Using pervaporation technique to separate water from organics

This paper is focused on how water may be separated from dioxan, butanone and butyric acid under constant operating conditions. The analysis is presented in terms of variations in the permeation flux, individual partial fluxes and separation factors. As in a membrane process, in order to separate a liquid mixture, pervaporation relies on differences in membrane permeability as well as the vapour pressures of the components in the mixture. It is found that the separation factors reach infinity as the total permeate pressure is reduced to the vapour pressure of the organic permeant. The permeation flux increases with increasing water concentration in the feed. A drop in the flux has been observed on addition of an extra component. The PVA membrane confirmed its hydrophilic characteristics by not allowing butyric acid and butanone to permeate. Values of the activity coefficients and diffusion coefficients are reported versus the vapour composition for binary, ternary and multi-component systems. The diffusion coefficient increases with a decrease in mole fraction of the component in the membrane.     

On a rapid method to characterize intercrystalline defects in zeolite membranes using pervaporation data

This work presents a mass-balance-based model devoted to the characterization of intercrystalline defects active to permeation in film-like zeolite membranes using pervaporation data. Relevant structural information concerning such domains can be obtained from the slope and intercept of the line that describes the increase of the flux pervaporated through a membrane with the absolute pressure in the liquid feed. Capillary forces appear to govern mass transfer within intercrystalline pores. The suitability of the model is assessed by using a collection of zeolite NaA membranes prepared on our premises for the separation of ethanol/water mixtures. The results show that, although a membrane displays high selectivity, a reduced number of defects in the zeolite layers cannot be ruled out. The model offers the advantage of enabling the characterization of large defects in pervaporation membranes at experimental conditions similar to those in which they are likely to be used.     

Microemulsion Formation and Detergency with Oily Soil: V. Effects of Water Hardness and Builder

In this study, the impact of water hardness and builder on the phase diagrams of motor oil microemulsions and the detergency of oil removal from a polyester/cotton blend was investigated. Water hardness and builder were found to have insignificant effects on the microemulsion phase diagram with motor oil. A mixed surfactant system of two parts C_14–15(PO)₃SO₄Na, and 98 parts C_12–14H_25–29O(EO)₅H of the total actives at 4% salinity was used to study the effect of water hardness and builders sodium tripolyphosphate (STPP) or ethylenediaminetetraacetic acid (EDTA) on detergency at 30 °C at a total active concentration of 0.3%. This formulation is in the Winsor Type III microemulsion regime. The microemulsion-based formulation resulted in better detergency than a leading commercial liquid laundry detergent at all concentrations up to 0.5% actives. The microemulsion-based formulation showed a plateau in detergency at >80% oil removal above 0.1% actives. The total oil removal decreased with increasing water hardness while the interfacial tension increased. When hard water was used in laundering, the total oil removal improved with increasing concentrations of STPP or EDTA up to stoichiometric levels, with STPP being slightly more effective than EDTA on a molar basis. Even high builder concentration could not improve hard water detergency to that of soft water. A significant fraction of oil removal occurred in the rinse steps vs. the wash step. Increasing water hardness reduced this fractional oil removal in the rinse steps, but it was still over half of total oil removal at 1,000 ppm water hardness.

Microemulsion Formation and Detergency with Oily Soil: IV. Effect of Rinse Cycle Design

