青霉胺结晶热力学及拆分工艺研究

Study on the crystallization thermodynamics and chiral resolution of penicillamine

实验测定了DL-及D-青霉胺在273.15~333.15 K、不同质量比乙醇-水混合溶剂中的溶解度,以此确定了合适的结晶溶剂比例。绘制了273.15、283.15、293.15、303.15、313.15和323.15 K下青霉胺溶解度曲线。测定了D-和DL-青霉胺以及ee值为87%溶液的介稳区宽度。研究了不同ee值饱和溶液(饱和温度为313.15 K)在不同初始过冷度下起始成核情况及ee值为87%的饱和溶液在不同初始过冷度和晶种量下的等温结晶过程。最后考察了不同降温速率、晶种量对ee值为87%原料的结晶拆分情况。结果表明,对于等温结晶过程,随着结晶进行,产品ee值下降,且初始过冷度越大、晶种加入量越多,ee>99%的产品收率越高;对于降温结晶过程,产品ee值随收率增大而减小,且降温速率越慢、晶种加入量越多,ee>99%的产品收率越高。

The solubility of DL-and D-penicillamine in ethanol-water mixed solvents with different mass ratios at273.15—333.15 K was measured,and the appropriate crystallization solvent ratio was determined.The solubility curves of penicillamine at 273.15 K,283.15 K,293.15 K,303.15 K,313.15 K and 323.15 K were drawn.The width of the metastable zone of D-and DL-penicillamine and the solution with ee value of 87%was measured.The initial nucleation of saturated solutions with different ee values(saturation temperature of 313.15 K)under different initial subcooling,and the thermostatic crystallization process of saturated solutions with ee value of 87%under different initial subcooling and seed amount were studied.Finally,the crystallization resolution of raw materials with an ee value of 87%,different cooling rates and seed amounts were preliminarily investigated.The results show that,for the thermostatic crystallization process,as the crystallization progresses,the ee value of the product decreases,and the greater of initial subcooling,the more of seeds,the higher of the yield of the product with ee>99%.For the cooling crystallization process,the ee value of the product decreases as the yield increases,and the slower of the cooling rate,the more of seeds,the higher of the yield of the product with ee>99%.