Evaluation of the ratio of the evaporation energy to the activation energy for estimating the thermodiffusion coefficient

Thermodiffusion has an important role in displacements of hydrocarbon reservoir. The ratio of the evaporation energy to the activation energy of viscous flow in pure limits, τ_pure,k, is of a great importance in estimating the thermodiffusion coefficient for non‐associating fluid mixtures. Several methods may be used to estimate τ_pure,k which causes different values for thermodiffusion coefficients. A fixed value for τ_pure,k was considered to predict the thermodiffusion coefficient. In this paper, Abbasi et al.'s [J. Non‐Equilib. Thermodyn. 2010;35:1–14] model and Shukla and Firoozabadi's model have been applied to predict thermodiffusion coefficients for linear chain hydrocarbon binary mixtures. The results show a very good performance of the simple approach in respect to the previous models in estimating thermodiffusion coefficients. © 2011 Canadian Society for Chemical Engineering     

New algebraic expressions for thermodiffusion in binary n‐alkane mixtures

Following a detailed analysis of the experimental data on thermodiffusion coefficients of numerous binary hydrocarbon mixtures from over 90 experiments, four new algebraic expressions are proposed. As per these formulations, the thermodiffusion coefficient of binary n‐alkane mixtures can be expressed as a function of the chemical composition of the mixture and the mixture properties such as density and viscosity. Detailed experimental validation is presented using four n‐alkane series containing a wide range of combinations of n‐alkanes. Additionally, comparison with recently proposed neural network model and a model based on the principles of non‐equilibrium thermodynamics is also presented. It has been found that the proposed algebraic models are simple in formulations, are evaluated with least computational effort and yet have a very high accuracy in predicting the thermodiffusion coefficients. © 2012 Canadian Society for Chemical Engineering     

Effect of operation conditions in the pervaporation of ethanol–water mixtures with poly(1‐trimethylsilyl‐1‐propyne) membranes

Poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) is known to show preferential permeation of ethanol in the pervaporation of ethanol–water mixture. Although this polymer presents good characteristics for the separation of organic–water solutions, operation conditions and membrane characteristics, such as thickness, affect its pervaporation performance. The effect of temperature and feed concentration on pervaporation was studied. During pervaporation of 10 wt % ethanol–water solution, the separation factor (α_H2O^EtOH) remains almost constant, whereas the permeation flux (F) increases exponentially with operation temperature. On the other hand, the separation factor decreases, whereas the permeation flux increases with ethanol content in the feed mixture. The membrane thickness also affects the performance of PTMSP polymer films: selectivity increases sharply with membrane thickness up to 50 μm, whereas it remains constant for thicker membranes. The permeation flux decreases with membrane thickness in the whole range studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94:1395–1403, 2004     

Effects of solvent adsorption on solution properties of poly(vinyl alcohol)/dimethylsulfoxide/water ternary systems

In this study, the solvent adsorption phenomena of poly(vinyl alcohol) (PVA) in cosolvent mixtures of dimethylsulfoxide (DMSO; solvent 1) and water (solvent 2) were investigated. Typically, this cosolvent mixture could form hydrogen‐bonded DMSO/(water)₂ complexes, involving one DMSO and two water molecules. Because of the complex formation in the cosolvent mixtures, PVA chains preferentially adsorb water molecules at DMSO mole fraction X₁ < 0.33, but preferentially adsorb DMSO molecules at X₁ > 0.33. The preferential adsorption of DMSO (a good solvent for PVA) could cause the relatively extended conformation of PVA chains in solutions because of the increase in excluded volume effect. Because of various interactions between PVA chains and cosolvent mixtures, the aggregation and gelation behaviors of PVA solutions were significantly affected by the composition of cosolvent mixture. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3211–3217, 2004     