The objective of this work was to apply a microemulsion-based formulation for the removal of motor oil in laundry detergency at low salinity. To produce the desired phase behavior, three surfactants were used: alkyl diphenyl oxide disulfonate (ADPODS), sodium dioctyl sulfosuccinate (AOT) and sorbitan monooleate (Span 80). The mixed surfactant system of 1.5% ADPODS, 5% AOT and 5% Span 80 (13 parts ADPODS, 43.5 parts AOT, and 43.5 parts Span 80 of the total actives) was found to form a middle phase microemulsion (Type III) at a relatively low salinity of 2.83% NaCl. When this formulation was diluted, detergency performance increased with increasing total surfactant concentration and leveled off above about 0.1% total actives on the three types of fabrics studied (pure cotton, 65/35 polyester/cotton blend, and pure polyester). Detergency was found to improve with increasing hydrophilicity of the fabric with cotton being cleanest after washing and polyester the most difficult to clean. To achieve a specified oil removal, less rinse water can be used if a higher number of lower-volume rinses are employed. An interesting characteristic of microemulsion-based formulations is that a substantial fraction of oil removal occurs during the rinse cycle. In this work, this removal is shown to be due to the low oil/water interfacial tension during initial rinsing and is therefore strongly correlated to residual surfactant concentration in the rinse steps. As a result, the number of rinses and the volume of water per rinse can profoundly affect detergency in these systems.

Filled poly(2,6-dimethyl-1,4-phenylene oxide) dense membranes by silica and silane modified silica nanoparticles: characterization and application in pervaporation

The effects of silica and silane modified silica fillers on the pervaporation properties of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) dense membranes have been studied. Crystallinity, thermal and mechanical properties of unfilled and filled PPO membranes with silica and silane modified silica nanoparticles were investigated. The surface energy together with the solubility parameters of the membranes and the nanoparticles were determined. Pervaporation separation of methanol/methyl tert butyl ether (MTBE) mixtures over the entire range of concentration were carried out using both filled and unfilled membranes. The results are discussed in terms of the solubility and the diffusivity of each liquid component in the membranes. Flory-Huggins theory was used to predict the sorption methanol selectivity. Compared to the unfilled PPO membrane, the filled PPO membranes exhibit higher methanol selectivity and lower permeability. For methanol concentration in liquid feed mixture lower than 50 wt%, methanol selectivity of the filled PPO membranes with silane modified silica is better than that of the silica filled and unfilled PPO membranes.     

油井缓蚀剂的研究与应用技术

本文介绍了根据中原油田油系统腐蚀特性优选了4种类型的端点前移防腐剂，通过腐蚀挂片、测铁、示踪显示技术确定了合理的加药工艺，实现了端点停止加药而前移至油井，同时保护整个油系统之目的。     

Modeling of the pervaporation process for isobutanol purification from aqueous solution using intelligent systems

In this study, intelligent systems (ANN-GA and GMDH) was employed to develope a model based on experimental data to predict the performance of the pervaporation process. The ANN system was coupled with the genetic algorithm (GA) to choose initial connection weights and biases of the multi-layer feed forward neural network (FFNN). The input parameters were the feed concentration, membrane thickness, and Reynolds number, while the outputs were total flux and permeate concentration. The RMSE of the estimated total flux for the ANN-GA and GMDH were 0.09170 and 0.0903, respectively. Also, the RMSE of estimated permeate concentration for the ANN-GA and GMDH were 0.0994 and 0.0975, respectively. The results indicated that the models had sufficient accuracy, but that GMDH could provide a better outcome. Finally, the relative importance of input variables on the network outputs was determined. Sensitive analysis showed that the membrane thickness and feed concentration are the most effect on the total flux and permeate concentration, respectively. Other variables also have important effect on the PV process and cannot be ignored.     

Chemical aspects of chlorophyll breakdown products and their relevance to canola oil stability

The production of prooxidant compounds brought about through subjecting chlorophyll a or pheophytin a to laboratory-scale processing in the presence of canola oil or tricapryloylglycerol was investigated. The addition of chlorophyll a (60 ppm) to canola oil prior to processing resulted in an oil of lowered stability. No large contribution to the produced instability by any one processing step was found when pheophytin a was added (60 ppm) to canola oil prior to processing. To isolate the effect of processing on the pigment, tricapryloylglycerol was used in the place of unsaturated canola oil as a carrier for pheophytin a (60 ppm). A control consisted of processed tricapryloylglycerol that had no added pheophytin prior to processing. The subsequent addition of pigment-treated processed tricapryloylglycerol to linseed oil (1:1, w/w) caused a decrease in the stability of the latter, when compared with the control. No differences were observed between the prooxidant tricapryloylglycerol and the control tricapryloylglycerol by methods involving ultraviolet spectroscopy and thin-layer or gas chromatography.     

