Separation of aromatics

Table 7. Separation of Aromatics from Nonaromatics in Light Cycle Oil...

The rotating-disk contactor (RDC), developed in the Netherlands (158) in 1951, uses the shearing action of a rapidly rotating disk to interdisperse the phases (Eig. 15b). These contactors have been used widely throughout the world, particularly in the petrochemical industry for furfural [98-01-1] and SO2 extraction, propane deasphalting, sulfolane [126-33-0] extraction for separation of aromatics, and caprolactam (qv) [105-60-2] purification. Columns up to 4.27 m in diameter are in service. An extensive study (159) has provided an excellent theoretical framework for scale-up. A design manual has also been compiled (160). Detailed descriptions and design criteria for the RDC may also be found (161). 

TURBINE fuels), are both in demand. Solvent extraction is also extensively used to meet the growing demand for the high purity aromatics such as ben2ene, toluene, and xylene (BTX) as feedstocks for the petrochemical industry (see BTX PROCESSING FEEDSTOCKS,PETROCHEMICALS). Additionally, the separation of aromatics from aUphatics is one of the largest appHcations of solvent extraction (see Petroleum, refinery processes survey). 

Separation of Aromatic and Aliphatic Hydrocarbons. Aromatics extraction for aromatics production, treatment of jet fuel kerosene, and enrichment of gasoline fractions is one of the most important appHcations of solvent extraction. The various commercial processes are summarized in Table 4. 

New stationary phases for specific purposes in chromatographic separation are being continually proposed. Charge transfer adsorption chromatography makes use of a stationary phase which contains immobilised aromatic compounds and permits the separation of aromatic compounds by virtue of the ability to form charge transfer complexes (sometimes coloured) with the stationary phase. The separation is caused by the differences in stability of these complexes (Porath and Dahlgren-Caldwell J Chromatogr 133 180 1977). 

The interactions between solute and the pha.ses are exactly the same as those present in LC separations, namely, dispersive, polar and ionic interactions. At one extreme, the plate coating might be silica gel, which would offer predominately polar and induced polar interactions with the solute and, con.sequently, the separation order would follow that of the solute polarity. To confine the polar selectivity to the stationai y phase, the mobile phase might be -hexane which would offer only dispersive interactions to the solute. The separation of aromatic hydrocarbons by induced polar selectivity could be achieved, for example, with such a system. 

Suitable organic solvents, such as ether, benzene, naphtha and the like, are more soluble than in water. This makes it possible to separate them from other substances which may accompany them in the water solution but which are not soluble in the solvents employed. Hence, one application of solvent extraction is the analytical determination of unsaponifiable oils and waxes in admixture with fatty material by submitting the mixture to vigorous saponification with alcoholic potash or, if necessary, sodium ethylate, and to dilute the product with water and extract with petroleum ether. The soaps remain in the aqueous solution while the unsaponifiable oils and waxes dissolved in the ether. The addition of a salt to an aqueous solution prior to extraction is sometimes practiced in some processes. In older processes, SOj is employed in the separation of aromatic and highly saturated hydrocarbons, taking advantage of the much greater solubility of the solubility of the aromatics and... 

Certain highly porous solid materials selectively adsorb certain molecules. Examples are silica gel for separation of aromatics from other hydrocarbons, and activated charcoal for removing liquid components from gases. Adsorption is analogous to absorption, but the principles are different. Layers of adsorbed material, only a few molecules thick, are formed on the extensive interior area of the adsorbent - possibly as large as 50,000 sq. ft./lb of material. 

Chiralcel OB is associated with the separation of aromatic and nonaromatic sulfoxides and Chiralcel OD with aromatic alcohols. 

Waksmundzka-Hajnos, M., Chromatographic separation of aromatic amino acids, /. Chromatogr. B, 717, 93, 1998. 

Replacement of the hydrophilic acrylamide by the more hydrophobic N-iso-propylacrylamide, in combination with the pre-functionalization of the capillary with (3-methacryloyloxypropyl) trimethoxysilane, afforded a monolithic gel covalently attached to the capillary wall. A substantial improvement in the separations of aromatic ketones and steroids was observed using these fritless hydrogel columns, as seen by the column efficiencies of 160,000 found for hydrocortisone and testosterone [92]. The separations exhibited many of the attributes typical of reversed-phase chromatography and led to the conclusion that, in contrast to the original polyacrylamide-based gels, size-exclusion mechanism was no longer the primary mechanism of separation. 

Horvath et al. sintered the contents of a capillary column packed with 6 pm oc-tadecylsilica by heating to 360 °C in the presence of a sodium bicarbonate solution [101]. These conditions also strip the alkyl ligands from the silica support, thus significantly deteriorating the chromatographic properties. However, the performance was partly recovered after resilanization of the monolithic material with dimethyloctadecylchlorosilane allowing the separation of aromatic hydrocarbons and protected aminoacids with an efficiency of up to 160,000 plates/m. 

