将化工热力学溶液理论和化工流程模拟有机结合,设计了正己烷-甲基环戊烷萃取精馏计算型实验。通过类导体屏蔽电荷真实溶液模型(conductor-like screening model for real solvents,COSMO-RS)计算,基于溶解性、选择性指标筛选离子液体溶...将化工热力学溶液理论和化工流程模拟有机结合,设计了正己烷-甲基环戊烷萃取精馏计算型实验。通过类导体屏蔽电荷真实溶液模型(conductor-like screening model for real solvents,COSMO-RS)计算,基于溶解性、选择性指标筛选离子液体溶剂;通过量子化学计算及屏蔽电荷密度曲线分析溶剂和溶质分子相互作用,探究离子液体促进分离过程的机理;基于筛选的溶剂,利用Aspen Plus软件计算优化萃取分离工艺。该综合实验融合了化工热力学、化工原理和过程系统工程等专业课程内容,同时将学科理论知识与工程实践应用有机结合,强化了专业基本功训练,激发了研究兴趣,提升了创新能力。展开更多
真实溶剂似导体屏蔽模型(COSMO-RS,Conductor-likescreening model for real solvents)是Klamt等在连续介质溶剂化模式COSMO的基础上,结合统计力学方法发展起来的定量计算溶剂化现象的新方法。本文简单介绍了COSMO-RS的基本原理、概念,...真实溶剂似导体屏蔽模型(COSMO-RS,Conductor-likescreening model for real solvents)是Klamt等在连续介质溶剂化模式COSMO的基础上,结合统计力学方法发展起来的定量计算溶剂化现象的新方法。本文简单介绍了COSMO-RS的基本原理、概念,以及应用该模式的基本步骤。综述了COSMO-RS应用于离子性化合物、聚合物溶液体系、高温高压体系以及预测复杂生物体系的分配系数和药物设计的进展。评述了简化分子表面屏蔽电荷分布计算的COSMOfrag和GC-COSMO(group contribution COSMO)方法,对不同版本的COSMO-RS之间以及其与基团贡献方法的对比研究也作了详细的讨论,并指出了COSMO-RS的不足之处和进一步发展该模式的建议。展开更多
依据真实溶剂类导体屏蔽模型(Conductor-like Screening Model for Real Solvents,COSMO-RS),通过计算筛选出银杏叶中类黄酮提取所用的天然低共熔溶剂(Natural Deep Eutectic Solvents,NADESs)。以类黄酮得率为考察指标,在单因素实验的...依据真实溶剂类导体屏蔽模型(Conductor-like Screening Model for Real Solvents,COSMO-RS),通过计算筛选出银杏叶中类黄酮提取所用的天然低共熔溶剂(Natural Deep Eutectic Solvents,NADESs)。以类黄酮得率为考察指标,在单因素实验的基础上,采用Box-Behnken响应面法对提取工艺进行优化。结果表明:氯化胆碱/甘油体系(摩尔比1∶2)为较优的NADESs,当银杏叶与NADESs固液比为1∶30.7(g/mL),73.2℃下提取4.1 h时,回归模型预测类黄酮理论得率可高达5.70%,与验证试验值5.68%基本一致。本研究采用计算机模拟与实验相结合方法,为天然产物提取所用溶剂的筛选及后续工艺优化提供参考。展开更多
本文基于量子化学理论,采用真实溶剂似导体屏蔽模型(Conductor like Screening Model for Realistic Solvents,COSMO-RS)模拟了单一制冷工质的饱和蒸汽压和混合制冷工质的气液相平衡性质。将模拟结果与实验数据进行比较,最大误差不超过5...本文基于量子化学理论,采用真实溶剂似导体屏蔽模型(Conductor like Screening Model for Realistic Solvents,COSMO-RS)模拟了单一制冷工质的饱和蒸汽压和混合制冷工质的气液相平衡性质。将模拟结果与实验数据进行比较,最大误差不超过5%。模拟结果与实验数据有很好的一致性,表明:运用该方法预测制冷剂的热力学性质是可行的。展开更多
The adjustable parameters in the popular conductor-like screening model for real solvents(COSMO-RS)within the Amsterdam density functional(ADF)framework have been re-optimized to fit for the systems containing ionic l...The adjustable parameters in the popular conductor-like screening model for real solvents(COSMO-RS)within the Amsterdam density functional(ADF)framework have been re-optimized to fit for the systems containing ionic liquids(ILs).To get the optimal values of misfit energy constant a^0,hydrogen bond coefficient c_(hb)and effective contact surface area of a segment a_(eff),2283 activity coefficient data points at infinite dilution and 1433 CO_2 solubility data points exhaustively collected from references were used as training set.The average relative deviations(ARDs)of activity coefficients at infinite dilution and CO_2 solubility between experimental data and predicted values are 32.22%and17.61%,respectively,both of which are significantly lower than the original COSMO-RS versions.Predictions for other activity coefficients of solutes in ILs,solubility data of CO_2 in pure ILs and the binary mixtures of ILs at either high or low temperatures,and vapor–liquid equilibrium(VLE)for binary systems involving ILs have also been performed to demonstrate the validity of the parameterization of COSMO-RS model for ILs.The results showed that the predicted results by COSMO-RS model with the new optimized parameters are in much better agreement with experimental data than those by the original versions over a wide temperature and pressure range.The COSMO-RS model for ILs presented in this work improves the prediction accuracy of thermodynamic properties for the systems containing ILs,which is always highly desirable for general chemical engineers.展开更多
