Azeotropic mixture Batch processes

The first successful appHcation of heterogeneous azeotropic distillation was in 1902 (87) and involved using benzene to produce absolute alcohol from a binary mixture of ethanol and water. This batch process was patented in 1903 (88) and later converted to a continuous process (89). Good reviews of the early development and widespread appHcation of continuous azeotropic distillation in the prewar chemical industry are available (90). 

If components of a mixture form a heteroazeotrope or by the addition of an entrainer (E) a heteroazeotrope can be formed, the azeotropic composition can be crossed by decantation. In the pharmaceutical and fine chemical industries batch processes including the batch heteroazeotropic distillation (BHD) are widely applied. As far as we know the BHD was exclusively applied in the industry in batch rectifiers (equipped with a decanter) in open operation mode (with continuous top product withdrawal). The batch rectifier (BR) was investigated with variable decanter holdup by Rodriguez-Donis et al. (2002) and with continuous entrainer feeding by Modla et al. (2001, 2003) and Rodriguez-Donis et al. (2003), respectively. Recently the BHD was extensively studied for the BR and multivessel columns by Skouras et al. (2005a,b). 

In the solvent process, polycondensation is carried out in the presence of a hydrocarbon solvent (usually xylene), which is immiscible in water and is capable of forming an azeotropic mixture. Solvent is commonly used in amounts from 3-10% of the batch. The solvent method is generally used in the preparation of short oil polyester resin. 

Even though the simple distillation process has no practical use as a method for separating mixtures, simple distillation residue curve maps have extremely usehil appHcations. These maps can be used to test the consistency of experimental azeotropic data (16,17,19) to predict the order and content of the cuts in batch distillation (20—22) and, in continuous distillation, to determine whether a given mixture is separable by distillation, identify feasible entrainers/solvents, predict the attainable product compositions, quaHtatively predict the composition profile shape, and synthesize the corresponding distillation sequences (16,23—30). By identifying the limited separations achievable by distillation, residue curve maps are also usehil in synthesizing separation sequences combining distillation with other methods. 

Process synthesis and design of these non-conventional distillation processes proceed in two steps. The first step—process synthesis—is the selection of one or more candidate entrainers along with the computation of thermodynamic properties like residue curve maps that help assess many column features such as the adequate column configuration and the corresponding product cuts sequence. The second step—process design—involves the search for optimal values of batch distillation parameters such as the entrainer amount, reflux ratio, boiler duty and number of stages. The complexity of the second step depends on the solutions obtained at the previous level, because efficiency in azeotropic and extractive distillation is largely determined by the mixture thermodynamic properties that are closely linked to the nature of the entrainer. Hence, we have established a complete set of rules for the selection of feasible entrainers for the separation of non ideal mixtures... 

The ratio of cycHc to linear oligomers, as well as the chain length of the linear siloxanes, is controlled by the conditions of hydrolysis, such as the ratio of chlorosilane to water, temperature, contact time, and solvents (60,61). Commercially, hydrolysis of dimethjidichlorosilane is performed by either batch or a continuous process (62). In the typical industrial operation, the dimethyldichlorosilane is mixed with 22% azeotropic aqueous hydrochloric acid in a continuous reactor. The mixture of hydrolysate and 32% concentrated acid is separated in a decanter. After separation, the anhydrous hydrogen chloride is converted to methyl chloride, which is then reused in the direct process. The hydrolysate is washed for removal of residual acid, neutralized, dried, and filtered (63). The typical yield of cycHc oligomers is between 35 and 50%. The mixture of cycHc oHgomers consists mainly of tetramer and pentamer. Only a small amount of cycHc trimer is formed. 

