A generalized correlation for the prediction of phase behaviour in supercritical systems

A generalized two parameter model is presented which uses molecular properties of pure fluids to predict interaction parameters in the attractive term of the Peng-Robinson equation of state. The predictive method is based on a consideration of London (dispersive) forces and includes attractive forces between polar and non-polar molecules that result from induction. Polar-polar effects and quantum forces are omitted. A large body of experimental vapor-liquid equilibrium data measured at near and supercritical conditions (that excludes quantum components and polar-polar systems) was used to calibrate the generalized model. Overall bubble point pressure deviations calculated using the proposed generalization were 5.66% for 3240 data points which compares to average deviations of 3.27% obtained by using regressed binary interaction parameters. Average vapor mole fraction deviations were just under 0.01 using both the generalized and the regressed interaction parameters. The sensitivity of predicted phase envelopes to dispersive and inductive term in the generalized correlation is shown graphically for several systems. Comparisons are also made to another recent interaction parameter generalization presented by Nishiumi et al. (1988).     

超临界CO2二元系统相平衡的数值模拟

应用微扰理论,借助微扰状态方程,对超临界CO2 系统相平衡进行了模拟。编制了求解程序,介绍了状态方程中各参数的确定方法和程序模块的设计思想。针对超临界CO2 /非极性体系、超临界CO2 /极性体系,在不同温度、压力条件下的气液相平衡进行了计算,将计算结果与实验结果进行了比较,结果表明:微扰状态方程适合模拟超高压下的CO2 二元体系的相平衡。     

超临界CO2中异丁醇的相平衡研究

Vapor-liquid phase equilibrium data including composition, densities, molar volume and equilibrium constant of isobutanol in supercritical carbon dioxide from 313.2 K to 353.2 K were measured in a variable-volume visual cell. The properties of critical point were obtained by extrapolation. The results showed that critical temperature, critical pressure and critical compressibility factor of CO2-isobutanol system decreased with the increase of critical CO2 content. The phase equilibrium model was established by Peng-Robinson equation of state and van der Waals-2 mixing regulation, and model parameters were determined by optimization calculation of nonlinear least square method. The correlation between calculated values and the experimental data showed good agreement.     

CO2-H2O-HAc三组分系统高压相平衡

超临界状态下的CO2在含有有机溶剂的水溶液中可作为萃取剂。这种情况可用于水和有机酸的分离，也可以用于从水溶液中萃取产品。要设计这样的过程，CO2-H2O-有机酸系统相平衡的数据是必不可少的。为此，在实验室建立了一套高压相平衡装置。为了验证这套装置的可靠性，测定了CO2-H2O-HAc体系在313K以及压力在15、20、25和30MPa下的相平衡数据，用Peng-Robinson方程^[1,2]进行了计算，并与文献值进行了比较。     

An architecture of deep learning in QSPR modeling for the prediction of critical properties using molecular signatures

Deep learning rapidly promotes many fields with successful stories in natural language processing. An architecture of deep neural network (DNN) combining tree-structured long short-term memory (Tree-LSTM) network and back-propagation neural network (BPNN) is developed for predicting physical properties. Inspired by the natural language processing in artificial intelligence, we first developed a strategy for data preparation including encoding molecules with canonical molecular signatures and vectorizing bond-substrings by an embedding algorithm. Then, the dynamic neural network named Tree-LSTM is employed to depict molecular tree data-structures while the BPNN is used to correlate properties. To evaluate the performance of proposed DNN, the critical properties of nearly 1,800 compounds are employed for training and testing the DNN models. As compared with classical group contribution methods, it can be demonstrated that the learned DNN models are able to provide more accurate prediction and cover more diverse molecular structures without considering frequencies of substructures.     