1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combi...1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combining 25 cations and 8 anions,in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model.The extraction mechanism was investigated with the help ofσ-profile and interaction energy analyses.Both the cation and anion have impacts on the extraction efficiency,where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL.The IL composed of long alkyl-chain in cation and the anion of[PF6]-or[TF2 N]-,which has theσ-profile more likely distributed in the nonpolar region but less distributed in the polar region,is favorable for extraction.The experimental liquid-liquid equilibrium demonstrated the effects of cation and anion on extraction performance,which validated the reliability of COSMO-RS model in IL screening for PDA extraction.The IL[IM-1,8][PF6]could serve as a promising extractant for the downstream separation process of the biological production of PDA.展开更多
As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the...As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the present study,a rapid solvent screening tool,Conductor-like Screening Model for Real Solvents(COSMO-RS),was used to predict the solubility of toluene in 816 ILs.The effects of four structure characters,namely,the type and alkyl chain length of the cations and anions on the solubility of toluene were discussed.The following conclusions were drawn from the results:(1)ILs with pyrrolidinium-based cations showed better solubility than pyridinium-and imidazoliumbased ones.(2)The solubility of toluene in PF6-based ILs increased with the increasing alkyl chain length,while its solubility in Ac-based ILs exhibited the opposite trend.(3)Toluene showed greater solubility in Cl-based ILs than those based on other anions.(4)The solubility of toluene increased with the anion alkyl chain length.Ac-based ILs were chosen as the most promising potential solvents,and further studied to determine the relationship between various interaction energy parameters and toluene solubility.The results showed that the misfit energy played a dominant role during the absorption process.Furthermore,several ILs were selected for experimental verification of the predicted solubility behavior using liquid and gaseous toluene.The results demonstrated that COSMO-RS could be used to semi-quantitatively and qualitatively predict the solubility of toluene,and this model had promising prospects in screening ILs for VOCs absorption.In summary,this study provided a fundamental basis and practical data for the control and treatment of VOCs.展开更多
A suitable ionic liquid for methyl chloride drying experiment was screened out from 210 ionic liquids by COSMO-RS model.Moreover,the experimental mechanism of ionic liquids drying is further explained by the COSMO-RS ...A suitable ionic liquid for methyl chloride drying experiment was screened out from 210 ionic liquids by COSMO-RS model.Moreover,the experimental mechanism of ionic liquids drying is further explained by the COSMO-RS model,and it is further confirmed by analyzing the binding energy.The solubility of methyl chloride in[EMIM][BF4]and TEG and[EMIM][BF4]+H2O was completed,and the experimental results well proved the reliability of the UNIFAC-Lei