Solutions azeotrope

Pervaporation is a membrane separation process where the liquid feed mixture is in contact with the membrane in the upstream under atmospheric pressure and permeate is removed from the downstream as vapor by vacuum or a swept inert gas. Most of the research efforts of the pervaporation have concentrated on the separation of alcohol-water system [1-20] but the separation of acetic acid-water mixtures has received relatively little attention [21-34]. Acetic acid is an important basic chemical in the industry ranking among the top 20 organic intermediates. Because of the small differences in the volatility s of water and acetic acid in dilute aqueous solutions, azeotropic distillation is used instead of normal binary distillation so that the process is an energy intensive process. From this point of view, the pervaporation separation of acetic acid-water mixtures can be one of the alternate processes for saving energy. 

The alcohol forms a constant-boiling mixture with water (hat contains 91% v/v of 2-propanol. Isopropyl alcohol is used primarily us a disinfectant for the skin and for surgical instruments. The alcohol is rapidly baciericitlal in the concentration range of 50 to 95%. A 407p eoneentration is considered equal in antiseptic efficacy to a 60% ethanol in water solution. Azeotropic isopropyl alcohol, USP, is u.scd on gauze pads for sterilization of the skin prior to hypodermic injections. Isopropyl alcohol is also used in pharmaceuticals and toiletries us a. solvent and preservative. 

Solute Azeotrope Solute y Reference Partition coefficient ... 

The toluene-phenylacetone solution should be distilled through a Claisen adapter packed with some pieces of broken glass to effect fractionation. Tbe first of the toluene should be distilled at normal pressure to remove water from solution azeotropically. The b.p. of the azeotrope is 85 °C, while water-free toluene boils at 110 °C. 

Now the mixture should be distilled. The toluene should be mostly distilled at atmospheric pressure to dry the solution azeotropically. When most of the toluene has distilled off, vacuum distillation may be commenced. An oil bath is preferred to heat the flask, as direct heat generally causes bumping with this substance. A vacuum, which distills safrole at about 110°C, will distill bromosafrole at about 140-145°C. Some chlorosafrole will come over at about 125°C. The Yield is about 66-75% conversion to bromosafrole, with the remainder being unconverted safrole, and some chlorosafrole. It smells like phenylacetone, and may turn pink on standing. It s recommended to store it in the freezer. 

Solute Azeotrope Solubility of solute in X (ppm) Solute H atom/ mole fraction UCST (°C)... 

Consideration of these characteristics makes it clear that only very special liquid pairs could conceivably form ideal solutions. It would be necessary that the molecules of the constituents be very similar in every respect, for example in structure, size, and chemical nature. Thus, solutions of optical isomers, adjacent members of an homologous series, and similar mixtures would be expected to be nearly ideal, but actually all solutions can at best only approach ideality as a limit. Solutions which form immiscible liquid phases are of necessity extremely nonideal, and extraction operations depend upon this. The extent to which solutions depart from ideality is manifested by deviations of the properties of the solutions from the characteristics listed above, and a study of these deviations will permit us to some extent to predict their behavior in extraction operations. The most useful characteristics of the ideal solution for these purposes is that of vapor pressure, since considerable information has now been accumulated for many mixtures on this and related properties such as boiling points of solutions, azeotropism, and vapor-liquid equilibria. Classifications of compounds according to the effect of intermolecular forces on properties of mixtures also provide much useful material, but the second and third characteristics in the list above are of limited value owing to lack of experimental data to which we can refer. 

FIGURE 3.4 Evaporation of a mixture of acetone and cyclohexane at 25°C. If a mixture of acetone-cyclohexane (50 50) is allowed to evaporate, the vapour that comes off will have a composition of = 69 31, i.e. acetone will evaporate preferentially. This progressively changes the composition of the mixture until, at 74% acetone, the vapour that comes off is also 74% acetone. This constant evaporation mixture will then evaporate until dry. Similarly if one starts with a mixture of acetone-cyclohexane (90 10), the v our that comes off will have a composition of = 83 17, i.e. cyclohexane will evaporate preferentially until the azeotropic composition of 74% acetone is reached. The change of solubility parameters of the solvent will affect the stability, viscosity, etc. of a polymer solution. Azeotropes are usually described as constant boiUng mixtures, but their behaviour at room temperature is more important for conservators. There are fewer published details of the mixtures at room temperature. The effect of the dissolved polymer on the relative evaporation rates has yet to be elucidated. 

At z in the curve, however (the minimum of vapour pressure), the solution and vapour are in equilibrium and the liquid at this point will distil without any change in composition. The mixture at z is said to be azeotropic or a constant boiling mixture. The composition of the azeotropic mixture does vary with pressure. 