Modification of poly(vinyl alcohol) using maleic acid and its application to the separation of acetic acid-water mixtures by the pervaporation technique

The ‘solution technique’ modification of poly(vinyl alcohol) (PVA) using maleic acid was carried out with the help of triethanolamine/water catalysts. The resulting PVA membranes were characterized by differential scanning calorimetry, infrared spectroscopy, and tensile studies to investigate the reaction between PVA polymer and maleic acid. It was found that the resulting PVA membranes had two portions, branched and crosslinked, and there were no more branched than cross-linked portions. For the pervaporation separation of the acetic acid-water system, two reaction densities (X_cr = mole maleic acid per mole monomeric unit of PVA) of 0.05 and 0.1 were studied for the separation of the entire range of mixture compositions at 25° C. The separation factors of the X_cr = 0.05 modified PVA membranes were higher than those of the X_cr 0.1 modified ones and the highest separation factor of 7.80 was obtained at 70wt% water in the feed with the X_cr = 0.05 modified PVA membrane.     

我国煤制油技术的现状和发展

澄清替代燃料的概念,简述我国为什么要搞煤制柴油,详细说明煤制油发展历史,特别说明中国科学院在山西、内蒙2省区和伊泰潞安集团的支持下,经过几代科学家的艰苦努力取得的煤基间接合成油技术成果推向产业化,为国家能源安全做出重大贡献。叙述间接液化的技术关键和发展趋向,目前,国内的技术已经成熟,可以自行建设成套大型化的煤制柴油装置。     

Characterization of shale oil solids removed by the high-gradient magnetic separation technique

The high-gradient magnetic separation (HGMS) technique has been previously shown to remove solid particles successfully from several types of shale oil. The nature of the separated solids was investigated in this study, principally by thermomagnetic measurements over the temperature range 4.2–1173 K and in applied fields up to 1600 kA m^?1. Several phase transformations were identified in the magnetization profiles as a function of temperature. These transitions varied depending on the particular sample, although the low-temperature behaviour was qualitatively similar for all the solids. The magnetization increased over the range of external field studied. The magnetometric data reflect the differences in composition of the different solid samples and indicate the general occurrence of a paramagnetic phase mixed with a trace amount of ferromagnetic component. The bulk mineralogy and elemental composition of the solids were similar to those of the oil shales prior to retorting. Relatively large concentrations of iron sulphides were identified.     

Effect of transfer in the vapour phase on the extraction by pervaporation through organophilic membranes: experimental analysis on model solutions and theoretical extrapolation

Mass transfer in pervaporation is usually regarded as limited by the solution-diffusion step inside the dense selective polymer layer. In the case of pervaporation for the extraction of volatile organic compounds through organophilic membranes, especially at low feed temperature (about 300 K), the influence of the downstream pressure cannot be neglected. A contribution to the study of the operating parameters on the vapour side in a pilot plant — from the membrane to the condenser — to the overall mass transfer is presented.

A “convection-diffusion” model has been established to calculate the partial pressure gradients in the vapour phase up to the downstream face of the membrane. This equation has been combined with a relation for the mass transfer inside the membrane with a driving force expressed as a difference in fugacities.

The partial permeate pressures and the pervaporate fluxes obtained first with a pure compound (water) and secondly with binary mixtures (water-ethanol) pervaporated through membranes of polydimethylsiloxane (PDMS) on a pilot plant scale are well predicted by the model. Moreover, on the permeate side, the effects of unavoidable non-condensable gases, of the condenser temperature and of the distance between the module and the condenser on the flux and on the selectivity have been established for different total permeate pressures (300–3000 Pa). At high pressure, the pervaporation selectivity towards ethanol exhibits a minimum value as a function of the permeate circuit design.     