model.The unknown interaction parameters were obtained through the solubility data of this work and the experimental data in the literatures.The methyl chloride drying experiment was completed in the laboratory,and the water content of the methyl chloride can be reduced to below 200 ppm.The simulation of the methyl chloride drying process using[EMIM][BF4]or TEG as absorbents was carried out by ASPEN software on an industrial scale.The final simulation results show that the[EMIM][BF4]drying process has lower energy consumption and better drying effect.展开更多
文摘将化工热力学溶液理论和化工流程模拟有机结合,设计了正己烷-甲基环戊烷萃取精馏计算型实验。通过类导体屏蔽电荷真实溶液模型(conductor-like screening model for real solvents,COSMO-RS)计算,基于溶解性、选择性指标筛选离子液体溶剂;通过量子化学计算及屏蔽电荷密度曲线分析溶剂和溶质分子相互作用,探究离子液体促进分离过程的机理;基于筛选的溶剂,利用Aspen Plus软件计算优化萃取分离工艺。该综合实验融合了化工热力学、化工原理和过程系统工程等专业课程内容,同时将学科理论知识与工程实践应用有机结合,强化了专业基本功训练,激发了研究兴趣,提升了创新能力。
文摘真实溶剂似导体屏蔽模型(COSMO-RS,Conductor-likescreening model for real solvents)是Klamt等在连续介质溶剂化模式COSMO的基础上,结合统计力学方法发展起来的定量计算溶剂化现象的新方法。本文简单介绍了COSMO-RS的基本原理、概念,以及应用该模式的基本步骤。综述了COSMO-RS应用于离子性化合物、聚合物溶液体系、高温高压体系以及预测复杂生物体系的分配系数和药物设计的进展。评述了简化分子表面屏蔽电荷分布计算的COSMOfrag和GC-COSMO(group contribution COSMO)方法,对不同版本的COSMO-RS之间以及其与基团贡献方法的对比研究也作了详细的讨论,并指出了COSMO-RS的不足之处和进一步发展该模式的建议。
文摘依据真实溶剂类导体屏蔽模型(Conductor-like Screening Model for Real Solvents,COSMO-RS),通过计算筛选出银杏叶中类黄酮提取所用的天然低共熔溶剂(Natural Deep Eutectic Solvents,NADESs)。以类黄酮得率为考察指标,在单因素实验的基础上,采用Box-Behnken响应面法对提取工艺进行优化。结果表明:氯化胆碱/甘油体系(摩尔比1∶2)为较优的NADESs,当银杏叶与NADESs固液比为1∶30.7(g/mL),73.2℃下提取4.1 h时,回归模型预测类黄酮理论得率可高达5.70%,与验证试验值5.68%基本一致。本研究采用计算机模拟与实验相结合方法,为天然产物提取所用溶剂的筛选及后续工艺优化提供参考。
文摘本文基于量子化学理论,采用真实溶剂似导体屏蔽模型(Conductor like Screening Model for Realistic Solvents,COSMO-RS)模拟了单一制冷工质的饱和蒸汽压和混合制冷工质的气液相平衡性质。将模拟结果与实验数据进行比较,最大误差不超过5%。模拟结果与实验数据有很好的一致性,表明:运用该方法预测制冷剂的热力学性质是可行的。
基金financially supported by the National Natural Science Foundation of China under Grants (Nos. 21476009, 21406007 and U1462104)
文摘The adjustable parameters in the popular conductor-like screening model for real solvents(COSMO-RS)within the Amsterdam density functional(ADF)framework have been re-optimized to fit for the systems containing ionic liquids(ILs).To get the optimal values of misfit energy constant a^0,hydrogen bond coefficient c_(hb)and effective contact surface area of a segment a_(eff),2283 activity coefficient data points at infinite dilution and 1433 CO_2 solubility data points exhaustively collected from references were used as training set.The average relative deviations(ARDs)of activity coefficients at infinite dilution and CO_2 solubility between experimental data and predicted values are 32.22%and17.61%,respectively,both of which are significantly lower than the original COSMO-RS versions.Predictions for other activity coefficients of solutes in ILs,solubility data of CO_2 in pure ILs and the binary mixtures of ILs at either high or low temperatures,and vapor–liquid equilibrium(VLE)for binary systems involving ILs have also been performed to demonstrate the validity of the parameterization of COSMO-RS model for ILs.The results showed that the predicted results by COSMO-RS model with the new optimized parameters are in much better agreement with experimental data than those by the original versions over a wide temperature and pressure range.The COSMO-RS model for ILs presented in this work improves the prediction accuracy of thermodynamic properties for the systems containing ILs,which is always highly desirable for general chemical engineers.