Solvent effects on esterification equilibria

Solvents are known to have strong impacts on the yields of equilibrium reactions. This work focuses on the thermodynamic investigation of these solvent effects on esterification reactions of acetic acid and propionic acid with ethanol. Esterification of acetic acid was performed in the solvents acetone, acetonitrile (ACN), dimethylformamide (DMF), and tetrahydrofurane as well as in mixtures thereof. ACN promotes the esterification of acetic acid, whereas it is strongly suppressed by DMF. The esterification of propionic acid was investigated with various reactant concentrations in acetone. The experimental equilibrium data in pure solvents and solvent mixtures were modeled using the thermodynamic equilibrium constant K_a and the reactant/product activity coefficients predicted by the perturbed chain‐statistical associating fluid theory (PC‐SAFT). For a given K_a, PC‐SAFT is able to predict the influence of the solvent and even solvent mixtures on the equilibrium concentrations of esterification in almost quantitative agreement with the experimental data. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3000–3011, 2015     

Dehydration of light oil by pervaporation using poly(vinyl alcohol)–poly(acrylic acid‐co‐maleic acid) membranes

A new blended membrane was prepared and tested by pervaporation of light oil, a mixture of five alcohols plus water. The blended membrane was synthesized by blending poly(vinyl alcohol) and poly(acrylic acid‐co‐maleic acid) sodium salt in the presence of sulfuric acid to dope the reaction. We tested several membranes in order to choose the adequate composition to have the best permselectivity. The PVA(60)–PAA‐co‐maleic acid(40) membrane was selected as it was found to be highly selective. Sorption experiments were performed using binary and ternary water–alcohol solutions. The influence of temperature and feed composition on the selectivity and flux in pervaporation was investigated for two different binary mixtures (water/ethanol, water/isobutanol) and one ternary system (water/ethanol/isobutanol). This membrane presents good permselective properties, high water flux, and good selectivity and can even be used for high‐water activities The performances of this new membrane were compared to those obtained with the PVA(90)–PAA(10) membrane synthesized recently: The fluxes observed for the water–ethanol separation were of the same order of magnitude but the selectivity was found to be much higher. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1709–1716, 2002     

Hydrothermal liquefaction of wheat straw in hot compressed water and subcritical water–alcohol mixtures

Hydrothermal liquefaction of lignocellulosic biomass (wheat straw) into bio-oil has been investigated under subcritical conditions (temperature up to 350 °C, pressure up to 200 bar) in water and water–alcohol mixtures using ethanol and isopropanol in a continuously operated tubular reactor. The effect of different reaction parameters such as temperature, pressure and water–alcohol ratio on the biomass conversion, cracking products yield and the higher heating value (HHV) of the received bio-oil was studied. The water–ethanol mixture was found to be a very reactive medium showing a complete biomass conversion and >30 wt% yield of high caloric oil (HCO). A maximum HHV of 28 MJ/kg for HCO was achieved. In addition, Ru (5 wt%) on H-Beta support was used as catalyst in a run with hydrogen in the feed showing deeper deoxygenation of reaction intermediates and highest HHV of the product oil (30 MJ/kg). This work demonstrated the usability of water–ethanol mixtures for an effective depolymerization of lignocellulosic biomass to bio-oils under subcritical reaction conditions with more than doubled HHV compared to the feedstock, in particular using a catalyst and the presence of hydrogen for further deoxygenation.     

局部组成型的互扩散系数模型

根据局部组成概念建立了混合物中互扩散系数与自扩系数的关系,并以分子集团迁移的概念建立了混合物中组分的自扩散系数的预测方法,由此预测二元系的自扩散系数和互扩散系数与实验结果符合良好,比经典的Ｈａｒｔｌｅｙ模型有了很大地改进。     

Studies on poly(acrylic acid)/attapulgite superabsorbent composites. II. Swelling behaviors of superabsorbent composites in saline solutions and hydrophilic solvent–water mixtures

