ASOG模型推算溶液表面张力

本文将ＡＳＯＧ基团贡献模型引入Ｂｕｔｌｅｒ方程，使ＡＳＯＧ模型能够推算溶液的表面张力。对９０个二元体系和８个元体系的表面张力作了推算，并与ＵＮＩＦＡＣ推算表面张力的结果作了比较，结果令人满意。     

Synergistic effect of salt ions and water-soluble amphiphilic compounds of acidic crude oil on surface and interfacial tension

This study investigated the effect of solubility of amphiphilic compounds of acidic crude oil in water on the surface and interfacial tension (IFT) with NaCl, MgCl₂, CaCl₂, and Na₂SO₄ salts. Accordingly, distilled water, along with the salts mentioned in zero ionic strength up to 2 mol were put in contact with crude oil to become saturated with amphiphilic compounds. The effects of these compounds were investigated on the properties of contact water by pH, total organic carbon (TOC), FTIR (Fourier transform infrared spectroscopy), water-air surface tension (ST), and water-n-decane IFT tests. The results showed that some of the organic components of crude oil, especially acidic and basic compounds, are present or soluble in water, which have a significant effect on reducing the surface and IFT. The IFT reduction of water-n-decane was greater than the water-air ST system. Also, the observations showed that for both NaCl and Na₂SO₄ salt water, with increasing ionic strength of water, there was an optimum salinity within the range of 0.1-0.25 mol/L for both salts with the amount of surface and IFT minimized at this point. In the other two salts, this point was delayed upon elevation of ionic strength and was observed at high salinity. In this case, divalent cations reduce tension rate compared to monovalent cations. Due to solubility of acidic and basic groups in water, pH of salt water illustrates an acidic trend. Results of the FTIR test confirmed solubility of these compounds as well.     

Polysiloxaneimide membranes for removal of VOCs from water by pervaporation

For the separation of volatile organic compounds (VOCs) from water by pervaporation, three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three aromatic dianhydrides of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA) with a siloxane‐containing diamine. The PSI membranes were characterized using ¹H‐NMR, ATR/IR, DSC, XRD, and a Rame‐Hart goniometer for contact angles. The degrees of sorption and sorption selectivity of the PSI membranes for pure organic compounds and organic aqueous solutions were investigated. The pervaporation properties of the PSI membrane were investigated in connection with the nature of organic aqueous solutions. The effects of feed concentration, feed temperature, permeate pressure, and membrane thickness on pervaporation performance were also investigated. The PSI membranes prepared have high pervaporation selectivity and permeation flux towards hydrophobic organic compounds. The PSI membranes with 150‐μm thickness exhibit a high pervaporation selectivity of 6000–9000 and a high permeation flux of 0.031–0.047 kg/m² h for 0.05 wt % of the toluene/water mixture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2691–2702, 2000     

Use of ionic liquids for biocatalytic synthesis of sugar derivatives

Sugar‐based compounds are widely used in pharmaceuticals, cosmetics, detergents and food. They are mainly produced by chemical methods, but the use of enzymes as ‘a greener alternative’ to organic synthesis has been investigated for more than 20 years. Due to the low polar substrate solubility in organic solvents compatible with enzymes, research has focused on the application of substitutes for biocatalysis, especially ionic liquids (ILs). After introducing the main properties of ILs and especially their ability to solubilize sugars, this review focuses on one of their applications, the biocatalytic synthesis of carbohydrate derivatives. In this context, they can be used in pure IL systems, in IL/IL systems or in IL/organic solvent systems. Finally, this review provides an update on the environmental fate of ILs. Their exploitation in ‘green’ processes is still limited due to their low degradability but research is currently under way to design new more ‘eco‐friendly’ ILs. Copyright © 2012 Society of Chemical Industry     

Fractionation of Pre‐Hydrolysis Products from Lignocellulosic Biomass by an Ultrafiltration Ceramic Tubular Membrane

