半萜组分体系汽液平衡性质

Vapor-liquid equilibrium data of turpentine sesquiterpene components + (green solvent, surfactants and entrainers) systems are determined using headspace-gas chromatography and an improved vapor-liquid equilibrium Ellis still with stirring function. Fitting the saturated vapor pressure parameters of turpentine sesquiterpene components, establishing the vapor liquid equilibrium model of binary, ternary and quaternary for turpentine sesquiterpene components system, predicting the thermodynamic properties such as the excess Gibbs free energy and excess enthalpy of turpentine sesquiterpene components system. The solid-liquid, vapor-liquid-solid equilibrium data of (single solute and solvent, single solute multi solvent, multi solute and solvent) systems when turpentine is used as a green solvent are determined a dynamic method with laser diffraction monitoring observation-automatic temperature control-computer collecting technique to identify solid-liquid equilibrium point. The relationship between molecular structure, intermolecular forces and the solubility of turpentine sesquiterpene components system are investigated according to molecular thermodynamics. The molar evaporation enthalpy, entropy and Gibbs free enthalpy of turpentine sesquiterpene components are determined using differential scanning calorimetry(DSC), and then their correlation models with temperature are established. The non-isothermal decomposition process of turpentine sesquiterpene components is investigated via differential method and integral method, and the thermal decomposition model of which in different atmosphere is established. The results will provide basic thermodynamic data for the development of turpentine sesquiterpene components and their green solvent system.

采用顶空-色谱法和具有搅拌功能的改进Ellis汽液平衡釜，测定松节油倍半萜组分+绿色溶剂、松节油倍半萜组分+表面活性剂和松节油倍半萜组分+夹带剂体系的汽液平衡数据，拟合松节油倍半萜组分饱和蒸汽压参数，建立松节油倍半萜组分二元、三元和四元体系汽液平衡模型，预测其过量Gibbs自由能和超额焓等热力学性质。采用激光衍射监视-自动控温-计算机采集技术识别固液平衡终点的动态法测定松节油作为绿色溶剂体系的单溶质单溶剂、单溶质多溶剂、多溶质多溶剂的固-液、汽-液-固平衡数据，从分子热力学的角度研究松节油倍半萜组分体系分子结构、分子间力与溶解度之间的关系。采用差示扫描量热仪测定松节油倍半萜组分的摩尔蒸发焓、熵和自由焓，建立其与温度的关联模型；采用微分法和积分法研究松节油倍半萜组分体系非等温热分解过程，建立不同气氛中松节油倍半萜组分体系热分解模型，为松节油倍半萜组分及其绿色溶剂体系的开发提供热力学基础数据。

采用带真空夹套的镀银玻璃精馏柱提纯松节油倍半萜组分β-石竹烯，获得β-石竹烯纯度为99%。采用具有搅拌功能的改进Ellis汽液平衡釜，测定松节油倍半萜组分β-石竹烯、莰烯以及3-蒈烯的饱和蒸汽压参数，根据稀溶液理论采用Raoult 定律拟合松节油倍半萜组分的饱和蒸汽压，使用EVIEWS 数理统计软件回归出Antoine 方程的各参数，建立松节油倍半萜组分β-石竹烯、莰烯以及3-蒈烯的饱和蒸汽压与温度的关联式。采用顶空-色谱法和具有搅拌功能的改进Ellis汽液平衡釜，测定松节油倍半萜组分β-石竹烯+双戊稀、对伞花烃+β-石竹烯、3-蒈烯+β-石竹烯、3-蒈烯+对伞花烃、莰烯+柠檬烯、莰烯+（+）-3-蒈烯、（+）-3-蒈烯+柠檬烯、莰烯+对伞花烃、莰烯+α-蒎烯、（+）-3-蒈烯+α-蒎烯、α-蒎烯+（-）-β-石竹烯、莰烯+（-）-β-石竹烯十二组二元体系和β-石竹烯+对伞花烃+3-蒈烯、莰烯+（+）-3-蒈烯+柠檬烯三元体系等压汽液平衡数据及313.15K、373.15K和433.15K条件下莰烯和（+）-3-蒈烯体系三组等温汽液平衡数据，用Herrington规则对所测体系的相平衡数据进行热力学一致性检验，在符合热力学一致性的基础上采用活度系数模型对所测数据进行拟合和关联，获得相应的能量参数，建立相应松节油倍半萜组分二元和三元体系汽液平衡模型，预测其过量Gibbs自由能和超额焓等热力学性质。采用差示扫描量热仪测定松节油倍半萜组分β-石竹烯和3-蒈烯的摩尔蒸发焓，获得了摩尔蒸发焓与温度的关联模型；采用微分法和积分法研究松节油倍半萜组分体系非等温热分解过程，建立不同气氛中松节油倍半萜组分体系热分解模型。采用激光衍射监视-自动控温-计算机采集技术识别固液平衡终点的动态法测定松节油作为绿色溶剂用于石蜡精制体系中，常压下、283K～321K温度范围内石蜡在α-蒎烯、碳酸二甲酯、丁酮和甲苯四种溶剂中的固-液、汽-液-固平衡数据，从分子热力学的角度研究松节油倍半萜组分体系分子结构、分子间力与溶解度之间的关系。利用量热法测定了松节油倍半萜组分β-石竹烯+对伞花烃、3-蒈烯+β-石竹烯和3-蒈烯+对伞花烃三个二元体系在298.15 K下的超额焓HE，采用Redlich-Kister方程进行关联。为松节油倍半萜组分及其绿色溶剂体系的开发提供了热力学基础数据。