The effect of the attapulgite content on the swelling for a series of poly(acrylic acid)/attapulgite superabsorbent composites in water was studied. The effects of the temperature and pH values on the water absorbency of the superabsorbent composites were investigated. The swelling behavior of the superabsorbent composites in various saline solutions was also investigated. The water absorbency in various salt solutions decreased with an increase in the ionic strength of the solutions. At a high ionic strength (>1 × 10^?3M), the water absorbency in monovalent cationic solutions was higher than that in multivalent cation solutions. This dramatic reduction of the water absorbency in multivalent cationic solutions of high ionic strength may have been due to the complexing ability of the carboxylate groups inducing the formation of intramolecular and intermolecular complexes, which resulted in an increased crosslink density of the network. The swelling behavior of the superabsorbent composites in mixtures of water and hydrophilic solvents, including methanol, acetone, ethanol, and dimethyl sulfoxide (DMSO), was also investigated. The water absorbency decreased with an increase in the concentration of any of the four organic solvents, and two transitions were observed in the superabsorbent composite/hydrophilic solvent–water mixture systems. The main transition for the four hydrophilic solvent–water mixtures was a collapse of the swollen gel (at 50–80% methanol, 30–80% acetone, 50–80% ethanol, and 50–80% DMSO). For the methanol–water system, the magnitudes of the first and second transitions for the poly(acrylic acid)/attapulgite superabsorbent composites containing lower proportions of attapulgite were larger than those for the superabsorbent composites with higher attapulgite contents. The effect of the mixture temperature on the water absorbency of the superabsorbent composites in 10 min was also reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1869–1876, 2004     

Sorption,diffusion, and pervaporation separation of water–acetic acid mixtures through the blend membranes of sodium alginate and guar gum‐grafted‐polyacrylamide

Nonporous homogeneous dense membranes were prepared from the blends of sodium alginate (Na–Alg) with guar gum‐grafted polyacrylamide (GG‐g‐PAAm) in the ratios of 3 : 1 and 1 : 1 and these were tested for the pervaporation separation of water–acetic acid mixtures at 30°C. Blend compatibility was studied in solution by measuring the viscosity and the speed of sound. Membranes were crosslinked by glutaraldehyde. The GG‐g‐PAAm polymer and the crosslinked blend membranes were characterized by Fourier transform infrared spectra. High separation selectivity was exhibited by the pure Na–Alg membrane for water–acetic acid (HAc) mixtures containing 20 mass % of water. The permeation flux increased with increasing mass percent of water in the feed as well as with an increase in the amount of GG‐g‐PAAm in the blend, but separation selectivity decreased. Sorption selectivity was higher for the Na–Alg membrane than for the blend membranes, but it decreased with increasing mass percent of GG‐g‐PAAm in the blends. Diffusion selectivity values vary systematically with the blend composition, but not with the amount of water in the feed. Diffusion coefficients of the water–HAc mixtures were calculated from Fick's equation using sorption data and compared with those calculated from flux values obtained in pervaporation experiments. The Arrhenius activation parameters were calculated for the 20 mass % of water in the feed using flux and diffusion data obtained at 30, 40, and 50°C. The diffusion and pervaporation results are explained in terms of solution–diffusion concepts. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 259–272, 2002     

Purification of Monoglycerides From Palm Stearin by Liquid–Liquid Extraction With Aqueous Ethanol

Monoglycerides obtained by glycerolysis of palm stearin can be purified by extraction with aqueous ethanol, a process much less expensive than molecular distillation, which is the method that is commonly used at the industrial level. Liquid–liquid equilibrium data were measured for the six pseudoternary systems involved in the purification of the crude monoglyceride mixture obtained by glycerolysis of palm stearin. These systems are monoglycerides–ethanol–water, diglycerides–ethanol–water, triglycerides–ethanol–water, monoglycerides–diglycerides–(65 wt% ethanol + 35 wt% water), monoglycerides–triglycerides–(65 wt% ethanol + 35 wt% water), and diglycerides–triglycerides–(65 wt% ethanol + 35 wt% water). Measurements were performed at 343.15 K using a thermostated view cell. The experimental tie‐line data for the six systems were correlated using the NRTL model for activity coefficients. Results from a simulation study using the binary interaction parameters determined for the NRTL model indicate that liquid–liquid extraction with aqueous ethanol can be used to obtain a 90 wt% monoglycerides product with up to 70% yield, in a simple process.     

