Alcohol-water-entrainer

Figure 8.18 Effect of entrainer/feed ratio on the concentration profiles in the RD column displaying in a ternary diagram alcohol-water-entrainer.

Ammonium lactate [34302-65-3] ia coaceatrated aqueous solutioas has beea coaverted to ammonia and the ester by alcoholysis at temperatures ranging from 100—200°C usiag a variety of alcohols and water entrainers, such as toluene. Ester yields ranging from 50—80% were obtained. This method has also been suggested as a recovery and purification method from impure solutions of lactate (29). However, a considerable amount of the lactate is not converted to the recoverable ester and is lost as lactamide (6). 

Azeotropic distillation involves either an embedded azeotrope, present in the feed mixture, or a contrived azeotrope, formed by the addition of an extraneous component called an entrainer. Benzene-water may be separated into high-purity benzene and the benzene-water azeotrope this is frequently practiced to remove water from benzene when very dry benzene is needed for chemical processing. More commonly encountered are distillation separations that are enhanced through the addition of an entrainer to form an azeotrope. Perhaps the best known separation of this type is the production of anhydrous ethanol from the ethanol-water azeotrope. Here, benzene is added as the entrainer, with the result that a low-boiling ternary azeotrope is formed between benzene, ethanol, and water. This permits the higher-boiling ethanol to be taken from the bottom of the column. The distillate condenses to a heterogeneous mixture of benzene and alcohol-water phases. 

Table 16.3 Partition coefificients (% w/w) between water and entrainer for ternary azeotropes of alcohol, water and entrainer (aU at 20/25°C except those marked)...

Tert. from sec. amines and alcohols Azeotropic water entrainment... 

Benzotriazole, allyl alcohol, mercuric acetate, and sulfuric acid monohydrate in benzene stirred and refluxed with azeotropic water-entrainment until water separation ceases after 5 hrs. —> N-allylbenzotriazole. Y 67%. F. e., with lower yields, s. H. Hopff and H. Liissi, Helv. 46, 1052 (1963). 

Dihydroresorcinol and ethyl N-phenylformimidate heated 1 hr. at 130° then 10 min. at 140-150° with continuous distillation of the resulting alcohol 2-(N-phenylformimidoyl) cyclohexane-1,3-dione (Y 85%) refluxed 1.5 hrs. with phenylhydrazine in ethanol 2-phenylhydrazonomethylcyclohexane-1,3-dione (Y 81%) refluxed 1 hr. with a little p-toluenesulfonic acid in benzene with azeotropic water entrainment 4-oxo-l-phenyl-4,5,6,7-tetrahydroindazole (Y 86%) (startg. m. f. 924). F. e. s. G. Lehmann, H. Wehlan, and G. Hilgetag, B. 100, 2967 (1967). 

Spreading velocities v are on the order of 15-30 cm/sec on water [39], and v for a homologous series tends to vary linearly with the equilibrium film pressure, it", although in the case of alcohols a minimum seemed to be required for v to be appreciable. Also, as illustrated in Fig. IV-3, substrate water is entrained to some depth (0.5 mm in the case of oleic acid), a compensating counterflow being present at greater depths [40]. Related to this is the observation that v tends to vary inversely with substrate viscosity [41-43]. An analysis of the stress-strain situation led to the equation... 

The reaction rate is increased by using an entraining agent such as hexane, benzene, toluene, or cyclohexane, depending on the reactant alcohol, to remove the water formed. The concentration of water in the reaction medium can be measured, either by means of the Kad-Eischer reagent, or automatically by specific conductance and used as a control of the rate. The specific electrical conductance of acetic acid containing small amounts of water is given in Table 6. 

Direct, acid catalyzed esterification of acryhc acid is the main route for the manufacture of higher alkyl esters. The most important higher alkyl acrylate is 2-ethyIhexyi acrylate prepared from the available 0x0 alcohol 2-ethyl-1-hexanol (see Alcohols, higher aliphatic). The most common catalysts are sulfuric or toluenesulfonic acid and sulfonic acid functional cation-exchange resins. Solvents are used as entraining agents for the removal of water of reaction. The product is washed with base to remove unreacted acryhc acid and catalyst and then purified by distillation. The esters are obtained in 80—90% yield and in exceUent purity. 

Figure 12.33 Separation of isopropyl alcohol (IPA) and water mixture using di-isopropyl ether (DIPE) as entrainer in heterogeneous azeotropic distillation.

Chemically, the preparation of a "stable" foam or emulsion requires the use of a surfactant to aid in dispersion of the internal phase and prevent the collapse of the foam (or emulsion) into separate bulk phases. The selection of a surfactant is made on the basis of severity of conditions to be encountered, the gas to be entrained (N2, C02, LPG, CH, or air), the continuous phase liquid (water, alcohol, or oil), and half-life of foam stability desired. 

Isomerization processes produce sour water and caustic wastewater. The ether manufacturing process utilizes a water wash to extract methanol or ethanol from the reactor effluent stream. After the alcohol is separated, this water is recycled back to the system and is not released. In those cases where chloride catalyst activation agents are added, a caustic wash is used to neutralize any entrained hydrogen chloride. This process generates a caustic wash water that must be treated before being released. This process also produces a calcium chloride neutralization sludge that must be disposed of off-site. 

The decomposition of the diazonium sulfate in the presence of alcohol may take place with considerable violence, and it is necessary to watch the reaction carefully so as to be able to check it, if necessary, by the external application of cold water. Acetaldehyde is rapidly evolved, and some will generally escape from the condenser. It is therefore advisable to lead the escaping gases through water, not only in order to avoid possibility of fire, but to retain any nitrotoluene which may be entrained. 

Azeotropic Distillation. The concept of azeotropic distillation is not new. The use of benzene to dehydrate ethyl alcohol and butyl acetate to dehydrate acetic acid has been in commercial operation for many years. However, it was only during World War II that entrainers other than steam were used by the petroleum industry. Two azeotropic processes for the segregation of toluene from refinery streams were developed and placed in operation. One used methyl ethyl ketone and water as the azeo-troping agent (81) the other employed methanol (1). 

Further improvement in the technology of methyl fatty ester synthesis can be achieved by dual esterification [4], This takes advantage of the fact that the sulfated zirconia catalyst has similar activity for normal alcohols, over the series C1-C8. However, methanol manifests about twice the activity [20], The removal of water produced by the esterification with methanol is solved simply, by employing a heavy alcohol immiscible with water, such as 2-ethyl-hexanol, which acts simultaneously as a reactant and an entrainer. As a result, the two fatty esters are obtained in the bottom product in the desired ratio by adjusting the feeds. For example, in a preferable operation mode the ratio of fresh feed reactants is acid methanol 2-ethyl-hexanol 1 0.8 0.2. 

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