Separation of Diacteone Alcohol‐Water Mixtures by Membrane Pervaporation

Abstract

A study was conducted to evaluate membrane pervaporation for the separation of diacetone alcohol‐water mixtures using commercially available membranes for organic enrichment and dehydration. Empirical correlations for the effect of the process parameters of feed concentration, feed temperature, permeate‐side pressure, and scale‐up were developed. The solvent‐water mixture was successfully separated with a poly(vinyl alcohol) based Sulzer PERVAP 2210 dehydration membrane. Various dehydration membranes were evaluated and a comparison of the flux and separation factor was made. The membrane performance in separating acetone‐water mixtures was also studied. An overall model to predict the membrane area needed for a scale‐up was developed based on the results.     

Separation of Acetic Acid/Water Mixtures by Pervaporation through Poly(Vinyl Alcohol)–Sodium Alginate Blend Membranes

Abstract

Dense pervaporation (PV) membranes were prepared by blending hydrophilic polymers, poly(vinyl alcohol) (PVA), and sodium alginate (SA), which were then crosslinked with glutaraldehyde (GA) for the separation of acetic acid/water mixtures. These membranes (PVA‐SA) were characterized for morphology, intermolecular interactions, thermal stability, and physico‐mechanical properties using XRD, FTIR, TGA and tensile testing respectively. The effect of experimental parameters such as feed composition and permeate pressure on separation performance of the crosslinked membranes was determined. Sorption studies and porosity measurement were carried out to evaluate the extent of interaction and degree of swelling of the polyion membranes, in acetic acid and water as well as in mixtures of acetic acid and water. Further the results were compared with the commercial membrane (Sulzer pervap 2205). The membrane appears to have a good potential for dehydrating 90 wt% acetic acid with a reasonably high selectivity of 21.5 and a substantial water flux of 0.24 kg/m²/h/10 µm. Separation factor was found to improve with decreasing feed water concentration whereas the corresponding flux decreased. Higher permeate pressures caused a reduction in both flux and selectivity.     

Pervaporation of Methanol/Methyl‐t‐Butyl Ether Mixtures Through Poly(Vinyl Alcohol)/Poly(Acrylic Acid) Blend Membranes

Abstract

Membranes obtained by blending poly(vinyl alcohol) (PVOH) and poly(acrylic acid) (PAA) have been investigated for the separation of methanol and methyl‐t‐butyl ether (MTBE) liquid mixtures through a pervaporation process. Experiments were performed by contacting one side of a polymer dense film with the liquid mixture and removing the vapor on the other side with an inert gas flux, a setup for a process with sweeping gas. The blend membranes, with a COOH/OH ratio in the 0.5–2.5 range, are permeated by methanol preferentially. Higher values of flux and lower values of selectivity are observed when the methanol content in the feed increases. The ratio PAA/PVOH of the membrane influences both flux and selectivity in the same way. A maximum of both flux and selectivity is observed at a COOH/OH ratio of about 2. The swelling of membranes of different composition in the presence of different liquid composition explains the flux behavior in the pervaporation experiments. The observed membrane swelling has been explained on the basis of the solubility parameters of the components of the system.     

Development of Novel NH4Y Zeolite‐Filled Chitosan Membranes for the Dehydration of Water‐Isopropanol Mixture Using Pervaporation

Abstract

NH₄Y zeolite‐filled chitosan membranes were developed for the separation of water‐isopropanol mixture using pervaporation process. The NH₄Y zeolite‐filled chitosan membranes were prepared using a solution technique with the variation of NH₄Y zeolite loading (0, 0.1, 0.2, 0.3, 0.4, 0.5 wt.%). The membranes morphologies were studied using Scanning Electron Microscopy (SEM) and the membranes mechanical strength were tested using the parameter of tensile strength and percent strain at maximum. The effects of NH₄Y zeolite loading on the liquid sorption characteristics and pervaporation performance were also evaluated. The diffusion coefficient of water and isopropanol for the chitosan membranes at different NH₄Y zeolite loading is estimated. The presence of NH₄Y zeolite in the chitosan membranes caused non‐homogeneous dispersion of NH₄Y zeolite crystals and membrane swelling due to its hydrophilic properties. However, the presence of NH₄Y zeolite was able to improve both tensile strength and percent strain at maximum of chitosan membranes. The presence of NH₄Y zeolite also increased the total permeation flux and separation factor simultaneously. The Pervaporation Separation Index shows that 0.2 wt.% of NH₄Y zeolite‐filled membrane gave the optimum performance in the pervaporation process. The diffusion coefficient estimated proves that the membranes were highly water selective.     