Abstract

Development of the lignocellulosic‐biomass‐based biorefinery for making transportation fuels requires the production of valuable byproducts, minimizing the chemical consumables, and efficient water recovery and reuse. Our focus is on a liquid stream containing a variety of soluble lignin species and alkalinity that is produced by a novel extrusion reactor that was used to break down corn stover to cellulose, sugar acids, and lignin. We report on the ambient temperature fractionation of this byproduct stream with a γ‐alumina ceramic tubular membrane. There are four primary figures‐of‐merit investigated in this study: permeance decline, total organic carbon recovery (TOC) and sodium recovery, and the average molecular mass of organic compounds rejected and permeated. These fractionation results are compared relative to differing feed compositions, recovery, and flux. There was definite fractionation between organic (mostly soluble lignin) compounds. The average molar mass of the organic compounds in the permeate remained around 1000 g/mol; however, they ranged from 1500–4000 g/mol in the retentate. In contrast to the TOC, there was no rejection of sodium ions by the membrane (a desirable objective.) With respect to flux decline, the primary form of resistance (>99%), causing significant permeance decline, was a gel/deposition layer formed on the membrane surface. However, this could be flushed away with periodic rinses using water and/or 0.1 M NaOH. After operation at a cumulative filtration load of ～4.9 Mg/m² with various soluble lignin containing streams, 70% of the membrane's virgin pure water permeance could be recovered by a more vigorous cleaning with 0.1 M NaOH including soaking and permeation. Our results seem very consistent with those previously observed for membrane applications within the pulp and paper industry.     

Ethanol oxidation on carbon supported platinum-rhodium bimetallic catalysts

Platinum is the most investigated catalyst for the electrochemical oxidation of small organic molecules. This metal presents high overpotentials for the oxidation of organic compounds and the poisoning of active sites by strongly adsorbed intermediates, mainly CO, which decrease the efficiency of a direct alcohol fuel cell (DAFC). Ethanol is an ideal fuel for these DAFC systems due to its high energy density, but one of the problems with the electro-oxidation of this fuel is the low yield for the total oxidation to CO₂. The purpose of the work reported here was to study the influence of the composition of Pt-Rh/C catalysts on the CO₂ yields. In addition, using the differential electrochemical mass spectrometry (DEMS) technique, it is shown that Pt-Rh/C catalysts enhance the total ethanol oxidation with respect to pure Pt/C by driving the reaction via the CO₂ route. The faradaic current efficiency for the oxidation of ethanol to CO₂ increased from 0.08 on pure Pt/C to 0.5 on the Pt₄₇Rh₅₃/C catalyst at 0.7 V vs. RHE. It was concluded that electronic effects play a key role in the mechanism of ethanol oxidation on Pt-Rh/C electrodes.     

基团贡献法推算有机混合液体表面张力

本文在作者曾经提出的推算液体混合物表面张力计算方法的基础上,考查了不同纯组分摩尔表面积的计算公式对液体混合物表面张力推算精度的影响.通过对100个二元体系、10个三元体系和2个四元体系的推算,找到了合适的计算公式.二元体系、多元体系的推算偏差分别为2.45%和4.42%,对于非含一元醇-水体系,式(3)为好,其偏差为2.45%,对含一元醇-水体系式(6)有明显的改善,其推算偏差为6.98%.     

非电解质水溶液黏度的关联

许多化工过程的设计需要估算含水体系的黏度,但目前的黏度关联方法用于含水体系时误差较大.今以作者所在课题组近期提出的非水液体混合物黏度关联方程为基础,通过引入形状因子,得出了一个非电解质水溶液的黏度方程.该方程可用于二元非电解质水溶液黏度的关联,且能利用二元黏度得到的关联参数推算三元非电解质水溶液的黏度.该方程对54个二元非电解质水溶液体系黏度(总计2876个黏度数据点)关联的总平均相对偏差为4.60%;对7个三元非电解质水溶液体系黏度(总计352个黏度数据点)推算的总平均相对偏差为3.75%.结果表明,该方程具有较高的关联精度和推算精度.     

Development of corresponding states model for estimation of the surface tension of chemical compounds

The gene expression programming (GEP) strategy is applied for presenting two corresponding states models to represent/predict the surface tension of about 1,700 compounds (mostly organic) from 75 chemical families at various temperatures collected from the DIPPR 801 database. The models parameters include critical temperature or temperature/critical volume/acentric factor/critical pressure/reduced temperature/reduced normal boiling point temperature/molecular weight of the compounds. Around 1,300 surface tension data of 118 random compounds are used for developing the first model (a four‐parameter model) and about 20,000 data related to around 1,600 compounds are applied for checking its prediction capability. For the second one (a five‐parameter model), about 10,000 random data are applied for its development, and 11,000 data are used for testing its prediction ability. The statistical parameters including average absolute relative deviations of the results form dataset values (25 and 18% for the first and second models, respectively) demonstrate the accuracy of the presented models. © 2012 American Institute of Chemical Engineers AIChE J, 59: 613–621, 2013     

Hydrodynamics and mass transfer in bubble column: Influence of liquid phase surface tension

