Alcohol recovery with pervaporation: Effect of high 2‐butanol concentration

Poly dimethyl siloxane (PDMS) membrane was used to separate a synthetic mixture consisting of isopropanol, ethanol, 2‐butanol, and n‐butanol using the pervaporation separation technique. These alcohols are found to occur in naphtha reformate as a result of vapor‐phase reaction of the alkenes in the presence of water and a catalyst. In this work the pervaporation separation efficiency of PDMS membrane toward different alcohols was evaluated by estimation of fluxes and separation factors at different temperatures and pressures. The coupling effect resulting from the presence of identical functional groups was investigated. The activation energies for the transport of each of these alcohols through the membrane were also evaluated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3164–3171, 2001     

Simulation of Multicomponent Distillation Using a Nonequilibrium Stage Model

Abstract

A nonequilibrium stage model is used to predict composition profiles for binary and multicomponent distillation in a column of spheres and cylinders with a known interfacial area. The profiles generated by the model are compared with experimental data for the binary systems methanol—isopropanol, methanol—water, and isopropanol—water, and for the ternary systems methanol—isopropanol—water and acetone—n—hexane—cyclohexane. The model predicts with a high accuracy the experimental data with an average deviation lower than 1 mol%.     

A comparative study of a fluidised bed reactor and a gas lift loop reactor for the ibe process: Part III. Reactor performances and scale Up

Continuous fermentations using Clostridium spp. DSM 2152 immobilised in calcium alginate beads to produce butanol and isopropanol from glucose were carried out in a fluidised bed reactor with liquid recycle (FBR, 10.9 dm³ working volume, 41 % solids) and in a gas lift loop reactor (GLR, 11.4 dm³ working volume, 32% solids). In the FBR in-situ produced non-coalescing gas bubbles had a negligible influence on the fluidisation pattern and the steady state results of the fermentation were in accordance with those predicted by a reactor model. The FBR was operated reliably for 5 weeks without decrease of activity. The GLR behaved as a three phase reactor because of the recycled fermentation gas. The steady state fermentation results were as predicted by the GLR model. Scale up to a 50 m³ FBR and a 65 m³ GLR led to development of a plug flow with recycle model for the FBR and a stirred tank model for the GLR. On the basis of overall reactor performance and ease of integration with a simultaneous product recovery the FBR is preferred to the GLR for application in a large scale butanol/isopropanol process using immobilised Clostridia spp.     

Application of lipase immobilized on nylon‐6 for the synthesis of butyl acetate by transesterification reaction in n‐heptane

A purified alkaline thermotolerant bacterial lipase from Bacillus coagulans BTS‐3 was immobilized on nylon‐6 matrix activated by glutaraldehyde. The matrix showed ～ 70% binding efficiency for lipase. The bound lipase was used to perform transesterification in n‐heptane. The reaction studied was conversion of vinyl acetate and butanol to butyl acetate and vinyl alcohol. Synthesis of butyl acetate was used as a parameter to study the transesterification reaction. The immobilized enzyme achieved ～ 75% conversion of vinyl acetate and butanol (100 mmol/L each) into butyl acetate in n‐heptane at 55°C in 12 h. When alkane of C‐chain lower or higher than n‐heptane was used as an organic solvent, the conversion of vinyl acetate and butanol to butyl acetate decreased. During the repetitive transesterification under optimal conditions, the nylon bound lipase produced 77.6 mmol/L of butyl acetate after third cycle of reuse. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Dissolution of coal with NaOH-alcohol: Effect of alcohol species

Methanol, ethanol, straight-chain propanol, isopropanol, straight-chain butanol, sec-butanol, tert-butanol, straight-chain pentanol, and iso-pentanol were used for the reaction of coal with NaOH-alcohol at 290 °C for 1 h. All the products dissolved in pyridine with an extraction yield > 80 wt%. Straight-chain alcohols are less reactive than the secondary alcohols owing to the differences in hydrogen donating ability.     