Zeolite 4A-Incorporated Polymeric Membranes for Pervaporation Separation of Methanol–Methyl Acetate Mixtures

Zeolite 4A-incorporated poly(vinyl alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) membranes were prepared for pervaporation separation of methanol/methyl acetate mixtures. These membranes were characterized by Infrared spectroscopy, X-ray diffraction and Scanning electron microscopy. The results showed that crystallinity of the membrane decreased with the increase of zeolite 4A content. The effect of zeolite loading, feed composition and temperature on the membrane separation performance were discussed in detail. With the increase of zeolite 4A content, permeation flux increased continuously, but separation factor first increased and then decreased. The addition of 2.5 wt% zeolite 4A in the polymer membrane improved the separation factor from 12.9 (for PVA/PVP membrane) to the maximum value of 34.4 for 20 wt% methanol in feed at 45 °C. The separation factor decreased with increasing feed temperature, however, the flux increased with increasing feed temperature. Zeolite 4A-incorporated PVA/PVP membranes provide an effective method for the separation of methanol/methyl acetate azeotropic mixtures.     

Dehydration of 2‐Butanol by Pervaporation Through Blend Membranes of Chitosan and Hydroxy Ethyl Cellulose

Abstract

Blend membranes of chitosan (CS) and hydroxyethylcellulose (HEC) were synthesized and cross‐linked with glutaraldehyde for the separation of 2‐butanol/water mixtures. The blends were characterized by fourier transform infrared (FTIR) spectroscopy and wide‐angled X‐ray diffraction (WAXD) to assess the intermolecular interactions and occurrence of cross‐linking, respectively. The pervaporation performance was evaluated by varying experimental parameters such as feed composition, membrane thickness, and permeate pressure and found to be promising. Sorption studies were conducted to evaluate affinity and degree of swelling of both the unmodified and cross‐linked blend membranes in pure as well as binary mixtures of the two liquids. The blends were found to have good potential for breaking the aqueous azeotrope of 2‐butanol (77 wt.%). Upon cross‐linking, the blend membranes exhibited a substantial improvement in performance. Amongst the various blend combinations used for the dehydration studies, the membrane constituting 70 wt.% of CS and 30 wt.% HEC yielded a flux of 2.1 kg/m² · h · 10 µm and a selectivity of 554, which was optimum.     

Physical and Gas Transport Properties of Novel Hyperbranched Polyimide – Silica Hybrid Membranes

Summary Physical and gas transport properties of novel hyperbranched polyimide – silica hybrid membranes were investigated. Hyperbranched polyamic acid as a precursor was prepared by polycondensation of a triamine monomer, 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), and a dianhydride monomer, 4,4-(hexafluoro-isopropylidene)diphthalic anhydride (6FDA), and subsequently modified the end groups by 3-aminopropyltrimethoxysilane (APTrMOS). The hyperbranched polyimide – silica hybrid membranes were prepared using the polyamic acid, water, and tetramethoxysilane (TMOS) via a sol-gel technique. 5 % weight-loss temperature and glass transition temperature of the hyperbranched polyimide – silica hybrid membranes determined by TG-DTA measurement considerably increased with increasing silica content, indicating effective cross-linking at polymer – silica interface mediated by APTrMOS moiety. CO₂, O₂, and N₂ permeability coefficients of the hybrid membranes increased with increasing silica content. It was pointed out that the increased gas permeabilities are mainly attributed to increase in the gas solubilities. On the contrary, CH₄ permeability of the hybrid membranes decreased with increasing silica content because of decrease in the CH₄ diffusivity and, as a result, CO₂/CH₄ selectivity of the hybrid membranes remarkably increased. It was concluded that the 6FDA-TAPOB hyperbranched polyimide – silica hybrid membranes have high thermal stability and excellent gas selectivity, and are expected to apply to a high-performance gas separation membrane.     

Separation of Acetic Acid‐Water Mixtures through Poly(Vinyl Alcohol)/Poly(Acrylic Acid) Alloy Membranes by Using Evapomeation and Temperature Difference Evapomeation Methods

Abstract

Separation of acetic acid‐water mixtures by using evapomeation (EV) method were carried out over the full range of compositions at temperatures varying from 30 to 55°C using poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) (75/25) (v/v) alloy membranes. PVA/PAA membranes gave separation factors of 110–5711 and permeation rates of 2.3×10^?4–1.53×10^?1 kg/m²h, depending on the operation temperature and feed mixture composition. The temperature dependence of the permeation in EV was expressed by the Arrhenius type expression and the activation energy was calculated as 9.15 kcal/mol. More efficient EV technique, which is called temperature difference evapomeation method (TDEV) was also applied to PVA/PAA membranes to separate acetic acid‐water mixtures; high permeation rates (1.7×10^?3–3.0×10^?1 kg/m²h) and separation factors (1335–8924) were obtained for each of the studied feed compositions. Azeotropic mixture of acetic acid and water was also separated by TDEV method with a separation factor of 297 and permeation rate of 1.50×10^?1 kg/m²h.     