Phase behavior of semicrystalline polyester resin in supercritical fluid solvents and solvent mixtures: Implications for supercritical fluid processing

Cloud‐point data between 40 and 240°C and pressures to 2750 bar are presented for a low molecular weight, semicrystalline polyester resin of 53.4 mol % adipic acid and 46.6 mol % 1,4‐cyclohexanedimethanol in supercritical CO₂, dimethyl ether (DME), and chlorodifluoromethane (CDFM), and in mixtures of CO₂ with DME, CDFM, methanol, ethanol, butanol, octanol, hexafluoroisopropanol, acetone, and cyclohexane. Carbon dioxide, by itself, is an extremely weak supercritical fluid (SCF) solvent because this polyester only dissolves at pressures in excess of 2000 bar and at temperatures over 180°C. However, DME and CDFM are excellent solvents for this polyester, which dissolves at 16 bar and 40°C in CDFM and at 167 bar and 55°C in DME. The melting point of this polyester is reduced from 105 to 40°C in CDFM and to 55°C in DME, which makes the polyester amenable to high intensity mixing for the efficient dispersion of inorganics or crosslinking agents and other hard to deposit materials. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2642–2648, 2001     

红外光谱测量法研究超临界CO2中夹带剂与溶质的相互作用

利用红外光谱技术研究了在超临界CO₂中加入不同夹带剂时,水杨酸中基团的伸缩振动频率的位移及夹带剂与溶质的相互作用。以乙醇为夹带剂时,水杨酸中C=O基团、O—H基团的伸缩振动频率均向低频方向移动;以丙酮为夹带剂时,水杨酸中C=O基团伸缩振动频率向高频方向移动。研究结果表明：当以乙醇为夹带剂时,水杨酸的溶解度远大于以丙酮为夹带剂时的结果,夹带剂对溶质增溶的作用能力,形成氢键的作用远大于溶剂极性的作用。     

超临界体系相行为实验测定方法研究进展

超临界相行为研究及其实验测定是超临界流体技术领域发展的基础和重要研究内容之一,从超临界相行为测量的意义和基本原理出发,对相行为及临界参数实验测定方法作了综述,主要介绍了可视观察法、光谱色谱法、脉冲加热法等测定方法,并对其优缺点和适用范围作了点评,最后对其未来发展方向做了展望。     

超临界流体萃取中的相平衡研究

本文综述了超临界流体萃取过程中的相平衡模型及其实验研究的新进展，特别着重介绍了压缩气体模型，膨胀液体模型，经验模型和计算机模拟模型，研究体系包括液体／ＳＣＦ，固体／ＳＣＦ，固体／ＳＣＦ／夹带剂体系。     

A Comparison of the Phase Behaviour of Polystyrene in Cycloalkanes and n-Alkanes

Cloud point curves for several narrow fractions of polystyrene dissolved in cycloheptane, in cyclooctane and in cyclodecane have been established, and the critical solution temperatures extrapolated to give the respective temperatures. All three cycloalkanes are good solvents for the polymer. A comparison is made between the phase behaviour of polystyrene dissolved in cyclic alkanes and in n-alkanes using free volume polymer solution theory.     

Phase behaviour of hyperbranched polyesters and polyethers with modified terminal OH groups in supercritical solvents

Hyperbranched polyethers and polyesters have been synthesized, and their phase behaviour in carbon dioxide and light hydrocarbons explored as a function of concentration and temperature. The synthesis includes modifications of the terminal OH groups with aliphatic carboxylic acids derivatives, trimethylchlorosilane, and trifluoroacetic acid anhydride. Modified polyesters show good solubility in carbon dioxide, ethane and propane. The comparison with the literature data shows that the silane and fluorinated derivatives of the hyperbranched polyesters are soluble in carbon dioxide to the same extent as the most CO₂-philic polymeric materials synthesized till now. It seems that the nature of the end groups is an important factor that influences phase equilibria of hyperbranched macromolecules in supercritical solvents. However, the nature of the interior of the macromolecule is also significant. The results obtained show that in general hyperbranched polyesters are better soluble in carbon dioxide than hyperbranched polyethers. In light hydrocarbons as solvents the opposite effect is observed.     