Conversion of carbohydrates into 5‐hydroxymethylfurfural in a green reaction system of CO2‐water‐isopropanol

In this work, a green reaction system of CO₂‐water‐isopropanol was developed for 5‐hydroxymethylfurfural (HMF) production. The conversion of fructose in a CO₂‐water system was first investigated, and the results showed this system could promote the formation of HMF compared to a pure water system. Then, isopropanol was introduced into the CO₂‐water system and the HMF formation became better because the solvent effect of isopropanol increased the tautomeric composition of fructofuranose, which was easy to form HMF. The existence of isopropanol was found to greatly suppress secondary reactions where HMF was converted to levulinic acid and insoluble humin. Meanwhile, the effects of reaction parameters on the conversion of fructose to HMF in the CO₂‐water‐isopropanol system were analyzed, and a high HMF yield of 67.14% was obtained. Finally, to further illustrate the merits of CO₂‐water‐isopropanol system, productions of HMF from other carbohydrates were tested and satisfactory yields were achieved. © 2016 American Institute of Chemical Engineers AIChE J, 63: 257–265, 2017     

A Study of the Separation of 1-Dodecene and 1-Tetradecene Hydroformylation Products in Aqueous Medium

Abstract

Experimental results of the solubilization of olefins in hydroformylation model systems, comprising 1-dodecene and 1-tridecanal or 1-tetradecene and 1-pentadecanal, water, butanol, sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and/or tri(m-sulfofenyl)phosphine trisodium salt (TPPTS-Na) are presented. The selected systems were used for the hydroformylation of 1-dodecene and 1-tetradecene whereby high yields of aldehydes were obtained. After the reaction, the mixture spontaneously separated into an organic phase with the reaction products and an aqueous phase comprising the catalyst and excess phosphine ligand.     

Reaction Kinetics of Steam Reforming of n‐Butanol over a Ni/Hydrotalcite Catalyst

Pyrolytic lignin can be transformed to liquid transportation fuels by hydrotreatment, which requires hydrogen (H₂). Bio‐oil is a suitable renewable feedstock for H₂ production. Here, n‐butanol was chosen as a model compound representing alcohols in the bio‐oil aqueous fraction. H₂ production from steam reforming of n‐butanol was investigated in a fixed‐bed reactor using a commercial Ni/hydrotalcite catalyst. A plausible reaction pathway in the presence of Ni was discussed. An increase in reforming temperature, space time, and steam/carbon ratio in the feed enhanced the n‐butanol conversion and H₂ yield. Reaction kinetics was studied in the defined chemical control regime. The reaction order with respect to n‐butanol (one) and the activation energy were determined.     

Phase Separation of Lactan Gum from Fermentation Broths by Addition of Water-Miscible Organic Solvents

Abstract

A microbial polysaccharide (lactan gum) produced by bacterium ATCC 55046 was precipitated from fermentation broths by the addition of ethanol, acetone, isopropanol, or tert-butanol. Compositions of the precipitate and supernatant phases were determined as a function of organic solvent concentration and used to construct binodal solubility curves. Lactan did not precipitate at bulk-mixture organic solvent concentrations below 35% (wt) ethanol, 35% acetone, 33% isopropanol, or 25% tert-butanol. At organic solvent concentrations just exceeding the solubility transition point, the precipitates were soft, moist, and sponge-like in texture, with low lactan concentrations. At higher organic solvent concentrations the precipitates were compact and dense. The maximum lactan concentration in the precipitate was 25–37%, depending on the organic solvent type and concentration. Increasing the organic solvent concentration beyond 50% for ethanol, or 70% for acetone, decreased the lactan concentration in the precipitate. No such decrease occurred for isopropanol and tert-butanol. Thus, organic solvent usage, from greatest to least, was in the order ethanol, acetone, isopropanol, and tert-butanol, but the maximum lactan concentration in the precipitate, from greatest to least, was in the order acetone, isopropanol, ethanol, and tert-butanol.     