The ability to separate a mixture of two liquid phases is critical to the successful operatiou of mauy chemical aud petrochemical processes. Besides its obvious importauce to liquid-liquid extractiou aud washing operations, liquid-liquid phase separation can be a critical factor in other operations including two-liquid-phase reaction, azeotropic distillation, and industrial wastewater treatment. Sometimes the required phase separation can be accomplished within the main process equipment, such as in using an extraction column or a batch-wise, stirred-tank reactor but in many cases a stand-alone separator is used. These include many types of gravity decanters, filter-type coalescers, coalescers filled with granular media, centrifuges, and hydrocyclones. 

Distillation is a method of separation based on the difference in composition between a liquid mixture and the vapor formed from it. The composition difference is due to differing effective vapor pressures, or volatilities, of the components of the liquid. When such a difference does not exist, as at an azeotropic point, separation by distillation is not possible. The most elementaiy form of the method is simpledistillation in which the liquid mixture is brought to boiling and the vapor formed is separated and condensed to form a product if the process is continuous, it is called flash distillation or an equilibrium flash, and if the feed mixture is available as an isolated batch of maleiial. the process is a form of batch distillation and the compositions of the collected vapor and residua] liquid are thus time dependent. 

Most monomers have different reactivity ratios, which lead to production of copolymers that do not have the same composition of the monomer mixture. In batch copolymerization, the copolymer produced at the beginning of the process is richer in the most reactive monomer, while the copolymer becomes richer in the less reactive monomer at the end of the batch. This composition drift causes the production of heterogeneous polymer mixtures, which may be deleterious for the performance of the polymer material. With the exception of the azeotropic reactions, most copolymerization systems experience composition drifts during batch copolymerizations, which must be corrected if homogeneous copolymer materials are to be produced. For this reason, copolymerizations are usually performed in semibatch (with manipulation of monomer feed flow rates) or continuous mode. 

The reaction requires an initial heat-up. Typical heat-up rates are 70 - 90 °C per hour initially followed by a phase where water distillation starts and further heats up at rates of around 15 - 25 °C per hour. Heating is continued until a predetermined batch temperature above 200 °C is reached. The equilibrium is shifted to the right by reaction water removal. For this purpose, the reactor is equipped with a distillation column (for the purpose of separating glycols and reaction water), a condenser and a receiver to collect the reaction water. Water removal is facilitated by applying nitrogen as the inert gas or a vacuum. Alternatively, an azeotropic distillation process may be applied. A solvent is used for water removal, e.g. xylene. In a separator, the xylene-water mixture is separated, the xylene is recirculated back into the reactor and the reaction water is collected in the receiver. 

Batch distiUalion is commonly used in the fine chemicals industries, speeialty polymer, bioehemieal, pharmaceutieal, and food. In these types of applications, the production scale is usually small, whieh justifies rumiing the separation process in batch mode. When the mixture contains an azeotrope, the separation methods mentioned in previous chapters can also be operated in batch mode. We will start this chapter by studying the operation of batch extractive distillation for two systems. One is to separate acetone and methanol using water as the entrainer. The other system is to separate IPA and water using DMSO as the entrainer. 

A mixture of ester is obtained, and the ratio of monoester to diester is controlled by ratios of the compounds charged to the reactor. Excess polyoxyethylene is used to maximize monoester production (5), and excess fatty acid is used to maximize diester formation (6). Because of the existing equilibrium, it is important that water be removed with an azeotroping agent such as toluene, xylene, etc., and/or by use of an inert-gas sparge to carry off water as it is formed to force the equilibrium toward the desired product. Catalysts such as sulfuric acid (7), benzene sulfonic acid, and other aromatic sulfonic acids (5, 8, 9), as well as cationic ion-exchange resins such as polystyrene-sulfonic acids (5, 9), are used. The latter compounds have the advantage of easy removal from batch reactions and of use in a fixed bed for continuous processes. Metals such as tin, iron, and zinc, as well as their salts in powdered form, have been used as catalysts (10,11). Catalysts can improve the yield of monoester. Of course, use of a monohydroxyl-functional polyoxyethylene, such as that from methanol-started ethylene oxide polymers (methoxy-polyoxyethylene), can be esterified with fatty acids to yield effectively all monoester. 

---