Comparison of UNIFAC and LSER Models for Calculating Partition Coefficients in the Hexane–Acetonitrile System Using Middle Distillate Petroleum Products as an Example

Efimov, Ignaty; Поваров, В. Г.; Rudko, Viacheslav A.

doi:10.1021/acs.iecr.2c01093

Cited by 8 publications

(3 citation statements)

References 44 publications

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“…It is a widely accepted law in chemistry that molecular structures determine molecular properties, − and the structural increments represent the molecular groups or structures in the SOL method. Thus, the calculation model of product properties by structural incremental contribution method, abbreviated as property calculation model, was built up to calculate the properties of distillation range, density, and cetane number (CN) of diesel in our previous study .…”

Section: Resultsmentioning

confidence: 99%

Simulation of Reaction Pathways of Sulfur Compounds and Product Properties Based on the Molecular-Level Hydrotreating Reaction Model

Ye,

Murad,

Qin

et al. 2023

Ind. Eng. Chem. Res.

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A molecular-level reaction model for the diesel hydrotreating process was established by using the structure-oriented lumping (SOL) method. A molecular composition matrix was applied to represent the hydrotreating feed molecular composition and was calculated as the model input. By following the 38 hydrotreating reaction rules, each molecule of the feed molecular composition matrix was able to react and automatically generate reaction pathways and eventually form a large reaction network containing 37,097 reactions. The SOL model had the advantage of carrying out the molecular kinetic difference, especially for sulfurcontaining molecules. The hydrodesulfurization reaction (HDS) of dibenzothiophene preferred the direct desulfurization pathway rather than the hydrogenation pathway (HYD), while 4,6-dimethyl dibenzothiophene was more dependent on HYD for HDS. The hydrotreating model could calculate the product distribution and molecular composition accurately. Combined with the structural increment contribution method, the model extended the function of predicting the product properties. The hydrotreating reaction model realized the molecular-level description of the whole process including the feed molecular composition, the reaction process, and the product molecular composition and properties.

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Section: Resultsmentioning

confidence: 99%

Simulation of Reaction Pathways of Sulfur Compounds and Product Properties Based on the Molecular-Level Hydrotreating Reaction Model

Ye,

Murad,

Qin

et al. 2023

Ind. Eng. Chem. Res.

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“…LSER models are directly applicable to predict the solubility of APIs in solvents [309]. LSER models are widely used in the field of chromatography for characterizing columns and estimating retention times [310,311] or in the analysis of petroleum distillate conditions with group contribution activity coefficient models such as UNIFAC [312], but they do not appear to have been used more broadly (in reverse) in mixed solvent replacement schemes, although environmentally related partition coefficients are incorporated into life-cycle assessment tools, such as EPA's CompTox chemical dashboard system [313] or machine learning studies for solvent characterization factors [314].…”

Section: Linear Solvation Energy Relationships (Lser)mentioning

confidence: 99%

Solvent Replacement Strategies for Processing Pharmaceuticals and Bio-Related Compounds—A Review

