Study On Solubility Of M-Nitro Aniline,p-Nitroaniline And Their Mixture In Supercritical Carbon Dioxide

Nowadays, supercritical fluid science and technology has a wide application prospect in some fields such as chemical industry, pharmaceuticals industry, dyeing, new material preparation and so on. Carbon dioxide (CO2), which is one of green chemical solvents has some unique properties such as mild critical condition, nontoxic. Thus, supercritical CO2technology is more and more welcomed in some different kinds of application fields. Measuring solubility of some solid solutes in supercritical CO2is a significant step for designing the chemical engineering with supercritical fluid technology; however, the study on some experimental data and the related theory is relatively less. In this thesis, m-nitroaniline (m-NA) and p-nitroaniline (p-NA) were investigated, which has two different functional groups (amino-NH2and nitro-NO2).The solubility of m-NA,p-NA and their mixture in supercritical CO2with and without cosolvent was measured by dynamic method at five pressures (11.0,13.0,15.0,18.0and21.0) MPa and three temperatures (308,318and328) K. Cosolvents are ethanol, ethyl acetate, n-hexane and the mixed ethanol and n-hexane (mole ratio1:1), and the range of concentration is from (1.0to4.0) mol%. In this thesis, the experimental data of120groups were measured to enrich the chemical database, and supplied the reliable data for the industry project.Base on experimental research, the effect of temperature, pressure, positions and types of functional groups, concentrations and polarity of cosolvent on the solubility of the amine solutes in SCCO2was investigated. In this thesis, the effect factor of cosolvent (f), enhancement factor (e) in the mixed solute and supercritical CO2system, separation factor (h) and separation efficiency (HE) were calculated and analyzed. With Gaussian03software, the interactions between solute molecule and solvent molecule are calculted, which provides a new method to estimate the solubility of solid solute in supercritical CO2by establishing the relationship between solubility and substance properties.The solubility of pure amine solutes in supercritical CO2were correlated with the Chrastil model、the Kumar-Johnston (K-J) model、the Bartle model、 the Mendez-Santiago and Teja (MST) model, th Sung-Shim (S-S) model and the Jouyban-Chan (J-C) model; Moreover, the solubility of amine solutes in supercritical CO2with cosolvent was correlated with the modified Chrastil (M-Chrastil) model, the Sovova model, the modified MST (M-MST) model and the modified Sovova (M-Sovova) model. In all, the correlated results were satisfactory, and the experimental data was correlated by MST model and determined the self-consistency of experimental data.For the mixed solute in supercritical CO2ternary system, a new semi-empirical model (Sovova-G model) which based on the chemical associated theory was proposed.462solubility experimental data of13kinds of two mixed solutes were used to test and verify the accuracy of Sovova-G model. The correlated results showed the Sovova-G model with AARD of4.42%was better than that of Sovova model (7.45%) and M-Sovova model (5.96%).This thesis was financially supported by the funds awarded by National Natural Science Foundation of China (No.21176012) and Natural Science Foundation of Jiangsu Province (No. BK2012595).