Aromatic Hydrocarbon Separation

Solv useful to separate aromatic hydrocarbons from their mixts)... 

Analytical Properties Has been used to separate aromatic hydrocarbons, heterocyclic compounds, phenols, and aryl amines using methanol/water/phosphate buffer extent of adsorption affects retention times also used as a mobile phase modifier to provide a dynamically modified silica Reference 51-57... 

The ability to bind the additional amount of aromatic hydrocarbons is also characteristic of complexes with other binary acid systems, for example, of the complexes A HF BFj. This property of ternary complexes can be used to separate aromatic hydrocarbons from saturated ones and to separate aromatic hydrocarbons differing in their basicity (for the use of complexes with HCl and AlCl, see > with HF and BF3 see ° )- References recording the formation of the ternary complexes A HY mMY and of their solvates for hydrocarbons of the benzene series are listed in Table 1. 

Sherwood, P. (1965) Separating aromatic hydrocarbons by clathration. British Chemical Engineering, 10, 382-385. 

Nitromethane can be used in an extractive process to separate aromatic hydrocarbons from aliphatic hydrocarbons due to the lower solubility of the aliphatic fractions in nitromethane [3]. Nitroparaffins are used to separate lactic acid from fermentation beers [4], nitrocellulose from the nitrating solution [5], and plutonium (IV) from aqueous solutions [6]. Nitropropane is used to extract rosin from pine lumber at elevated temperatures [7]. Toluene can be separated from similar boiling-point aliphatic paraffins by azeotropic distillation with nitromethane [8]. Ethylbenzene forms an azeotrope with nitromethane which allows its separation from styrene through a distillation process. 

Sulfolane, another highly polar solvent, is used to separate aromatic hydrocarbons from aliphatic hydrocarbons [10]. The extraction process first developed by Shell Oil in 1959 and which is referred to as the Sulfolane process is used worldwide. The solvency of sulfolane for certain fatty acids and fatty acid esters is the basis for upgrading animal and vegetable fatty acids used in food products, paints, plastics, resins, and soaps. Aqueous solutions containing 30-70 wt% sulfolane are used to remove lignin from wood chips [11]. Sulfolane is used to remove acidic components like hydrogen sulfide and carbon dioxide from gas feed stocks. 

It is particularly valuable in separating aromatic hydrocarbons which tend to form constant-boiling mixtures with many other hydrocarbons. Solvents such as aniline, furfural, phenol, nitrobenzene, or chlorex are introduced at the top of the fractionating column and withdrawn at the bottom. The solvent is recovered from the bottoms products by means... 

Since aliphatic hydrocarbons (unlike aromatic hydrocarbons, p. 155) can be directly nitrated only under very special conditions, indirect methods are usually employed for the preparation of compounds such as nitroethane, CjHsNO. When ethyl iodide is heated with silver nitrite, two isomeric compounds are formed, and can be easily separated by fractional distillation. The first is the true ester, ethyl nitrite, C,HiONO, of b.p. 17° its identity is shown by the action of hot sodium hydroxide solution, which hydrolyses it, giving ethanol and... 

Picrates, Many aromatic hydrocarbons (and other classes of organic compounds) form molecular compounds with picric acid, for example, naphthalene picrate CioHg.CgH2(N02)30H. Some picrates, e.g., anthracene picrate, are so unstable as to be decomposed by many, particularly hydroxylic, solvents they therefore cannot be easily recrystaUised. Their preparation may be accomplished in such non-hydroxylic solvents as chloroform, benzene or ether. The picrates of hydrocarbons can be readily separated into their constituents by warming with dilute ammonia solution and filtering (if the hydrocarbon is a solid) through a moist filter paper. The filtrate contains the picric acid as the ammonium salt, and the hydrocarbon is left on the filter paper. 

Aromatic and Nonaromatic Hydrocarbon Separation. Aromatics are partially removed from kerosines and jet fuels to improve smoke point and burning characteristics. This removal is commonly accompHshed by hydroprocessing, but can also be achieved by Hquid-Hquid extraction with solvents, such as furfural, or by adsorptive separation. Table 7 shows the results of a simulated moving-bed pilot-plant test using siHca gel adsorbent and feedstock components mainly in the C q—range. The extent of extraction does not vary gready for each of the various species of aromatics present. SiHca gel tends to extract all aromatics from nonaromatics (89). 