Activity and stability of lipases from different sources in supercritical carbon dioxide and near‐critical propane

The stability and activity of lipases from Pseudomonas fluorescens, Rhizopus javanicus, Rhizopus niveus, porcine pancreas and Candida rugosa in a non‐solvent system at atmospheric pressure, in supercritical carbon dioxide (SC CO₂), and near‐critical propane at 100 bar and 40 °C were studied. Esterification of n‐butyric acid with ethanol and isoamyl alcohol was used as a model system. In supercritical carbon dioxide there was a great loss in activity of the examined lipases. Decreased relative activity of lipases in SC CO₂ was attributed to the interactions between CO₂ and the enzyme. The second reason for this effect was the differences in water partitioning between the enzyme and its surroundings. In contrast, the use of near‐critical propane improved the activity of lipases in the comparison to the non‐solvent system by four‐ (porcine pancreas lipase) to nine‐times (Rhizopus javanicus lipase). The use of near‐critical propane also improved the thermal stability of porcine pancreas lipase compared with the non‐solvent system. The calculated deactivation constant for esterification between butyric acid and isoamyl alcohol, catalyzed by porcine pancreas lipase, showed that there was more than twice as much inactive as active enzyme in the non‐solvent system studied whereas the ratio in propane was 1. © 2001 Society of Chemical Industry     

A novel equation of state (EOS) for prediction of solute solubility in supercritical carbon dioxide: Experimental determination and correlation

Solubility data of organophosphorous metal extractants in supercritical fluids (SCF) are crucial for designing metal extraction processes. We have developed a new equation of state (EOS) based on virial equation including an untypical parameter as BP/RT, reduced temperature and pressure for prediction of solute solubility in supercritical carbon dioxide (SC CO₂). Solubility experimental data (solubility of tributylphosphate in SC CO₂) were correlated with the two cubic equations of state (EOS) models, namely the Peng–Robinson EOS (PR‐EOS) and the Soave–Redlich–Kwong EOS (SRK‐EOS), together with two adjustable parameter van der Waals mixing and combining rules and our proposed EOS. The AARD of our EOS is significantly lower than that obtained from the other EOS models. The proposed EOS presented more accurate correlation for solubility data in SC CO₂. It can be employed to speed up the process of SCF applications in industry.     

Cure behaviour and mechanical properties of Si3N4 ceramics with bimodal particle size distribution prepared using digital light processing

Digital light processing is a vital additive manufacturing technology used for manufacturing ceramic parts. The particle size distribution of ceramic suspensions significantly affects the cure behaviour and mechanical properties of ceramics. In this study, the cure behaviour and mechanical properties of Si₃N₄ ceramics with a bimodal particle size distribution were studied. The results indicated that the suspension with coarse particles had a higher cure depth for a lower absorbance but poor mechanical properties. The bending strength of the samples with the optimal ratio (coarse:fine particles = 3:7) reached a maximum of 728.7 ± 10.33 MPa, which is 16.5% higher than that of the samples prepared using only fine particles.     

Thermogravimetric investigations in prediction of coking behaviour and coke properties derived from inertinite rich coals

The coal quality, temperature, pressure, heating rate, various processes and reactor type affect coking behaviour of coal and resulting coke properties. Several petrographic and chemical methods were proposed earlier for prediction of coking behaviour of coals. Inertinite rich coal samples (I^mmf>30 vol%) having different petrographic compositions were selected for thermogravimetric investigations (DTA, DTG and TGA) and their coking behaviour was studied. The petrographic build up, micro-structural properties (porosity and cell wall thickness) and mechanical strength of the resulted cokes were also investigated. ΔH and ΔH_max (the main endothermic area of heat absorption and fast absorbing main endothermic area, respectively) were distinguished in DTA curves. ΔA and ΔA_max (the main decomposition area and fast disintegrating main decomposition area) under DTG curves were identified. ΔH_max/ΔA_max shows good correlation with Roga's indices (RI, caking properties) as well as with petrographic caking ratio (PCR). The coarse mosaic content of cokes seem to depend on LΔT_max/ΔT_max (ratio of weight loss during fast decomposing main reaction to temperature difference) under DTG. L^mΔT/ΔT (ratio of weight loss during main decomposing reaction to temperature difference) under DTG exhibits correlation with p₁ (mean pore size) and t₁ (mean cell wall thickness) of cokes. ΔA_max/(L^mΔT_max) also indicates good relationship with mechanical strength of cokes. (L^mΔT_A−T_B)/(L^mΔT) (i.e. ratio of weight loss during main endothermic reaction under DTA to weight loss during main decomposing reaction) appears to have relationship with DD (compactness) of cokes. The course of main endothermic reaction/main decomposition reaction under DTA, DTG and TGA seems to govern coking behaviour and the resulting coke strength, which in turn is controlled by microlithotypes.     