Adsorptive Separation of o‐/p‐Aminoacetophenones using Acidic Ion Exchange Resins

Abstract

Separation of o‐/p‐aminoacetophenones (o‐/p‐AAPs) is investigated by a two‐step process: selective solubilization in an organic solvent followed by reactive adsorption on functionalized polymers. Since, p‐AAP and o‐AAP show inter‐ and intra‐molecular hydrogen bonding, respectively, the former is solubilized to a much lesser extent than the latter in an organic solvent. For example, o‐AAP dissolves completely while p‐AAP shows only 1.8% saturation solubility in toluene. Selective solubilization of o‐AAP in toluene, therefore, gives pure p‐AAP as residual solid in high yields. In the subsequent adsorption step, a strongly acidic ion exchange resin removes selectively the trace amounts of p‐AAP from the toluene phase giving pure o‐AAP.     

Removal of Trace Concentrations of Heavy Metals Using Complexing Ion‐Exchange Resins

Abstract

Oak Ridge National Laboratory is examining potential new technologies for treating radiologically‐contaminated process wastewater. The current treatment facility is aging and is optimized to remove ⁹⁰Sr, but future wastewaters are likely to contain mostly activated metals, such as ⁵¹Cr and ⁶⁴Cu. Other low‐volume wastewaters may contain trace concentrations of Hg and U. Complexing ion‐exchange resins and other specialized sorbents were tested for removing trace concentrations of heavy metals. Short‐term column tests and batch loading tests were conducted using a surrogate wastewater and various sorbents. These tests showed that metal uptake was very rapid, and that good removal and relatively high loadings could be achieved from a very dilute wastewater surrogate. Forager M‐TU (Dynaphore, Inc.) showed the best overall results, removing 91.9% of the Cr, 99.3% of the Cu, >99.7% of the Hg, and >99.9% of the U with a contact time of 120 seconds in a short‐term column test.     

Separation of Gas Mixtures by the Absorption–Pervaporation Method

Absorption–pervaporation separation of gas mixtures is studied and compared with membrane gas separation. The absorption–pervaporation method ensures a much higher separation coefficient of the HCl–H₂mixture. An equation is derived for calculating the fluxes of the mixture components through the absorbent–membrane system.     

Ion‐Exchange Separation of Pu from Macro Concentration of Th in HNO3 Medium

Abstract

Sorption behavior of Th and Pu from anion‐ as well as cation‐exchange resin was investigated from nitric acid medium by both batch and column methods. The anion‐exchange studies involved anionic nitrate complexes of Pu⁴⁺ and Th⁴⁺ sorbed onto DOWEX 1x4 resin (50–100 mesh), and the cation‐exchange studies involved the sorption of Pu³⁺ and Th⁴⁺ onto BIORAD AG 50Wx8 (50–100 mesh) or DOWEX 50Wx4 (50–100 mesh) resin. The batch data gave a separation factor (K _d,Pu/K _d,Th) of 22 for the anion‐exchange method and 0.017 for the cation‐exchange method at 3 and 2 M HNO₃, respectively. A two‐stage ion‐exchange separation method was developed for the quantitative separation of Pu (8 g/L) from a macro amount of Th (200 g/L) in nitric acid medium. The first step involved the quantitative sorption of plutonium from the mixture while about 90% of Th could be washed in 6 column volumes. The plutonium, eluted (as Pu³⁺) using 0.5 M HNO₃ + 0.2 M hydrazinium nitrate (HN) + 0.2 M hydroxyl ammonium nitrate (HAN), and the residual (～10%) Th were subsequently loaded onto a cation‐exchange column in the second step. Greater than 99% Pu was recovered with 2 M HNO₃ (in ～8 column volumes) containing 0.2 M HN + 0.2 M HAN. The final elution of thorium from the cation‐exchange column was achieved in about 6 column volumes of 1 M α‐hydroxy isobutyric acid. A (Pu, Th)O₂ fuel scrap sample was dissolved in 16 M HNO₃ containing 0.005 M HF and was used subsequently as the feed for the anion‐exchange column. The eluted Pu was subsequently loaded onto a cation‐exchange column for final purification. The recovery of plutonium and thorium was found to be >99% and >98%, respectively, while the respective decontamination factors were estimated to be 215 and 292.     

