Solute solubility as criterion for the appearance of amorphous particle precipitation or crystallization in the supercritical antisolvent (SAS) process
Solute solubility as criterion for the appearance of amorphous particle precipitation or crystallization in the supercritical antisolvent (SAS) process
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DOI：
10.1016/j.supflu.2011.11.023
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发表时间：
2012-06-01
影响因子：
3.9
通讯作者：
Schluecker, Eberhard
中科院分区：
文献类型：
--
作者：
Rossmann, Matthias;Braeuer, Andreas;Schluecker, Eberhard
比较了两种不同的超临界抗溶剂(SAS)体系，一个沉淀体系和一个结晶体系的过程行为与溶质溶解度的关系。以醋酸钇(YAC)为溶质，二甲基亚砜(DMSO)为溶剂，二氧化碳(CO2)为抗溶剂的SAS体系YAc/DMSO/CO2析出无定形颗粒。以对乙酰氨基酚(PCM)为溶质、乙醇(EtOH)为溶剂、CO2为抗溶剂的SAS体系PCM/EtOH/CO2结晶结晶。采用原位弹性和非弹性光散射方法，测得沉淀SAS体系YAC/DMSO/CO2的第一次粒子产生位置的过饱和度(LFPG)比结晶SAS体系PCM/EtOH/CO2高4个数量级。这种差异与溶质的饱和溶解度有关，通过弹性光散射研究发现，结晶体系的饱和溶解度比沉淀体系的饱和溶解度大约四个数量级。因此，溶质在溶剂和抗溶剂混合物中的饱和溶解度可以作为区分无定形沉淀和结晶SAS体系的间接分类标准。此外，对于结晶的SAS体系，晶体既可以从超临界相产生，也可以从液体中产生，这与SAS普遍认为只能在液体中形成晶体的观点是相反的。(C)2011爱思唯尔B.V.保留所有权利。
Two different supercritical antisolvent (SAS) systems, one precipitating system and one crystallizing system, have been compared in their process behavior in dependence on the solute solubility. The SAS system YAc/DMSO/CO2, which is composed of yttrium acetate (YAc) as solute, dimethylsulfoxide (DMSO) as solvent and carbon dioxide (CO2) as antisolvent, precipitates amorphous particles. The SAS system PCM/EtOH/CO2, which is composed of paracetamol (PCM) as solute, ethanol (EtOH) as solvent and CO2 as antisolvent, crystallizes crystals. Applying in situ elastic and inelastic light scattering it was measured that for the precipitating SAS system YAc/DMSO/CO2 the supersaturation at the location of first particle generation (LFPG) is up to four orders of magnitude larger than for the crystallizing SAS system PCM/EtOH/CO2. This discrepancy correlates with the saturation solubilities of the solutes which found to be approximately four orders of magnitude larger for the crystallizing system than for the precipitating system, investigated by elastic light scattering. Hence, the saturation solubility of the solute in mixtures of solvents and antisolvents could be identified as the indirect classification criterion to distinguish between amorphous precipitating and crystallizing SAS systems. Furthermore, it is shown that for the crystallizing SAS system crystals may be generated from either a supercritical or a liquid phase which is in contrast to the widespread SAS opinion that crystals only can be formed in the liquid phase. (c) 2011 Elsevier B.V. All rights reserved.