Dehydration of Isopropanol by Pervaporation Using Aromatic Polyetherimide Membranes

Abstract

Aromatic polyetherimide membranes were prepared by the phase inversion method and tested for the pervaporation separation of water from isopropanol with emphasis on the breaking of azeotropic composition and the dehydration of high concentrations of isopropanol. It was found that the membrane selectivity was enhanced by partial evaporation of the solvent in the cast polymer films prior to the gelation step during membrane formation. The membrane performance was shown to be dependent on the feed concentration and the operating temperature. At a feed temperature of 25°C and a permeate pressure of 133 Pa, separation factors of 173 and 384 were achieved for the dehydration of isopropanol solutions at 0.68 (azeotropic composition) and 0.96 mole fractions isopropanol, respectively, with reasonably high permeation rates. The utility of the membranes for the proposed separation was demonstrated; however, these membranes were not prepared under optimized conditions and thus a continuous study is required to rationalize the effects of membrane preparation parameters on membrane performance.     

Study on the Synthesis of n‐Butyl Acetate by Catalytic Rectification

With Hβ zeolite as the catalyst and θ rings as the fillings, the technological process of synthesizing n‐butyl acetate with acetic acid and n‐butanol in a Φ 30 mm and 2 m tall catalytic rectifying column was studied. The influence of factors such as catalyst loading height, material feed site, reflux ratio and feed rate on the esterification reaction and the rectification effect was investigated. The study results suggested that the appropriate conditions of n‐butyl acetate synthesis by catalytic rectification include: The height ratio of the rectifying section, the reaction section and the stripping section is 1:1:1; acetic acid and n‐butanol are fed in upside and downside of the reaction section, respectively; the reflux ratio is 2.5; the liquid hourly space velocity of n‐butanol is 0.64 h^–1. Under these conditions, the mass fraction of n‐butyl acetate in the column bottom is 98.64 %, and the total yield of n‐butyl acetate is 91.5 %.     

电极的浸涂工艺

实验采用浸涂法来制作电极，分别比较了以正丁醇－异丙醇和水作溶剂的钌钛涂层以及以正丁醇－异丙醇作溶剂折钌钛锡和钌锡涂层的浸涂法和刷涂法制得电极的表面形貌和电性能的差异。并对以正丁醇－异丙醇和水作溶剂的钌钛涂层进行了浸涂次数与电极性能关系的比较实验。根据实验结果可知，浸涂法可以提高电极涂层的均匀怀，并能适当延长电极的寿命，特别是将浸涂法和梯度法结合起来的涂制方法对延长电极的寿命更有利。     

Acquisition of Water Solubility Diagrams in Ternary Systems (AOT/Organic Solvent/Alcohol) and Extraction of α-Lactalbumin Using Reverse Micellar Systems

In this study water solubility curves were constructed and calorimetric measurements obtained for reverse micellar systems consisting of an alcohol (isopropanol or butanol), surfactant (AOT) and organic solvent (isooctane or hexane). Also evaluated were the effects of alcohol and solvent type and surfactant concentration on the extraction of the α-lactalbumin (α–la). From the obtained solubility diagrams for ternary systems, it was concluded that isooctane presented the highest water solubility capacity in the center of the micelle systems with hexane, since isooctane has greater molecular volume and greater effect of the surfactant aggregation number. With respect to the alcohols, it was observed that isopropanol and butanol act in the system as a co-surfactant, since they prefer to adsorb at the water/solvent interface. It was also verified that butanol improved water solubility inside the reverse micellar due to its contribution to increase the critical packing parameter. The amount of α-la extracted increased proportionally with the AOT concentration for systems with isooctane and hexane. However, for systems with the latter solvent, the concentration of extracted protein first increases and then decreases. The extraction power of reverse micellar systems with isooctane was influenced by the type of alcohol with butanol showing better results. For systems containing hexane there was no effect of the alcohol added to the system on extraction power of α-lactalbumin.     

Synthesis of imine bond containing insoluble polymeric ligand and its transition metal complexes,structural characterization and catalytic activity on esterification reaction

In this study, synthesis of insoluble polymeric ligand (L) and its transition metal complexes [Cu(L)Cl₂]·2H₂O (1), [Co(L)Cl₂(H₂O)₂] (2) and [Ni(L)Cl₂(H₂O)₂] (3), having the azomethine groups, were synthesized by the condensation reactions of the diamines and dialdehydes. The structural properties were characterized by the analytical and spectroscopic methods using by elemental analysis, Fourier Transform Infrared, Thermo Gravimetric Analysis, Powder X-ray Diffraction, magnetic susceptibility and Inductively Coupled Plasma. The solubilities of the synthesized polymeric materials were also investigated and found as insoluble some organic and inorganic solvents. Additionally, their catalytic performance was carried out for the esterification reaction of acetic acid and butyl acetate. The highest conversion rate is 75.75% by using catalyst 1. The esterification of butanol gave butyl acetate with 100% selectivity.     