Effect of Receiving Phase Anion on Macrocycle-Mediated Cation Transport Rates and Selectivities in Water—Toluene—Water Emulsion Membranes

Abstract

Relative transport rates of metal nitrates (Na⁺, K⁺, Rb⁺, Cs⁺, Ag⁺, T1⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, and Pb²⁺) were measured alone and in combination with either Pb²⁺, Ag⁺, or T1⁺ in a water-toluene-water emulsion membrane system. The toluene phase contained the surfactant Span 80 and the crown ether dicyclohexano-18-crown-6 (DC18C6). The aqueous receiving phase contained the lithium salt of one of the following anions: pyrophosphate, thiosulfate, hydroxide, chloride, formate, nitrate. In the case of the metal combinations, chloride and formate ions were not studied. Unless significant complexation occurred both between the transported cation and the anion in the receiving phase and between the cation and DC18C6 in the membrane phase, there was little or no transport of the cation from the source phase to the receiving phase. Selective removal of Pb²⁺ and of Ag⁺ from binary mixtures of these cations with each of the cations listed was demonstrated using the emulsion membrane.     

Permeation and Separation Characteristics of Acetic Acid‐Water Mixtures by Pervaporation through Acrylonitrile and Hydroxy Ethyl Methacrylate Grafted Poly(vinyl alcohol) Membrane

Abstract

In this study, acrylonitrile (AN) and hydroxyl ethyl methacrylate (HEMA) were grafted onto poly(vinyl alcohol) (PVA) using cerium (IV) ammonium nitrate as initiator at 30°C. The graft copolymer was characterized using the Fourier transform infrared spectroscopy (FTIR) and elemental analysis. The grafted PVA membranes (PVA‐g‐AN/HEMA) were prepared by a casting method, and used in the separation of acetic acid‐water mixtures by pervaporation. The effects of the membrane thickness, operating temperature, and feed composition on the permeation rate and separation factor for acetic acid‐water mixtures were studied. Depending on the membrane thickness, the temperature and feed composition PVA‐g‐AN/HEMA membranes gave separation factors 2.26–14.60 and permeation rates of 0.18–2.07 kg/m²h. It was also determined that grafted membranes gave lower permeation rates and greater separation factors than PVA membranes. Diffusion coefficients of acetic acid‐water mixtures were calculated from permeation rate values. The Arrhenius activation parameters were calculated for the 20 wt.% acetic acid content in the feed using the permeation rate and the diffusion data obtained at between 25–50°C.     

Recovery of 1,4‐Dimethyl Piperazine from Aqueous Solutions Using Polymeric Adsorbent and Ion‐Exchange Resins

Abstract

Strong and weakly acidic ion exchange resins and polymeric adsorbents are used for recovery of 1,4‐dimethyl piperazine (DMP) from aqueous solutions. Sorption of the amine in undissociated form is the primary mechanism of uptake of DMP on the ion‐exchange resins. Equilibrium adsorption data for DMP on the resins, at various temperatures, are fitted in Langmuir adsorption isotherm. Kinetic studies show that intraparticle diffusional resistance controls the sorption of DMP into the resin matrix. A mathematical model based on intraparticle diffusion and external mass transfer is used for simulating breakthrough profiles and compared with the experimental results for a fixed bed of weakly acidic Indion‐652 resin. The DMP loaded bed of the resin was effectively regenerated with methanol.     

Evaluation of Surface Acido‐Basic Properties of Inorganic‐Based Solids by Model Catalytic Alcohol Reaction Networks

The characterization of acido‐basic properties of the surface of inorganic solids is essential to understand the behavior of catalysts during heterogeneous catalyzed reactions. The use of alcohols as reactive probe molecules to investigate these properties has been developed since the 1970s, and in 1991, a new alcohol, 2‐methylbut‐3‐yn‐2‐ol (MBOH), was proposed. This review sums up the knowledge accumulated for 15 years on this model reaction network and compares its advantages with those of other alcohols. The operating conditions are reviewed, and deactivation phenomena are analyzed. Then, from investigations of correlations with other techniques able to reveal the acido‐basic properties of surfaces, it is concluded that MBOH appears to be the most valuable reactive probe molecule as the nature of the sites involved in the different routes of its network is unambiguous. The links that may exist between the rate of a model reaction and the thermodynamic acido‐basic properties of the surface are then discussed. It is shown that even when true kinetics parameters are available, they are not necessarily correlated to thermodynamic parameters. What can be expected from a model reaction network is to evaluate the reactivity of a surface along an acidic or a basic route. In basic sites, this reactivity may be related to the nucleophilicity of the surface or to the way the deprotonated intermediate is stabilized on the surface. It can be used to follow the modifications of a series of materials during synthesis and to identify the factors governing a reaction of practical interest.     