According to literature, few experiments are performed in organic solvents which are mostly used in commercial gas-liquid reactors. However, it is commonly accepted that data obtained in aqueous solution allow to predict the surface tension effects, and to model the behaviour of organic solvents. In this work, we examine the validity of this approximation.In this objective, the flows observed in two pure media having similar viscosity but different surface tension—respectively, water (reference) and cyclohexane (solvent)—are successively compared at two scales: in a bubble column and in bubble plumes.In bubble plumes, as expected, the mean bubble size is smaller in the medium having the smallest surface tension (cyclohexane), but for this medium the destabilisation of flow is observed to occur at smaller gas velocity, due to break-up and coalescence phenomena. In bubble column, these phenomena induce the bubbling transition regime at lower gas velocity, whatever the operating conditions for liquid phase: batch or continuous. Consequently, when the two media are used at similar gas superficial velocity, but in different hydrodynamic regimes, greater gas hold-up and smaller bubble diameter can be observed in water; the interfacial area is then not always higher in cyclohexane.This result differs from the behaviour observed in the literature for aqueous solutions. The analysis of bubble plumes in aqueous solutions of butanol shows that this difference is due to a fundamental difference in coalescent behaviour between pure solvents and aqueous mixtures: the surface tension effect is less important in pure liquid than in aqueous solutions, because of the specific behaviour of surfactants.It is then still difficult to predict a priori the bubbling regime or the flow characteristics for a given medium, and all the more to choose an appropriate liquid as a model for industrial solvents.     

A general method of predicting the water activity of ternary aqueous solutions from binary data

An isopiestic method has been developed to predict a_w for ternary solutions from binary a_w data. Another method, previously outlined by Robinson and Bower, has been extended to include non-electrolytes. Both methods have been used to predict a_w's for 51 representative systems. The results show that the isopiestic method is as good as, or better than Robinson and Bower's in predicting a_w for ternary aqueous electrolyte/ electrolyte, electrolyte/non-electrolyte and non-electrolyte/non-dectrolyte systems. Calculated a_w values are in good agreement (<0.5%> error on the average) with experiment. The methods are applicable to relatively concentrated solutions up to 12 m.     

Separation of liquid mixtures by using polymer membranes. I. Permeation of binary organic liquid mixtures through polyethylene

The permeation characteristics and the separation behavior of 25 combinations of binary liquid mixtures through low-density polyethylene membrane have been investigated. The organic compounds studied were members of the homologous series of liquid aliphatic hydrocarbons between n-pentane and n-nonane as well as some aromatic and cyclic compounds. A special permeation cell was designed in order to study permeation rates at different temperatures ranging from 25 to 45°C. The rate of permeation increased with temperature, and it was found that the temperature dependence of the permeation rate for both pure compounds and mixtures could be expressed by Arrheniustype relationships. The efficiency of separation, however, decreased with increasing temperature. Activation energies of permeation rànged from 16–22 kcal/mol for pure compounds and binary mixtures of benzene, n-hexane, cyclohexane, and 2–2-dimethylbutane. The effects of chemical nature, molecular size, and molecular shape of the diffusing species on the permeation and separation were studied and qualitative guidelines were suggested. The effect of the composition of the binary mixtures on the permeation rate has been investigated for several systems. Permeation enhancement effects were observed in which the mixtures permeate considerably faster than either of the pure components. Maximum permeation rates occurred at about 50 wt-% mixtures for the systems benzene–n-hexane and benzene–cyclohexane. This phenomenon is explained in terms of a combined internal plasticizing and solubility effect.     

The use of solvents for purifying industrial naphthalene from coal tar distilled oils

The organic chemistry industry is based on organic compounds derived from coal, petroleum and gas. Coal tars derived from the carbonisation process are complex mixtures, of which the polycyclic aromatic hydrocarbons (PAH's) are the main component. One of the most important PAH's is naphthalene, which represents between 10 to 12% of the sample. In recent years, new applications for industrial naphthalene have been developed. However, the naphthalene required for high level industry must be extremely pure. New routes in the purification process are being studied to reduce the economic cost and environmental impact resulting from the increase in demand for pure naphthalene. Any alternative method to that of sublimation for purification in the distillation process and/or catalytic hydrogenation must improve the quality of industrial naphthalene, to make it suitable for the new applications. In the present work, an alternative method for purifying industrial naphthalene has been investigated. A new process based on extraction with solvents such as phosphoric acid and acetic acid is reported and discussed. Industrial naphthalene was purified by means of a new technique and the stability and good properties of the product were verified.     