Application of metal triflate catalysts for the trans-esterification of Jatropha curcas L. oil with methanol and higher alcohols

This paper describes an experimental study on the application of metal triflate salts for the (trans‐) esterification of fatty esters (triolein, methyl oleate, methyl linoleate), fatty acid (oleic acid), as well as Jatropha curcas L. oil with methanol and higher alcohols (ethanol, n‐propanol, iso‐propanol, iso‐butanol, tert‐butanol). The effect of the metal type (scandium, bismuth, aluminium, lanthanum, copper, zinc) and process conditions on reaction performance were evaluated. Highest conversions were obtained with Al(OTf)₃. Reaction of triolein with methanol gave 99 mol% conversion at 165 °C for 1 h and the main product was the methyl ester. In addition, partial methoxylation of the carbon–carbon double bonds in the fatty acid chains was observed, though their fraction in the mixture was less than 20 mol%. The trans‐esterification reaction was also successfully performed using higher alcohols, giving >95 % conversions for ethanol, n‐propanol, iso‐propanol and iso‐butanol, whereas tert‐butanol was not reactive. For the reaction of oleic acid with methanol, quantitative esterification, partial methoxylation of the carbon–carbon double bonds and the formation of small amounts of a lactone was observed. The methodology using Al(OTf)₃ was successfully performed on the trans‐esterification reaction of JO (FFA content of 2.1 wt%) with various alcohols. Key properties (viscosity, pour point and cloud points) of the (branched) Jatropha esters were determined. The best cold‐flow properties were obtained for the iso‐propyl esters of JO, with cloud point and pour point of ?3 and ?24 °C, respectively.     

Kinetics of hydrogen peroxide oxidation of alkyl dimethyl amines

We measured the absolute rate constants for the hydrogen peroxide oxidation of two different octyl dimethyl amines in isopropanol/water mixtures at 23°C. The amines were 1-octyl dimethyl amine (1) and 2-ethylhexyl dimethyl amine (2); their structures were analogous to those most often encountered in commercial alkyl dimethyl amine oxide production. The observed first-order rate constants for the disappearance of amine across a range of H₂O₂ concentrations (0.5–8 M) indicated that the overall rate was first-order in amine and 3/2-order in H₂O₂. Calculations showed k ₁=0.16 M⁻¹h⁻¹, k ₂=0.046 M⁻¹h⁻¹, and k ₁/k ₂=3.5. The rates appeared to decrease with increasing steric hindrance around the nitrogen atom. We also investigated the effect of water on the reaction rates. When [H₂O]<∼4.5 M in isopropanol, the rates increased with increasing [H₂O]; for [H₂O]>∼4.5 M, the rates were insensitive to [H₂O].     

Hydride Transfer: A Dominating Reaction of Ozone with Tertiary Butanol and Formate Ion in Aqueous Solution

This article provides evidences that hydride transfer is an important primary step in ozone reactions of formate and tertiary butanol in aqueous media. In both systems, one argument is the fact that the free hydroxyl radical yields are relative low ((40 ± 4)% and (7 ± 0.8)% for formate and tertiary butanol, respectively). Another hint is the high exergonicity of these reactions: ΔG = –249 kJ mol^?1 for formate/ozone system and ΔG = –114 kJ mol^?1 for hydride transfer followed by a methyl shift in the reaction between tertiary butanol and ozone. In addition, the main product of tertiary butanol ozonolysis is butan-2-one [(89 ± 3)%], a compound that is formed only via hydride transfer. For the reaction of ozone with formate an activation energy of (54.6 ± 1.2) kJ mol^?1 and a pre-exponential term of (2.5 ± 1.2) × 10¹¹ were determined (in the presence of tertiary butanol as ^?OH scavenger) whereas for tertiary butanol the two activation parameters were (68.7 ± 1.9) kJ mol^?1 and (2.0 ± 1.5) × 10⁹, respectively.     