Polymer-cosolvent systems: 6. Phase behaviour of polystyrene in binary mixed solvents of acetone with n-alkanes-examples of ‘classic cosolvency’

The demixing behaviour of polystyrene fractions in binary combinations of acetone (1) and a series of n-alkanes (2) containing up to twenty carbon atoms has been established and the data presented as phase contour diagrams. Each binary liquid system exhibits the characteristics of classic cosolvency and the maximum molecular weight of polymer that may be dissolved is ca. 10⁶ gmol^?1 in combinations of acetone and tridecane. The shapes of the phase contour diagrams can be related to the solvent behaviour of the n-alkane used towards polystyrene, although cosolvent action is not a simple linear function of the mixture composition.     

Miscibility,phase separation,and volumetric properties in solutions of poly(dimethylsiloxane) in supercritical carbon dioxide

Miscibility conditions and volumetric properties of solutions of poly(dimethylsiloxane) in supercritical carbon dioxide have been determined as a function of polymer molecular weight, polymer concentration, temperature, and pressure. Measurements have been conducted in a variable volume view cell equipped with an LVDT sensor to identify the position of a movable piston and thus the internal volume of the cell and consequently the density of the solution at a given pressure and temperature. The demixing data (in the form of P‐T curves for a given concentration, or as P‐x diagrams at a given T) and the density isotherms are presented for solutions of two polymer samples with different molecular weights (M_w = 38,600; M_w/M_n = 2.84 and M_w = 94,300; M_w/M_n = 3.01) at several concentrations in the range from 0.05 to 10 mass % over a temperature range from 302–425 K. Solution densities corresponding to the demixing points also have been identified. Representation of the demixing densities on the density isotherms, i.e., pressure‐density plots is a new methodology that gives a direct assessment of the volumetric expansion the solution must undergo before phase separation. The temperature–composition diagrams generated at selected pressures show that the poly(dimethylsiloxane) + CO₂ solutions display both lower critical solution and upper critical solution type behavior. The lower critical solution temperature moves to lower temperatures and the upper critical solution temperature moves to higher temperatures with decreasing pressure and they eventually merge together at lower pressures forming an hourglass‐shaped region of immiscibility. This behavior is linked to the solvent quality of supercritical carbon dioxide that changes with pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1397–1403, 2000     

Dispersed Phase Holdup in a Tall and Low Plate Free Area Liquid Pulsed Sieve-Plate Extraction Column

Dispersed phase holdup is studied in a tall and low plate free area pulsed sieve-plate extraction column. The 5.0 cm internal diameter column consists of 80 number of plates with percent free area of 13.5. The effects of pulse velocity (product of amplitude and frequency), superficial phase velocities, and solute addition are studied for five liquid-liquid systems with a wide range of interfacial tensions. The experimental holdup data is tested against the most widely recommended correlations and a new correlation has been developed that best fits the data.     

应用遗传算法求解多相化学反应体系的相稳定性及平衡组成

基于吉布斯自由能最小法原理,研究用遗传算法求解复杂化学体系的平衡问题。将相数和相态未知体系的平衡计算问题分解为两步最优化问题:假定相态数目下的吉布斯自由能最小化问题和相稳定性判据问题。通过序贯加入新相和用遗传算法交替求解两个最优化子问题,可得到最终体系的相数、相态和平衡组成。对合成甲醇和酯化反应两个多相复杂体系进行了的计算,结果验证了本研究方法的有效性。