Group contribution model for determination of molecular diffusivity of non-electrolyte organic compounds in air at ambient conditions

Determination of diffusion coefficients of pure compounds in air is of great interest for modeling of air pollution control processes. In this communication, a Group Contribution (GC) method is applied to represent/predict the molecular diffusivity of chemical compounds in air at 298.15 K and atmospheric pressure. 4661 compounds from various chemical families have been investigated to propose a comprehensive and predictive model. The final model is resulted from coupling the Artificial Neural Network (ANN) with group contributions. Using this dedicated model, we obtain satisfactory results quantified by the following statistical results: Squared Correlation Coefficient=0.995, Standard Deviation Error=0.02, and Average Absolute Deviation=1.4% for the calculated/predicted properties from existing experimental values.     

SURFACE TENSION OF POLAR LIQUIDS AND MIXTURES

The simple principle of corresponding states for surface tension, has been generalized to include polar compounds (including those exhibiting hydrogen bond) and their mixtures, by introducing an additional parameter to characterize molecular polarity. In addition the statistical tool of factor analysis has been used to correlate this parameter. For mixtures a binary interaction parameter is also needed, which has also been correlated with easily available properties. Good agreement has been obtained for a wide range of pure liquids and mixtures.     

Poly(vinyl alcohol)‐based polymeric membrane: Preparation and tensile properties

A series of poly(vinyl alcohol) (PVA)‐based single‐layer organic polymeric membranes were prepared via the crosslinking of PVA with different amounts of formaldehyde. Meanwhile, for comparison, both a three‐layer organic polymeric membrane and a hybrid composite membrane were also prepared by the layer‐upon‐layer method. Their thermal stability and tensile properties were investigated to examine the effect of crosslinking on the membrane performances. Thermogravimetric analysis and differential scanning calorimetry thermal analyses showed that the thermal degradation temperature of the single‐layer crosslinked membrane C reached up to 325°C. Tensile testing indicated that the three‐layer organic polymeric membrane E had excellent tensile strength among these single‐layer and three‐layer membranes. The swelling properties revealed that the swelling degree value of these membranes decreased with an increase in methanol concentration; this suggests that they were not easily swollen by the methanol solution, which is meaningful for the separation of organic mixtures. Field emission scanning electron microscopy images exhibited that the crosslinking of functional groups impacted their structures and confirmed that their mechanical properties were related to their structures. These findings suggest that the crosslinking of functional groups is an effective method for adjusting the tensile strength of PVA‐based organic polymeric membranes and related hybrid composite membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of liquid characteristics on the wetting,capillary migration,and retention properties of fibrous polymer networks

Fluid penetration through porous networks consists of two different phenomena: (1) pore fluid displacement and (2) fluid flow through the pores. The first phenomenon depends on the pore size, the fluid–fluid interfacial tension, and the contact angle. The second phenomenon is pore‐size‐ and viscosity‐dependent. We adapted an experimental methodology often used for measurements of liquid permeability and hydraulic conductivity of soils and applied it to polymeric medical textiles. The methodology made use of a pressure/flow cell in which a sample was mounted. The flow rates were measured during sequences of increasing and decreasing pressures applied to the displacing nonwetting fluid (aqueous solution). The effects of the liquid parameters on penetration were investigated. Surface tension effects were studied with water and two solutions with surface tensions lower than that of pure water; the liquids with lower surface tensions had lower displacement pressures. To study viscosity effects, we used water and two solutions with viscosities higher than that of pure water. Increasing the viscosity not only caused the flow rate to decrease but also caused deformation, that is, enlargement, of the pores. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 282–292, 2005     

An apparatus for the measurement of surface tensions at high pressures and temperatures

An apparatus for the measurement of surface tensions of organic liquids in contact with a gas has been developed which is capable of operation to 400°C and to 14 MPa. It is based on the maximum bubble pressure technique, modified for hydrocarbon oils at high pressures and temperatures. Accuracy of measurement is of the order of ±3% for non‐aqueous systems for values down to 5 mN/m. Only a 20 to 30 mL liquid sample is required, and small gas volumes. In practice, it was found that measurements with most organic liquids could only be made to a maximum of about 350°C because of the thermal instability of most of these compounds, in particular, for hydrocarbon liquids. Any thermal decomposition or coke deposition leads to inaccurate results. Results obtained for known liquids are compared with values given in the literature.     

SURFACE TENSION OF POLAR LIQUIDS AND MIXTURES

The simple principle of corresponding states for surface tension, has been generalized to include polar compounds (including those exhibiting hydrogen bond) and their mixtures, by introducing an additional parameter to characterize molecular polarity. In addition the statistical tool of factor analysis has been used to correlate this parameter. For mixtures a binary interaction parameter is also needed, which has also been correlated with easily available properties. Good agreement has been obtained for a wide range of pure liquids and mixtures.