Some Parametric Studies on Separation of Palladium from Perchloric Acid Medium by Radiolytic Reduction

Abstract

The radiolytic reduction of palladium ions to palladium metal in perchloric acid solutions has been studied with the aim of separating palladium from aqueous acidic waste. Fraction of Pd separated out as precipitate has been studied as a function of initial Pd concentration and strength of HClO₄. Addition of t‐butanol to the system has been found to cause substantial enhancement in the amount of Pd precipitated as compared to that in its absence. At a given absorbed dose, the extent of Pd separated is found to increase with the concentration of HClO₄ in presence of t‐butanol. However, the converse is true for the radiolysis in absence of t‐butanol. The decrease in the extent of reduction of Pd(II) to Pd(0) has been found to be due to increasing formation of chloride ions that tend to form reduction resistant cholorocomplexes of Pd. This is supported by the red‐shifting in the absorption bands of Pd(ClO₄)₂ observed for the spectra of gamma radiolysed solutions of Pd(II) at higher HClO₄ concentrations. External addition of chloride ions to aqueous Pd(II)/HClO₄ system even in presence of t‐butanol has been found to cause substantial inhibition to the radiolytic reduction of Pd(II) owing to formation of reduction‐resistant complexes. Correspondingly, the addition of nitrate ions to Pd(II)/HClO₄/t‐butanol system showed inhibition effect at much greater stoichiometric amount of nitrate.     

Preparation and characterization of PVA membrane modified by water‐soluble hyperbranched polyester (WHBP) for the dehydration of n‐butanol

Water‐soluble hyperbranched polyester (WHBP) was synthesized through the esterification reaction of the fourth generation hyperbranched polyester and maleic anhydride. A novel cross‐linked WHBP/PVA membrane was prepared by adding WHBP into poly(vinyl alcohol) (PVA) solution with glutaraldehyde as the cross‐linker. WHBP was characterized by Nuclear Magnetic Resonance and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR‐FTIR), while WHBP/PVA membranes were characterized by ATR‐FTIR, X‐ray Diffraction, Scanning Electron Microscopy, Thermogravimetric Analysis, mechanical capacity, and water contact angle. Testing results showed that maleic anhydride was grafted on the surface of WHBP; compared with PVA membrane, WHBP/PVA membrane had lower crystallinity, weaker mechanical strength, higher hydrophilicity, and better thermal stability. Sorption and diffusion behaviors of n‐butanol and water in WHBP/PVA membrane were investigated; pervaporation performances of WHBP/PVA membrane were studied through the dehydration of the 90 wt % n‐butanol aqueous solution at 40°C. With an increase of the WHBP content from 0 to 30 wt %, both n‐butanol uptake and n‐butanol diffusion coefficient first decreased then increased; n‐butanol flux first decreased from 10 to 2 g·m^?2·h^?1 then increased to 213 g·m^?2·h^?1; both sorption selectivity and diffusion selectivity first increased then decreased; separation factor first increased from 88 to 1309 then decreased to 16. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43533.     

Teflon AF2400/Ultem composite hollow fiber membranes for alcohol dehydration by high‐temperature vapor permeation

High‐temperature vapor permeation has a stringent requirement of membrane stability under harsh feed environments. This work reports the design of Teflon AF2400/Ultem composite hollow fiber (HF) membranes for alcohol dehydration via vapor permeation. Fabrication parameters such as Teflon concentration and coating time were systematically investigated. Interestingly, the fabricated composite HF membranes possess an unusual surface with honeycomb‐like microstructure patterns. Owing to the Teflon protective layer, the newly developed composite HF shows a promising and stable separation performance with a flux of 4265 gm^?2 h^?1 and a separation factor of 383 for 95% isopropanol dehydration at 125°C. The composite HF also performs well under extreme vapor feed compositions from 87 to 99 wt % isopropanol. In addition, it exhibits impressive separation performance for the dehydration of ethanol and n‐butanol. This work may provide useful insights of designing thermal‐stable and high‐performance composite polymeric membranes for vapor permeation. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1747–1757, 2016