Distillation entrainer

Removal of cationic impurities from water. Careful analysis of water purified by various methods (see Table 7.10) indicates that the water that is obtained by passing ordinary distilled water through a small monobed deionizer (contained in polyethylene) and a submicrometer filter is equal or superior (with respect to cations) to water obtained by distillation in conventional quartz stills, and is distinctly superior to the product from systems constructed of metal.70 From the data available in the literature, simple distillation clearly does not produce high-purity water. In practice, two effects cause contamination of the distillate. Entrainment is the major factor that prevents the perfect separation of a volatile substance from nonvolatile solids during distillation. Rising bubbles of vapor break through the surface of the liquid with considerable force and throw a fog of droplets (of colloidal dimensions) into the vapor space... 

Keywords Reactive Distillation, Entrainer, Modelling, Fatty Acids... 

The choice of a selective solvent is easier the more the components to be separated differ in their chemical structure. It would be difficult or impossible, for instance, to hnd a selective solvent for the separation of stereoisomers. Nevertheless, the restrictions on extractive distillation solvents are less severe than those on azeotropic distillation entrainers, because the solvent recovery problem is virtually nonexistent due to the wide gap between the boiling points of the solvent and the components to be separated. 

MAJOR USES Used in manufacture of solvents and thinners organic synthesis antiknock agent spectrophotometric analysis determination of octane numbers of fuels azeotropic distillation entrainer. 

A high value of Pi/Pe (where subscript E denotes entrainer) coupled with a low value of 7e (the activity coefficient of the extractive distillation entrainer in low concentration in component 1) is ideal for these purposes. 

Elaborate fractionation is not necessary. In the case of lubricating-oil distillation, entrainment may discolor the products and increase treating costs, and poorly fractionated wax distillate or cylinder stock may result in trouble with dewaxing. Some asphalt or feed preparation towers employ only one or two bubble plates in addition to a mist separator (Fig. 7-27). More detail on vacuum-tower construction is presented in Chap. 16. 

In the first class, azeotropic distillation, the extraneous mass-separating agent is relatively volatile and is known as an entrainer. This entrainer forms either a low-boiling binary azeotrope with one of the keys or, more often, a ternary azeotrope containing both keys. The latter kind of operation is feasible only if condensation of the overhead vapor results in two liquid phases, one of which contains the bulk of one of the key components and the other contains the bulk of the entrainer. A t3q)ical scheme is shown in Fig. 3.10. The mixture (A -I- B) is fed to the column, and relatively pure A is taken from the column bottoms. A ternary azeotrope distilled overhead is condensed and separated into two liquid layers in the decanter. One layer contains a mixture of A -I- entrainer which is returned as reflux. The other layer contains relatively pure B. If the B layer contains a significant amount of entrainer, then this layer may need to be fed to an additional column to separate and recycle the entrainer and produce pure B. 

Figure 3.10 A typical azeotropic distillation using an entrainer.

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. 

Anhydrous Acetic Acid. In the manufacture of acetic acid by direct oxidation of a petroleum-based feedstock, solvent extraction has been used to separate acetic acid [64-19-7] from the aqueous reaction Hquor containing significant quantities of formic and propionic acids. Isoamyl acetate [123-92-2] is used as solvent to extract nearly all the acetic acid, and some water, from the aqueous feed (236). The extract is then dehydrated by azeotropic distillation using isoamyl acetate as water entrainer (see DISTILLATION, AZEOTROPIC AND EXTRACTIVE). It is claimed that the extraction step in this process affords substantial savings in plant capital investment and operating cost (see Acetic acid and derivatives). A detailed description of various extraction processes is available (237). 

Temperature and Product Yields. Most oil shale retorting processes are carried out at ca 480°C to maximize liquid product yield. The effect of increasing retort temperature on product type from 480 to 870°C has been studied using an entrained bed retort (17). The oil yield decreased and the retort gas increased with increased retorting temperature the oil became more aromatic as temperature increased, and maximum yields of olefinic gases occurred at about 760°C. Effects of retorting temperatures on a distillate fraction (to 300°C) are given in Table 6. 

The principle of azeotropic distillation depends on the abiHty of a chemically dissimilar compound to cause one or both components of a mixture to boil at a temperature other than the one expected. Thus, the addition of a nonindigenous component forms an azeotropic mixture with one of the components of the mixture, thereby lowering the boiling point and faciHtating separation by distillation. The separation of components of similar volatiHty may become economical if an entrainer can be found that effectively changes the relative volatiHty. It is also desirable that the entrainer be reasonably cheap, stable, nontoxic, and readily recoverable from the components. In practice, it is probably the ready recoverabiHty that limits the appHcation of extractive and azeotropic distillation. 

The majority of successful processes are those in which the entrainer and one of the components separate into two Hquid phases on cooling if direct recovery by distillation is not feasible. A further restriction in the selection of an azeotropic entrainer is that the boiling point of the entrainer is 10—40°C below that of the components. 