Absence of Donnan Exclusion at High‐Concentration Ion Exchange for Macroporous Anionic Resin

Abstract

High‐concentration ion exchange has been studied for an anionic macroporous resin. The mechanism of interaction of Lewatit MP‐500 (strong base resin) with several high‐concentration inorganic salts was analyzed in order to determine the effect of the Donnan potential in the process.

The systems under study were Cl^?, SO₄ ^2? as counter‐ions and K⁺, Na⁺ as co‐ions in different combinations as single electrolytes. These salts were chosen because of their interest as raw materials in the fertilizer industry. The study focuses mainly on the behavior of high‐concentration (over 1 M) counter‐ and co‐ions in the anionic resin. The results showed that Donnan exclusion does not take place completely and that electrolyte penetration inside the resin is observed. Furthermore, a certain amount of ion exchange was observed for the co‐ions (K⁺ and Na⁺) when the resin was presaturated with sulphate and chlorides that were present in the solution. Equilibrium and kinetics data were obtained under these special experimental conditions. Equilibrium constants were obtained for counter‐ions and adsorption constants for co‐ions using a constant separation factor isotherm, while diffusion coefficients were obtained using a pore diffusion model.     

High Throughput Determination and QSER Modeling of Displacer DC‐50 Values for Ion Exchange Systems

Abstract

In this paper, the displacer concentration required to displace 50% of proteins bound in batch adsorption systems, DC‐50, was employed as a means of ranking high‐affinity, low molecular weight displacers for ion‐exchange systems. A relatively large data set of cationic displacers with varying chemistries were evaluated with two proteins on two strong cation exchange resins in parallel batch screening experiments. Using this methodology, a significant number of high affinity displacers were identified that could displace both proteins at relatively low concentrations. In addition, the DC‐50 data was used in concert with molecular structural information of the displacers to produce predictive quantitative structure‐efficacy relationship (QSER) models based on a support vector machine (SVM) regression approach. The resulting models were well correlated and the predictive power of these models was demonstrated. Examination of the features selected in these models provided insight into the factors influencing displacer efficacy in cation exchange systems. These results demonstrate the utility of a combined DC‐50/QSER approach to identify and design high‐affinity displacers for ion‐exchange displacement chromatography.     

Efficient Separation of Cytosine‐Substituted Mildiomycin Analogue (MIL‐C) from the Fermentation Broth by Ion Exchange

Abstract

Cytosine‐substituted mildiomycin analogue (MIL‐C) was synthesized by supplementing cytosine into the culture medium of Streptoverticillium rimofaciens (one mildiomycin producer) and had a specific and strong inhibitory activity against powdery mildews. In order to facilitate the separation of MIL‐C from this fermentation broth, the cultivation conditions were optimized to increase MIL‐C productivity, and more than 0.9 g/l cytosine was added to the medium to inhibit the biosynthesis of mildiomycin (MIL). According to the ion‐exchange equilibrium and dynamics characteristic of MIL‐C, one weakly cationic resin (DK110) was screened out to separate MIL‐C from fermentation broth with one effective ion‐exchange method. When 2% ammonia aqueous solution was applied as eluent with 2 BVs/h, high recovery yield (97.6%) and purity (70.0%) of MIL‐C were achieved. This novel strategy of combining up‐stream biosynthetic controls and down‐stream purification is very promising for efficient production of this novel nucleoside antibiotic (MIL‐C).     

Some Characteristics of Pervaporation for Dilute Ethanol-Water Mixtures by Alcohol-Permselective Composite Membrane∗

Abstract

Zeolite-filled polydimethylsiloxane/polysulfone composite membranes were prepared and used to separate ethanol from dilute ethanol-water mixtures through a pervaporation process. During this process the relationship between flux (J) and temperature (T) is J = 597.95 exp(-E ₀/RT) (g/m²·h), E ₀ = 3.292 kJ/mol. The experimental results show that the flux decreases with increasing downstream pressure while the selectivity (α_EtOH/water) rises, the flux increases, and the selectivity decreases with a rise of feed concentration, and the flux as well as the selectivity increase with increasing bulk velocity on the upstream side of the membrane.