Production of Motor Fuel Grade Alcohol by Concentration Swing Adsorption

Abstract

A new cyclic process concept called “concentration swing adsorption” for separation of bulk binary liquid mixtures is described. The process carries out the primary separation by selective liquid-phase adsorption of one of the components of the feed mixture on an adsorbent. The adsorbed component is then desorbed by a desorbent liquid which is equally or more strongly adsorbed than the slectively adsorbed component of the feed mixture. The desorbent liquid is removed from the adsorbent by displacing it with the less strongly adsorbed component of the feed mixture so that the adsorbent can be resused. The process also includes a complementary step where the adsorbent is rinsed with the more strongly adsorbed component of the feed mixture so that two essentially pure products are produced from the feed mixture with high recoveries of both components. At least one simple distillation is also required by the process which separates the desorbent liquid from the less strongly adsorbed component of the feed mixture. The process can be used to separate liquid mixtures with close boiling components or azeotropic mixtures which require energy intensive distillation. A very efficient separation can be achieved in these cases by spending only a fraction of the distillation energy. An example of such an application, viz., separation of a bulk ethanol–water mixture for motor fuel grade alcohol production, is described. A local equilibrium model of the process is used to evaluate the performance of the process for that separation using an activated carbon as the adsorbent and acetone as the desorbent liquid. Experimentally measured equilibrium adsorption characteristics for ethanol–water, acetone–water, and acetone–ethanol binary liquid mixtures on the carbon as well as adsorption column dynamics for the steps of the process are reported.     

Natural rubber/poly(acrylic acid) semi‐interpenetrating polymer network membranes for the pervaporation of water–ethanol mixtures

Pervaporation membranes for the dehydration of water–ethanol mixtures were prepared from a semi‐interpenetrating polymer network (semi‐IPN) of natural rubber (NR) and crosslinked poly(acrylic acid) (PAA). The swelling studies revealed that hydrophilic PAA present in the semi‐IPN membranes caused the membranes to swell greatly in water. The swelling degree of the membranes in water was significantly affected by the amount ratio between the hydrophobic NR and the hydrophilic PAA. The sorption experiments of the NR/PAA membranes in various concentrations of water–ethanol mixtures suggested the preferential sorption to water. However, for the membrane with high PAA content, the water sorption selectivity decreased considerably at high water concentration of water–ethanol mixtures because the membrane was in the highly swollen state. Pervaporation separations of water–ethanol mixtures using NR/PAA membranes were performed and it was found that at low water concentrations of feed mixtures, increasing the PAA content of the membrane can enhance both water permeation flux and selectivity. Additionally, under low feed water concentration, increasing the feed temperature would increase the water flux with the decreasing of the ethanol flux. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Experimental measurement of the effective diffusion and thermodiffusion coefficients for binary gas mixture in porous media

Thermodiffusion or Soret effect, corresponding to a mass flux caused by a temperature gradient applied to fluid mixture, has been taken into account in many porous media applications, particularly in chemical engineering and geophysics. In the literature, the effective macro-scale diffusion coefficients are now well established, while uncertainty remains concerning the relationship between the effective thermodiffusion coefficient and micro-scale parameters (such as pore-scale geometry). Our previous study on theoretical model of effective thermodiffusion coefficient for a pure diffusion regime confirmed that the tortuosity factor acts in the same way on both Fick diffusion coefficient and on thermodiffusion coefficient.In this study, new experimental results obtained with a two bulb apparatus are presented. The diffusion and thermodiffusion of a helium–nitrogen and helium–carbon dioxide system through cylindrical samples filed with glass spheres of different diameter are measured at the atmospheric pressure. Concentrations are determined by analyzing the gas mixture composition in the bulbs with a katharometer device. A transient-state method for coupled evaluation of thermodiffusion and Fick coefficient in two bulbs system is proposed. The obtained results are in good agreement with theoretical results from previous study and emphasize the porosity of the medium influence on both diffusion and thermodiffusion process. The tortuosity of the medium calculated using both effective diffusion and effective thermodiffusion coefficients are the same.     

Solubility of Ketoconazole in Ethanol + Water Mixtures at Various Temperatures

Ketoconazole is an important drug with low water solubility. Its low aqueous solubility could be increased using various methods such as by the addition of a pharmaceutical cosolvent. The solubility of ketoconazole in ethanol + water mixtures at 293.2, 298.2, 303.2, and 308.2 K were determined, and the results showed that the addition of ethanol increased the solubility and the maximum value was obtained at 80% of ethanol. The generated data were mathematically represented using the Jouyban–Acree model within an acceptable accuracy.     