Sasol Fischer-Tropsch Process. 1-Propanol is one of the products from Sasol s Fischer-Tropsch process (7). Coal (qv) is gasified ia Lurgi reactors to produce synthesis gas (H2/CO). After separation from gas Hquids and purification, the synthesis gas is fed iato the Sasol Synthol plant where it is entrained with a powdered iron-based catalyst within the fluid-bed reactors. The exothermic Fischer-Tropsch reaction produces a mixture of hydrocarbons (qv) and oxygenates. The condensation products from the process consist of hydrocarbon Hquids and an aqueous stream that contains a mixture of ketones (qv) and alcohols. The ketones and alcohols are recovered and most of the alcohols are used for the blending of high octane gasoline. Some of the alcohol streams are further purified by distillation to yield pure 1-propanol and ethanol ia a multiunit plant, which has a total capacity of 25,000-30,000 t/yr (see Coal conversion processes, gasification). 

The fatty acids that emerge from the top of the column contain entrained water, partially hydroly2ed fat, and the Zn—soap catalyst. This product stream is passed into a vacuum dryer stage where the water is removed through vapori2ation and the fatty acid cooled as a result of this vapori2ation process. The dried product stream is then passed to a distillation system. 

An excess of crotonaldehyde or aUphatic, ahcyhc, and aromatic hydrocarbons and their derivatives is used as a solvent to produce compounds of molecular weights of 1000—5000 (25—28). After removal of unreacted components and solvent, the adduct referred to as polyester is decomposed in acidic media or by pyrolysis (29—36). Proper operation of acidic decomposition can give high yields of pure /n j ,/n7 j -2,4-hexadienoic acid, whereas the pyrolysis gives a mixture of isomers that must be converted to the pure trans,trans form. The thermal decomposition is carried out in the presence of alkaU or amine catalysts. A simultaneous codistillation of the sorbic acid as it forms and the component used as the solvent can simplify the process scheme. The catalyst remains in the reaction batch. Suitable solvents and entraining agents include most inert Hquids that bod at 200—300°C, eg, aUphatic hydrocarbons. When the polyester is spHt thermally at 170—180°C and the sorbic acid is distilled direcdy with the solvent, production and purification can be combined in a single step. The solvent can be reused after removal of the sorbic acid (34). The isomeric mixture can be converted to the thermodynamically more stable trans,trans form in the presence of iodine, alkaU, or sulfuric or hydrochloric acid (37,38). 

There are two serious problems associated with continuous tar distillation. Coal tar contains two types of components highly corrosive to ferrous metals. The ammonium salts, mainly ammonium chloride, associated with the entrained Hquor remain in the tar after dehydration, tend to dissociate with the production of hydrochloric acid and cause rapid deterioration of any part of the plant in which these vapors and steam are present above 240°C. Condensers on the dehydration column and fractionation columns are also attacked. This form of corrosion is controlled by the addition of alkaU (10% sodium carbonate solution or 40% caustic soda) to the cmde tar in an amount equivalent to the fixed ammonia content. 

The generated water vapor rises through a screen (demister) placed to remove entrained saline water droplets. Rising further, it then condenses on the condenser tube bank, and internal heat recovery is achieved by transferring its heat of condensation to the seawater feed that is thus being preheated. This internal heat recovery is another of the primary advantages of the MSF process. The energy performance of distillation plants is often evaluated by the performance ratio, PR, typically defined as... 

The second Hquefaction process is carried out at temperatures from 261 to 296 K, with Hquefaction pressures of about 1600—2400 kPa (16—24 atm). The compressed gas is precooled to 277 to 300 K, water and entrained oil are separated, and the gas is then dehydrated ia an activated alumina, bauxite, or siHca gel drier, and flows to a refrigerant-cooled condenser (see Drying agents). The Hquid is then distilled ia a stripper column to remove noncombustible impurities. Liquid carbon dioxide is stored and transported at ambient temperature ia cylinders containing up to 22.7 kg. Larger quantities are stored ia refrigerated iasulated tanks maintained at 255 K and 2070 kPa (20 atm), and transported ia iasulated tank tmcks and tank rail cars. 

In the example, the minimum reflux ratio and minimum number of theoretical plates decreased 14- to 33-fold, respectively, when the relative volatiHty increased from 1.1 to 4. Other distillation systems would have different specific reflux ratios and numbers of theoretical plates, but the trend would be the same. As the relative volatiHty approaches unity, distillation separations rapidly become more cosdy in terms of both capital and operating costs. The relative volatiHty can sometimes be improved through the use of an extraneous solvent that modifies the VLE. Binary azeotropic systems are impossible to separate into pure components in a single column, but the azeotrope can often be broken by an extraneous entrainer (see Distillation, A7EOTROPTC AND EXTRACTIVE). 

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. 

Fig. 18. Separation of ethanol from an ethanol—water—benzene mixture using benzene as the entrainer. (a) Schematic representation of the azeo-column (b) material balance lines where I denotes the homogeneous and the heterogeneous azeotropes D, the end points of the Hquid tie-line and A, the overhead vapor leaving the top of the column. The distillate regions, I, II, and III, and the boundaries are marked. Other terms are defined in text.

Fig. 19. Separation of ethanol and water from an ethanol—water—benzene mixture. Bottoms and are water, B is ethanol, (a) Kubierschky three-column sequence where columns 1, 2, and 3 represent the preconcentration, azeotropic, and entrainer recovery columns, respectively, (b) Material balance lines from the azeotropic and the entrainer recovery columns, A and E, respectively, where represents the overall vapor composition from the azeo-column, 2 1SP Hquid in equiUbrium with overhead vapor composition from the azeo-column, Xj, distillate composition from entrainer...

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