Another use is in various extraction and absorption processes for the purification of acetylene or butadiene and for separation of aHphatic hydrocarbons, which have limited solubiHty in DMF, from aromatic hydrocarbons. DMF has also been used to recover CO2 from flue gases. Because of the high solubiHty of SO2 iu DMF, this method can even be used for exhaust streams from processes using high sulfur fuels. The CO2 is not contaminated with sulfur-containing impurities, which are recovered from the DMF in a separate step (29). 

The carbon black (soot) produced in the partial combustion and electrical discharge processes is of rather small particle si2e and contains substantial amounts of higher (mostly aromatic) hydrocarbons which may render it hydrophobic, sticky, and difficult to remove by filtration. Electrostatic units, combined with water scmbbers, moving coke beds, and bag filters, are used for the removal of soot. The recovery is illustrated by the BASF separation and purification system (23). The bulk of the carbon in the reactor effluent is removed by a water scmbber (quencher). Residual carbon clean-up is by electrostatic filtering in the case of methane feedstock, and by coke particles if the feed is naphtha. Carbon in the quench water is concentrated by flotation, then burned. 

Extraction Solvent. Dimethyl sulfoxide is immiscible with alkanes but is a good solvent for most unsaturated and polar compounds. Thus, it can be used to separate olefins from paraffins (93). It is used in the Institute Fransais du Pntrole (IFF) process for extracting aromatic hydrocarbons from refinery streams (94). It is also used in the analytical procedure for determining polynuclear hydrocarbons in food additives (qv) of petroleum origin (95). 

Several solvent uses have been proposed. Dimethyl sulfate has been used as a solvent for the study of Lewis acid—aromatic hydrocarbon complexes (148). It also is effective as an extraction solvent to separate phosphoms haUde—hydrocarbon mixtures and aromatic hydrocarbons from aUphatics, and it acts as an electrolyte in electroplating iron (149—152). The toxicity of dimethyl sulfate precludes its use as a general-purpose solvent. 

The Diacel columns can be used for the separation of a wide variety of compounds, including aromatic hydrocarbons having hydroxyl groups, carbonyls and sulfoxides, barbiturates, and P-blockers (35,36). There are presendy nine different cellulose derivative-based columns produced by Diacel Chemical Industries. The different columns each demonstrate unique selectivities so that a choice of stationary phases is available to accomplish a separation. 

The carbonate groups are polar but separated by aromatic hydrocarbon groups. 

The induced counter-dipole can act in a similar manner to a permanent dipole and the electric forces between the two dipoles (permanent and induced) result in strong polar interactions. Typically, polarizable compounds are the aromatic hydrocarbons examples of their separation using induced dipole interactions to affect retention and selectivity will be given later. Dipole-induced dipole interaction is depicted in Figure 12. Just as dipole-dipole interactions occur coincidentally with dispersive interactions, so are dipole-induced dipole interactions accompanied by dispersive interactions. It follows that using an n-alkane stationary phase, aromatic... 

Alternatively, using a polyethylene glycol stationary phase, aromatic hydrocarbons can also be retained and separated primarily by dipole-induced dipole interactions combined with some dispersive interactions. Molecules can exhibit multiple interactive properties. For example, phenyl ethanol possesses both a dipole as a result of the hydroxyl group and is polarizable due to the aromatic ring. Complex molecules such as biopolymers can contain many different interactive groups. 

Silica gel, per se, is not so frequently used in LC as the reversed phases or the bonded phases, because silica separates substances largely by polar interactions with the silanol groups on the silica surface. In contrast, the reversed and bonded phases separate material largely by interactions with the dispersive components of the solute. As the dispersive character of substances, in general, vary more subtly than does their polar character, the reversed and bonded phases are usually preferred. In addition, silica has a significant solubility in many solvents, particularly aqueous solvents and, thus, silica columns can be less stable than those packed with bonded phases. The analytical procedure can be a little more complex and costly with silica gel columns as, in general, a wider variety of more expensive solvents are required. Reversed and bonded phases utilize blended solvents such as hexane/ethanol, methanol/water or acetonitrile/water mixtures as the mobile phase and, consequently, are considerably more economical. Nevertheless, silica gel has certain areas of application for which it is particularly useful and is very effective for separating polarizable substances such as the polynuclear aromatic hydrocarbons and substances... 

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. 

Paraffin and Aromatic Hydi ocarbon may be separated by the action of fuming sulphuric acid, 4iich forms the sulphonic and with the aromatic hydrocarbon. The product is poured into water. The sulphonic acid dissolves readily in water, whereas the paiaffin is insoluble. 

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