Solubility of N‐Guanylurea Dinitramide in Binary Solvent Mixtures

The solubility of N‐guanylurea dinitramide (GUDN, Fox‐12) in binary solvent mixtures was measured. Binary solvents such as dimethyl sulfoxide (DMSO)/water and N,N‐dimethylacetamide (DMA)/water were investigated. The temperature was in the range of 0 °C to 70 °C for DMA‐water and 20 °C to 70 °C for DMSO‐water. The temperature dependence on the solubility was higher in DMA‐water than in DMSO‐water at the same fraction of water. On the other hand, the modeling data was obtained by using the Apelblat equation. The average relative errors are less than 3 %. Supersaturation for crystallization of GUDN in solution can be easily generated by adding water in DMSO (or DMA).     

Densities,ultrasonic speeds,refractive indices,and COSMO analysis for binary mixtures of dichloromethane with acetone and dimethylsulfoxide at T = (298.15, 303.15, and 308.15) K

Experimental densities (ρ), ultrasonic speeds (u), and refractive indices (n_D) of binary mixtures of dichloromethane (DCM) with acetone (ACT) and dimethylsulfoxide (DMSO) were measured over the whole composition range at T?=?298.15, 303.15, and 308.15?K. From the experimental data, excess molar volume (V^E), deviations in isentropic compressibility (Δk_s), deviations in intermolecular free length (ΔL_f), deviations in refractive index (Δn_D), and deviations in ultrasonic speed (Δu) were calculated. Moreover, the Benson–Kiyohara theory was applied to the binary mixtures to obtain the theoretical Δk_s values. The COSMO calculations depending on density functional theory were utilized to estimate the σ-profiles for the DCM, ACT, and DMSO. The interpreted σ-profile trends were found supportive with the experimental findings. Applicability of different empirical and semi-empirical relations of refractive index data were tested against the measured results, and good agreement has been obtained. The possible results of intermolecular molecular interactions among mixture components were interpreted.     

Synthesis and characterization of polyacrylamide‐grafted sodium alginate copolymeric membranes and their use in pervaporation separation of water and tetrahydrofuran mixtures

Polyacrylamide‐grafted sodium alginate (PAAm‐g‐Na‐Alg) copolymeric membranes have been prepared, characterized, and used in the pervaporation separation of 10–80 mass % water‐containing tetrahydrofuran mixtures. Totally three membranes were prepared: (1) neat Na‐Alg with 10 mass % of polyethylene glycol (PEG) and 5 mass % of polyvinyl alcohol (PVA), (2) 46 % grafted PAAm‐g‐Na‐Alg membrane containing 10 mass % of PEG and 5 mass % of PVA, and (3) 93 % grafted PAAm‐g‐Na‐Alg membrane containing 10 mass % of PEG and 5 mass % of PVA. Using the transport data, important parameters like permeation flux, selectivity, pervaporation separation index, swelling index, and diffusion coefficient have been calculated at 30°C. Diffusion coefficients were also calculated from sorption gravimetric data of water–tetrahydrofuran mixtures using Fick's equation. Arrhenius activation parameters for the transport processes were calculated for 10 mass % of water in the feed mixture using flux and diffusion data obtained at 30, 35, and 40°C. The separation selectivity of the membranes ranged between 216 and 591. The highest permeation flux of 0.677 kg/m² h was observed for 93% grafted membrane at 80 mass % of water in the feed mixture. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 272–281, 2002     

利用二元体系的C H红外光谱推算汽液平衡数据

Prediction of vapor-liquid equilibrium （VLE） is extremely necessary to separate liquid mixture in chemical production, especially when the required experimental data are difficult to measure, or the measurement is not economical. The infinite dilution activities can be used to predict VLE. However, it needs both the ends of the activities that are difficult to obtain for many systems. In the present study, a new model is proposed for correlating the frequency shift of C-H stretching band of IR spectra over the whole concentration. Investigated mixtures in- clude water/2-propanol, water/N, N-dimethylformamide （DMF）, water/methanol, water/ethanol, water/1, 4-dioxane, and water/dimethylsulfoxide （DMSO） systems. Simultaneous correlations of C--H frequency shift and VLE data are made. Furthermore, the VLE data were predicted with satisfactory results by the parameters obtained from IR spectra coupled with one ot the intinite chlution activity coefficients.