The product of this reaction can be removed as an azeotrope (84.1% amide, 15.9% acetic acid) which boils at 170.8—170.9°C. Acid present in the azeotrope can be removed by the addition of soHd caustic soda [1310-73-2] followed by distillation (2). The reaction can also take place in a solution having a DMAC-acetic acid ratio higher than the azeotropic composition, so that an azeotrope does not form. For this purpose, dimethylamine is added in excess of the stoichiometric proportion (3). If a substantial excess of dimethylamine reacts with acetic acid under conditions of elevated temperature and pressure, a reduced amount of azeotrope is formed. Optimum temperatures are between 250—325°C, and pressures in excess of 6200 kPa (900 psi) are requited (4). DMAC can also be made by the reaction of acetic anhydride [108-24-7] and dimethylamine ... 

Ideal Adsorbed Solution Theory. Perhaps the most successful approach to the prediction of multicomponent equiUbria from single-component isotherm data is ideal adsorbed solution theory (14). In essence, the theory is based on the assumption that the adsorbed phase is thermodynamically ideal in the sense that the equiUbrium pressure for each component is simply the product of its mole fraction in the adsorbed phase and the equihbrium pressure for the pure component at the same spreadingpressure. The theoretical basis for this assumption and the details of the calculations required to predict the mixture isotherm are given in standard texts on adsorption (7) as well as in the original paper (14). Whereas the theory has been shown to work well for several systems, notably for mixtures of hydrocarbons on carbon adsorbents, there are a number of systems which do not obey this model. Azeotrope formation and selectivity reversal, which are observed quite commonly in real systems, ate not consistent with an ideal adsorbed... 

Pervaporation is a relatively new process with elements in common with reverse osmosis and gas separation. In pervaporation, a liquid mixture contacts one side of a membrane, and the permeate is removed as a vapor from the other. Currendy, the only industrial application of pervaporation is the dehydration of organic solvents, in particular, the dehydration of 90—95% ethanol solutions, a difficult separation problem because an ethanol—water azeotrope forms at 95% ethanol. However, pervaporation processes are also being developed for the removal of dissolved organics from water and the separation of organic solvent mixtures. These applications are likely to become commercial after the year 2000. 

In typical processes, the gaseous effluent from the second-stage oxidation is cooled and fed to an absorber to isolate the MAA as a 20—40% aqueous solution. The MAA may then be concentrated by extraction into a suitable organic solvent such as butyl acetate, toluene, or dibutyl ketone. Azeotropic dehydration and solvent recovery, followed by fractional distillation, is used to obtain the pure product. Water, solvent, and low boiling by-products are removed in a first-stage column. The column bottoms are then fed to a second column where MAA is taken overhead. Esterification to MMA or other esters is readily achieved using acid catalysis. 

Novolak Resins. In a conventional novolak process, molten phenol is placed into the reactor, foHowed by a precise amount of acid catalyst. The formaldehyde solution is added at a temperature near 90°C and a formaldehyde-to-phenol molar ratio of 0.75 1 to 0.85 1. For safety reasons, slow continuous or stepwise addition of formaldehyde is preferred over adding the entire charge at once. Reaction enthalpy has been reported to be above 80 kj /mol (19 kcal/mol) (29,30). The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent such as toluene. Toluene and xylene are used for azeotropic distillation. FoHowing decantation, the toluene or xylene is returned to the reactor. 

Cyclohexylamine is miscible with water, with which it forms an azeotrope (55.8% H2O) at 96.4°C, making it especially suitable for low pressure steam systems in which it acts as a protective film-former in addition to being a neutralizing amine. Nearly two-thirds of 1989 U.S. production of 5000 —6000 t/yr cyclohexylamine serviced this appHcation (69). Carbon dioxide corrosion is inhibited by deposition of nonwettable film on metal (70). In high pressure systems CHA is chemically more stable than morpholine [110-91-8] (71). A primary amine, CHA does not directiy generate nitrosamine upon nitrite exposure as does morpholine. CHA is used for corrosion inhibitor radiator alcohol solutions, also in paper- and metal-coating industries for moisture and oxidation protection. 

Deviations from Raonlt s law in solution behavior have been attributed to many charac teristics such as molecular size and shape, but the strongest deviations appear to be due to hydrogen bonding and electron donor-acceptor interac tions. Robbins [Chem. Eng. Prog., 76(10), 58 (1980)] presented a table of these interactions. Table 15-4, that provides a qualitative guide to solvent selection for hqnid-hqnid extraction, extractive distillation, azeotropic distillation, or even solvent crystallization. The ac tivity coefficient in the liquid phase is common to all these separation processes. 

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