基金The financial support from National Natural Science Foundation of China(21978096,21861132019,and 21776074)Natural Science Foundation of Shanghai(19ZR1412600)is greatly acknowledged
文摘1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combining 25 cations and 8 anions,in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model.The extraction mechanism was investigated with the help ofσ-profile and interaction energy analyses.Both the cation and anion have impacts on the extraction efficiency,where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL.The IL composed of long alkyl-chain in cation and the anion of[PF6]-or[TF2 N]-,which has theσ-profile more likely distributed in the nonpolar region but less distributed in the polar region,is favorable for extraction.The experimental liquid-liquid equilibrium demonstrated the effects of cation and anion on extraction performance,which validated the reliability of COSMO-RS model in IL screening for PDA extraction.The IL[IM-1,8][PF6]could serve as a promising extractant for the downstream separation process of the biological production of PDA.
基金supported by the National Natural Science Foundation of China(51474146,21806102)Graduate Program Funding of Shanghai Polytechnic University(A01GY18F022-d04,EGD18YJ0004)Gaoyuan Discipline of Shanghai–Environmental Science and Engineering(Resource Recycling Science and Engineering)
文摘As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the present study,a rapid solvent screening tool,Conductor-like Screening Model for Real Solvents(COSMO-RS),was used to predict the solubility of toluene in 816 ILs.The effects of four structure characters,namely,the type and alkyl chain length of the cations and anions on the solubility of toluene were discussed.The following conclusions were drawn from the results:(1)ILs with pyrrolidinium-based cations showed better solubility than pyridinium-and imidazoliumbased ones.(2)The solubility of toluene in PF6-based ILs increased with the increasing alkyl chain length,while its solubility in Ac-based ILs exhibited the opposite trend.(3)Toluene showed greater solubility in Cl-based ILs than those based on other anions.(4)The solubility of toluene increased with the anion alkyl chain length.Ac-based ILs were chosen as the most promising potential solvents,and further studied to determine the relationship between various interaction energy parameters and toluene solubility.The results showed that the misfit energy played a dominant role during the absorption process.Furthermore,several ILs were selected for experimental verification of the predicted solubility behavior using liquid and gaseous toluene.The results demonstrated that COSMO-RS could be used to semi-quantitatively and qualitatively predict the solubility of toluene,and this model had promising prospects in screening ILs for VOCs absorption.In summary,this study provided a fundamental basis and practical data for the control and treatment of VOCs.
基金financially supported by the National Natural Science Foundation of China(No.U1862103)and(No.21961160740)
文摘A suitable ionic liquid for methyl chloride drying experiment was screened out from 210 ionic liquids by COSMO-RS model.Moreover,the experimental mechanism of ionic liquids drying is further explained by the COSMO-RS model,and it is further confirmed by analyzing the binding energy.The solubility of methyl chloride in[EMIM][BF4]and TEG and[EMIM][BF4]+H2O was completed,and the experimental results well proved the reliability of the UNIFAC-Lei model.The unknown interaction parameters were obtained through the solubility data of this work and the experimental data in the literatures.The methyl chloride drying experiment was completed in the laboratory,and the water content of the methyl chloride can be reduced to below 200 ppm.The simulation of the methyl chloride drying process using[EMIM][BF4]or TEG as absorbents was carried out by ASPEN software on an industrial scale.The final simulation results show that the[EMIM][BF4]drying process has lower energy consumption and better drying effect.