Lee,

Chong,

Ota

et al. 2024

Liquids

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An overview of solvent replacement strategies shows that there is great progress in green chemistry for replacing hazardous di-polar aprotic solvents, such as N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), and 1,4-dioxane (DI), used in processing active industrial ingredients (APIs). In synthetic chemistry, alcohols, carbonates, ethers, eucalyptol, glycols, furans, ketones, cycloalkanones, lactones, pyrrolidinone or solvent mixtures, 2-methyl tetrahydrofuran in methanol, HCl in cyclopentyl methyl ether, or trifluoroacetic acid in propylene carbonate or surfactant water (no organic solvents) are suggested replacement solvents. For the replacement of dichloromethane (DCM) used in chromatography, ethyl acetate ethanol or 2-propanol in heptanes, with or without acetic acid or ammonium hydroxide additives, are suggested, along with methanol acetic acid in ethyl acetate or methyl tert-butyl ether, ethyl acetate in ethanol in cyclohexane, CO2-ethyl acetate, CO2-methanol, CO2-acetone, and CO2-isopropanol. Supercritical CO2 (scCO2) can be used to replace many organic solvents used in processing materials from natural sources. Vegetable, drupe, legume, and seed oils used as co-extractants (mixed with substrate before extraction) can be used to replace the typical organic co-solvents (ethanol, acetone) used in scCO2 extraction. Mixed solvents consisting of a hydrogen bond donor (HBD) solvent and a hydrogen bond acceptor (HBA) are not addressed in GSK or CHEM21 solvent replacement guides. Published data for 100 water-soluble and water-insoluble APIs in mono-solvents show polarity ranges appropriate for the processing of APIs with mixed solvents. When water is used, possible HBA candidate solvents are acetone, acetic acid, acetonitrile, ethanol, methanol, 2-methyl tetrahydrofuran, 2,2,5,5-tetramethyloxolane, dimethylisosorbide, Cyrene, Cygnet 0.0, or diformylxylose. When alcohol is used, possible HBA candidates are cyclopentanone, esters, lactone, eucalytol, MeSesamol, or diformylxylose. HBA—HBA mixed solvents, such as Cyrene—Cygnet 0.0, could provide interesting new combinations. Solubility parameters, Reichardt polarity, Kamlet—Taft parameters, and linear solvation energy relationships provide practical ways for identifying mixed solvents applicable to API systems.

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“…Empirical formulas for calculating Kd of substances based on their known physicochemical properties, such as molecular weight, boiling point, number of carbon atoms in a molecule also appeared [26]. The LSER model [27,28] that makes it possible to calculate the partition coefficients in previously studied solvent systems with a sufficiently high accuracy is most actively used in analytical practice. This made it possible to apply this method not only to confirm the results of identification, but also to check the assumptions about the structure of analyte molecules.…”

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confidence: 99%

Use of the UNIFAC model in the calculation of physicochemical properties of ecotoxicants for technological and ecoanalytical purposes

Поваров

Efimov

2023

PMI

Self Cite

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Modern development vector of environmental monitoring leads to elaboration of analytical methods for qualitative and quantitative analysis of different ecotoxicants. Many studies face the lack of information on isomers and homologues of already studied compounds. This problem cannot always be solved experimentally due to the difficulty of separating or synthesizing certain compounds; the use of group theories of solutions will help partly; using them, solubility in water or partition coefficient between two immiscible solvents is calculated for ecotoxicants. These parameters are important for solving the analytical and ecological problems. The partition coefficient in the octanol – water system is associated with a possibility of accumulation of different compounds in living organisms; the partition coefficient in the hexane – acetonitrile system can be used in gas chromatographic analysis. Solubility in water is closely associated with accumulation of ecotoxicants in water bodies, as well as with their ability to be transferred. This paper presents the capabilities of the UNIFAC model for solving physicochemical problems using the example of calculating the properties of real ecotoxicants on the basis of the available thermodynamic data. All the obtained calculated values were compared with those determined experimentally. In the case of pyrene derivatives, solubility data were obtained for the first time using a correlation group model to calculate the heat of fusion and melting temperature.

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Comparison of UNIFAC and LSER Models for Calculating Partition Coefficients in the Hexane–Acetonitrile System Using Middle Distillate Petroleum Products as an Example

Cited by 8 publications

References 44 publications

Simulation of Reaction Pathways of Sulfur Compounds and Product Properties Based on the Molecular-Level Hydrotreating Reaction Model

Simulation of Reaction Pathways of Sulfur Compounds and Product Properties Based on the Molecular-Level Hydrotreating Reaction Model

Solvent Replacement Strategies for Processing Pharmaceuticals and Bio-Related Compounds—A Review

Use of the UNIFAC model in the calculation of physicochemical properties of ecotoxicants for technological and ecoanalytical purposes

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