特殊油井结盐分析及防治

濮城油田部分低渗透、高矿化度复杂断块油藏油井结盐严重,影响油井正常生产。分析了油井结盐机理和结盐过程,通过应用抑盐剂防盐、热洗防盐、掺水除盐等配套工艺,减少了停井时间,避免了结盐卡泵,提高了清防盐效果,延长了检泵周期。     

Preparation of nanoclay incorporated PAN fibers by electrospinning technique and its application for oil and organic solvent absorption

In this work, polymer nanofibers (PAN/n-OMMT clay) were successfully produced by using an electrospinning process. The PAN/n-OMMT nanofibers were studied as an oil and solvent absorbent material due to their super hydrophobicity and super oleophilic properties. The generated composite nanofibers were found to have a very high oil and solvent absorption capacity in the case of 3% n-OMMT clay loading. It showed excellent absorption capacity up to 160 times its own weight for motor oil. The findings reported in this work might provide a fast and facile approach for the removal of oils and organic solvents on water surfaces.     

Heat transfer in layered media with application to oil shale materials

The problem of heat conduction in layered materials has been investigated. Equations for heat conduction developed earlier by Murakami et al. have been used to perform numerical studies for oil shale materials. The resulting solutions are compared to the solutions of the heat equation with effective thermal properties. The comparison yields limits on the validity of using effective medium values of thermal properties for time-dependent problems. The anisotropic nature of heat conduction in layered materials is also studied.     

Influence of operation parameters on the separation of mixtures by pervaporation and vapor permeation with inorganic membranes. Part 1: Dehydration of solvents

The separation performance of two different commercially available tubular inorganic membranes was studied for solvent dehydration. The separation layers consisted of A-type zeolite and microporous silica. The membrane characteristics were determined as function of operating conditions such as feed composition, temperature, and permeate pressure in pervaporation and vapor permeation. Among different membranes of the same batch, flux and selectivity were reproducible within 10%. The partial flux of water as the preferentially permeating component increases linearly with the water vapor pressure difference between feed and permeate and depends only marginally (viscosity influence) upon the properties of the organic component. The flux of the organic (retained) component is low and can best be described by assuming a substance and membrane specific permeance (flux over partial pressure difference) that is independent of composition. At very low water concentration in the feed one would expect a strong increase in permeability of the retained component through non-zeolite pores and larger silica pores as predicted by pure component measurements. However, this effect was not observed in mixtures within the concentration range studied here. A temperature rise improves flux rates exponentially while selectivity remains high. Thus, higher module cost in comparison to polymeric membranes can be compensated by reduced membrane area if a higher operating temperature can be chosen. Flux and selectivity decline as a function of permeate pressure with decreasing driving force. In vapor permeation with inorganic membranes superheating of the vaporous feed improves their performance while for polymeric materials a steep flux decline is observed. High flux and selectivity are obtained in the separation of water from alcohols. The normalized flux values of the A-type zeolite membrane are roughly 10 kg/m² h bar with a mixture selectivity of 2000 for methanol, 4000 for ethanol and 8000 for n-butanol. The average permeance of the amorphous silica membrane lies above 12 kg/m² h bar with mixture selectivity of 50 for methanol, 500 for ethanol and 2000 for n-butanol. The separation mechanism is mainly based on adsorption and diffusion enhanced by shape selectivity and size exclusion in some cases. The transport characteristics could be described with a simple transport model based on normalized permeate fluxes. With regard to the operation stability of the membranes, no deterioration of the performance was observed for the A-type zeolite in solvent dehydration or in separation of water from reaction mixtures. The silica membrane showed an initial conditioning effect involving a rearrangement of Si-OH groups with an increase in selectivity and decrease in flux of about 30%. After a few hours the performance stabilized and remained constant during further operation.     

