Azeotrope composition

If the light and heavy key components form an azeotrope, then something more sophisticated than simple distillation is required. The first option to consider when separating an azeotrope is exploiting change in azeotropic composition with pressure. If the composition of the azeotrope is sensitive to pressure and it is possible to operate the distillation over a range of pressures without any material decomposition occurring, then this property can be used to... 

The problem with using a pressure change is that the smaller the change in azeotropic composition, the larger is the recycle in Figs. 3.86 and 3.96. If the azeotrope is not sensitive to changes in pressure, then an extraneous material can be added to the distilla-... 

If an azeotropic mixture is to be separated by distillation, then use of pressure change to alter the azeotropic composition should be considered before use of an extraneous mass-separating agent. Avoiding the use of extraneous materials often can prevent environmental problems later in the design. 

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 ... 

Hydrazine forms a high (120.5°C) boiling azeotrope with water that has a composition of 58.5 mol % (71.48 wt %) N2H4 at 102.6 kPa (1.02 atm) pressure. This comphcates the separation of hydrazine from water in the manufacturing process because it necessitates the removal of a large amount of water in order to approach the azeotropic composition. 

The reactor effluent, containing 1—2% hydrazine, ammonia, sodium chloride, and water, is preheated and sent to the ammonia recovery system, which consists of two columns. In the first column, ammonia goes overhead under pressure and recycles to the anhydrous ammonia storage tank. In the second column, some water and final traces of ammonia are removed overhead. The bottoms from this column, consisting of water, sodium chloride, and hydrazine, are sent to an evaporating crystallizer where sodium chloride (and the slight excess of sodium hydroxide) is removed from the system as a soHd. Vapors from the crystallizer flow to the hydrate column where water is removed overhead. The bottom stream from this column is close to the hydrazine—water azeotrope composition. Standard materials of constmction may be used for handling chlorine, caustic, and sodium hypochlorite. For all surfaces in contact with hydrazine, however, the preferred material of constmction is 304 L stainless steel. 

Styrene Copolymers. Acrylonitrile, butadiene, a-methylstyrene, acryUc acid, and maleic anhydride have been copolymerized with styrene to yield commercially significant copolymers. Acrylonitrile copolymer with styrene (SAN), the largest-volume styrenic copolymer, is used in appHcations requiring increased strength and chemical resistance over PS. Most of these polymers have been prepared at the cross-over or azeotropic composition, which is ca 24 wt % acrylonitrile (see Acrylonithile polya rs Copolyp rs). 

Hquid—Hquid-phase spHt the compositions of these two feed streams He oa either side of the azeotrope. Therefore, column 1 produces pure A as a bottoms product and the azeotrope as distillate, whereas column 2 produces pure B as a bottoms product and the azeotrope as distillate. The two distillate streams are fed to the decanter along with the process feed to give an overall decanter composition partway between the azeotropic composition and the process feed composition according to the lever rule. This arrangement is weU suited to purifying water—hydrocarbon mixtures, such as a C —C q hydrocarbon, benzene, toluene, xylene, etc water—alcohol mixtures, such as butanol, pentanol, etc as weU as other immiscible systems. 

An azeotrope limits the separation that can be obtained between components by simple distillation. For the system described by cui ve B, the maximum overhead-product concentration that could be obtained from a feed with X = 0.25 is the azeotropic composition. Similarly, a feed with X = 0.9 could produce a bottom-product composition no lower than the azeotrope. 

Exploiting changes in azeotropic composition with total system pressure. 

This example clearly shows good distribution because of a negative deviation from Raonlt s lawin the extract layer. The activity coefficient of acetone is less than 1.0 in the chloroform layer. However, there is another problem because acetone and chloroform reach a maximum-boiling-point azeotrope composition and cannot be separated completely by distillation at atmospheric pressure. 

The phenomenon is illustrated for HF and HCl in Fig. 17.5. Conversely, when more concentrated aqueous solutions are boiled, the concentration of HX in the vapour is greater than that in the liquid phase which thereby becomes progressively diluted by distillation until the azeotropic mixture is again reached, whereupon distillation continues without change of composition and at constant temperature. The bps and azeotropic compositions at atmospheric pressure are listed below, together with the densities of the azeotropic acids at 25°C ... 

The existence of an azeotropic composition has some practical significance. By conducting a polymerization with the monomer feed ratio equal to the azeotropic composition, a high conversion batch copolymer can be prepared that has no compositional heterogeneity caused by drift in copolymer composition with conversion. Thus, the complex incremental addition protocols that arc otherwise required to achieve this end, are unnecessary. Composition equations and conditions for azeotropic compositions in ternary and quaternary eopolymerizations have also been defined.211,21... 

Cases have been reported where the application of the penultimate model provides a significantly better fit to experimental composition or monomer sequence distribution data. In these copolymerizations raab "bab and/or C BA rBBA- These include many copolymerizations of AN, 4 26 B,"7 MAH28" 5 and VC.30 In these cases, there is no doubt that the penultimate model (or some scheme other than the terminal model) is required. These systems arc said to show an explicit penultimate effect. In binary copolynierizations where the explicit penultimate model applies there may be between zero and three azeotropic compositions depending on the values of the reactivity ratios.31... 

Azeotropic compositions are rare for terpolymerization and Ham 14 has shown that it follows from the simplified eqs. 38-40 that ternary azeotropes should not exist. Nonetheless, a few systems for which a ternary azeotrope exists have now been described (this is perhaps a proof of the limitations of the simplified equations) and equations for predicting whether an azeotropic composition will exist for copolymerizations of three or more monomers have been formulated.20113 This work also shows that a ternary azeotrope can, in principle, exist even in circumstances where there is no azeotropic composition for any of the three possible binary copolymerizations of tire monomers involved. 

Numerical approaches for estimating reactivity ratios by solution of the integrated rate equation have been described.124 126 Potential difficulties associated with the application of these methods based on the integrated form of the Mayo-kewis equation have been discussed.124 127 One is that the expressions become undefined under certain conditions, for example, when rAo or rQA is close to unity or when the composition is close to the azeotropic composition. A further complication is that reactivity ratios may vary with conversion due to changes in the reaction medium. 

Equation (13.42) gives the condition that a copolymer azeotrope exists. The azeotropic composition is... 

The range shown is such that the products are on either side of the azeotropic composition of these two monomers. Furthermore, data were available for repeat runs of the same product so that reproducibility of the data can be ascertained. 

When the data for the X3 product were analyzed separately, the parameters estimated were significantly different in values from those for the other two products. Furthermore, the fit at higher conversion was as not as good as with the other products (E3,g3), This suggests that in the product with low levels of monomer A the phase equilibrium is different. It also indicates that the model may be limited to products containing concentrations less than the azeotropic composition. However, the model can still be applied as long as one recognizes that the model is semi-theoretical. 

Using copolymerization theory and well known phase equilibrium laws a mathematical model is reported for predicting conversions in an emulsion polymerization reactor. The model is demonstrated to accurately predict conversions from the head space vapor compositions during copolymerization reactions for two commercial products. However, it appears that for products with compositions lower than the azeotropic compositions the model becomes semi-empirical. 

Copolymerizations were performed at 70 C using an ampoule technique similar to that used for MMA. Monomers were purified by distillation. Most of the runs had an initial weight fraction styrene of 0.767 and 1.45 mole % AIBN initiator. Also utilized is one run using 0.235 wt. fraction styrene (0.350 mole % AIBN) and one at 0.557 (1.45 mole % AIBN). Gruber and Knell (10) used both the former compositions. The latter one is the calculated azeotropic composition using their values of the reactivity ratios. 

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