Fig. 3.107. Comparison of micro-HPLC separations of aromatic sulphonic acids in different mobile phases (a) 0.005 M tetrabutylammonium hydrogensulphate (TBAS) in 15 per cent (v/v) methanol in water (1) Laurent acid, (2) amino-F-acid, (3) Cleve-1,6- and Peri acids, (4) unidentified impurity, (5) Cleve-1,7-acid and (6) unidentified impurity, (b) 0.005 M tetrabutylammonium hydrogensulphate (TBAS) in 15 per cent (v/v) methanol in water with 0.01 M /Lcyclodextrin (CD) (1) Laurent acid, (2) amino-F-acid, (3) Cleve-1,6-acid, (4) Peri acids, (5) unidentified impurity, (6) Cleve-1,7-acid and (7) unidentified impurity. Column, Biosphere Si C18, 162 X 0.32 mm i.d. flow rate 5 pl/min, column temperature ambient, detection, UV, 220-230 nm. Reprinted with permission from P. Jandera et al. [164].

Important applications of liquid-liquid extraction include the separation of aromatics from kerosene-based fuel oils to improve their burning qualities and the separation of aromatics from paraffin and naphthenic compounds to improve the temperature-viscosity characteristics of lubricating oils. It may also be used to obtain, for example, relatively... 

Polymers and resins Water purification, including removal of phenol, chlorophenols, ketones, alcohols, aromatics, aniline, indene, polynuclear aromatics, nitro- and chlor-aromatics, PCB, pesticides, antibiotics, detergents, emulsifiers, wetting agents, kraftmill effluents, dyestuffs recovery and purification of steroids, amino acids and polypeptides separation of fatty adds from water and toluene separation of aromatics from ahphatics separation of hydroquinone from monomers recovery of proteins and enzymes removal of colours from symps ... 

Collier et al. (10) demonstrated that HPLC was an effective technique for the separation of aromatic hydrocarbon metabolites in exposed marine organisms. Radioactive bioconversion products were studied in liver and gall bladder of coho salmon dosed with H-naphthalene. Quantitative identifications of glucuronide, sulphate, dihydrodiol, glycoside, and 1-naphthol derivatives were obtained. Three additional polar compounds of unknown structure were found. A typical HPLC profile is shown in Figure 2. 

Figure 2.2 Separation of aromatic compounds using isocratic elution. Conditions column, 5 pm Cis-bonded silica gel, 15 cm x 4.6 mm i.d. eluent, 0.001 M phosphoric acid in 55% aqueous acetonitrile flow rate, 1ml min-1 temperature, ambient, detection, UV 254 nm. Peaks 1, phenol, 2, 4-methylphenol 3, 2,4-dimethylphenol 4, 2,3,5-trimethylphenol 5, benzene, 6, toluene, 1, ethylbenzene, 8, propylbenzene and 9, butylbenzene.

Separation of aromatic and nonaromatic fractions from high-boiling oils (ASTM D2549)... 

Dolezalova, M. and Tkaczykova, M., HPLC enantioselective separation of aromatic amino and hydrazino acids on a teicoplanin stationary phase and the enantiomeric purity determination of L-isomers used as drugs. Chirality, 11, 394, 1999. 

Narang AS, Choudhury DR, Richards A. 1982. Separation of aromatic amines by thin-layer and high-performance liquid chromatography. J Chromatogr Sci 20 235-237. 

The development of different processes and solvents for the separation of aromatics from aliphatics has reached a rather stable state. A number of different processes, some of them with capacities of several hundred thousand tons of aromatics per year, are in operation. The more important ones are listed in Table 10.1. 

Table 10.1 Different Processes for Separation of Aromatics from Aliphatics... 

The separation of aromatic hydrocarbons (benzene, toluene, ethyl benzene, and xylenes) from mefhane to n-decane aliphatic hydrocarbon mixtures is challenging since the boiling points of fhese hydrocarbons are in a close... 

Similar good results of the separation of aromatic and aliphatic hydrocarbons were recently obtained with ethyl(2-hydroxyethyl)dimethylammonium Ws(trifluoromethylsulfonyl)imide, [(Cj)2C2HOC2N][Tf2N], at 298.15 K [160]. The separation of m-xylene from n-octane by extraction with [(Ci)2C2HOC2N] [TfjN] was observed with the distribution ration of 0.3 and selectivities of range 22-31. The other ammonium salt as [(Ci)2C4HOC2N][Bp4] or 1,3-dihexyl-oxymethyl-imidazolium tetrafluoroborate was not so successful in this separation [161]. 

Arce, A. et al.. Separation of aromatic hydrocarbons from alkanes using the ionic liquid l-ethyl-3-methylimidazolium bis (trifluoromethyl)sulfonyl amide. Green Ghem., 9, 70, 2007. 

Domarfska, U., Pobudkowska, A., and Krolikowski, M., Separation of aromatic hydrocarbons from alkanes using ammonium ionic liquid C2NTf2 at T = 298.15 K, Fluid Phase Equilib., 259,173,2007. 

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