Transesterification of soybean frying oil to biodiesel using heterogeneous catalysts

In the present work, the transesterification reaction of soybean frying oil with methanol, in the presence of different heterogeneous catalysts (Mg MCM-41, Mg-Al Hydrotalcite, and K⁺ impregnated zirconia), using low frequency ultrasonication (24 KHz) and mechanical stirring (600 rpm) for the production of biodiesel fuel was studied. Selection of catalysts was based on a combination of porosity and surface basicity. Their characterization was carried out using X-ray diffraction, Nitrogen adsorption-desorption porosimetry and scanning electron microscopy (SEM) with energy dispersive spectra (EDS). The activities of the catalysts were related to their basic strength. Mg-Al hydrotalcite showed particularly the highest activity (conversion 97%). It is important to mention that the catalyst activity of ZrO₂ in the transesterification reaction increased as the catalyst was enriched with more potassium cations becoming more basic. Use of ultrasonication significantly accelerated the transesterification reaction compared to the use of mechanical stirring (5 h versus 24 h).     

Detergency of Vegetable Oils and Semi‐Solid Fats Using Microemulsion Mixtures of Anionic Extended Surfactants: The HLD Concept and Cold Water Applications

In spite of the increasing interest in cold temperature detergency of vegetable oils and fats, very limited research has been published on this topic. Extended surfactants have recently been shown to produce very promising detergency with vegetable oils at ambient temperature. However, the excessive salinity requirement (4–14 %) for these surfactants has limited their use in practical applications. In this work, we investigated the mixture of a linear C₁₀–18PO–2EO–NaSO₄ extended surfactant and a hydrophobic twin‐tailed sodium dioctyl sulfosuccinate surfactant for cold temperature detergency of vegetable oils and semi‐solid fats. Four vegetable oils of varying melting points (from ?10 to 28 °C) were studied, these were canola, jojoba, coconut and palm kernel oils. Anionic surfactant mixtures showed synergism in detergency performance compared to single surfactant systems. At temperatures above the melting point, greater than 90 % detergency was achieved at 0.5 % NaCl. While detergency performance decreased at temperatures below the melting point, it was still superior to that of a commercial detergent (up to 80 vs. 40 %). Further, results show that the experimental microemulsion phase behaviors correlated very well with predictions from the hydrophilic–lipophilic deviation concept.     

Dynamic crude oil fouling prediction in industrial preheaters using optimized ANN based moving window technique

The objective of this paper is to develop and validate a reliable, efficient and robust artificial neural network (ANN) model for online monitoring and prediction of crude oil fouling behavior for industrial shell and tube heat exchangers. To explore the complex dynamics of fouling, a new modeling strategy based on moving-window neural network approach is proposed. The essential character of this modeling approach is online updating of the ANN model whenever a new data block is available, so that it can effectively capture the slowly changing of process dynamics. The results of these models have been compared with appropriate sets of experimental data. The mean relative errors (MRE) of training and prediction subsets were about 6.61% and 8.06%, respectively. Since the data extraction in the refinery was performed every 2 h, the modeling approach led to an MRE of about 8% for fouling rate prediction of the next 50 h.     

Kinetic modeling of the hydrotreatment of light cycle oil and heavy gas oil using the structural contributions approach

The kinetics of the hydrodesulfurization of light cycle oil (LCO) and heavy gas oil (HGO) over a CoMo/Al₂O₃ catalyst were investigated in a perfectly mixed flow reactor with stationary basket of the Robinson-Mahoney type at temperatures of 330, 310 and 290 °C, H₂/HC molar ratios of 2.8, 3.6 and 7.2 and a pressure of 65 bar. Hougen-Watson type rate equations were derived for the conversion of dibenzothiophene, substituted (di)benzothiophene and their products. To avoid having to deal with a huge number of model parameters, a methodology based upon structural contributions was applied. In the absence of own kinetic data on key components a number of kinetic and adsorption parameters were taken from published work on a very similar catalyst. For a given value of H₂/HC only a small number of experiments was required to determine the value of the very complex denominators DEN_σ and DEN_τ appearing in the rate equations for the hydrodesulfurization of LCO and of HGO and of their evolution with the conversion of the feedstock. With the rate equations constructed in this way the calculated total conversion of DBT, its conversion into biphenyl and into cyclohexylbenzene were in excellent agreement with the experimental values.