Cycloparaffins

The general formula for cycloparaffins having a singie ring is There... 

More precisely, the rate of ozone formation depends closely on the chemical nature of the hydrocarbons present in the atmosphere. A reactivity scale has been proposed by Lowi and Carter (1990) and is largely utilized today in ozone prediction models. Thus the values indicated in Table 5.26 express the potential ozone formation as O3 formed per gram of organic material initially present. The most reactive compounds are light olefins, cycloparaffins, substituted aromatic hydrocarbons notably the xylenes, formaldehyde and acetaldehyde. Inversely, normal or substituted paraffins. 

Hydrogenation of the aromatic ring to form naphthenic compounds has been proposed as a route to faciUtate the separation of the Cg aromatic isomers (31). The spread in boiling points of the naphthenic compounds is 12°C vs a spread of 8°C for the aromatic compounds. However, the cycloparaffinic products obtained from OX and EB boil only 3°C apart, impeding the separation. 

Table 8 shows that the naphthas produced by the EDS process have higher concentrations of cycloparaffins and phenols than do petroleum-derived naphthas, whereas the normal paraffins are present in much lower concentrations. The sulfur and nitrogen concentrations in coal naphthas are high compared to those in petroleum naphthas. 

The principal class of reactions in the FCC process converts high boiling, low octane normal paraffins to lower boiling, higher octane olefins, naphthenes (cycloparaffins), and aromatics. FCC naphtha is almost always fractionated into two or three streams. Typical properties are shown in Table 5. Properties of specific streams depend on the catalyst, design and operating conditions of the unit, and the cmde properties. 

The cetane number of a fuel depends on its hydrocarbon composition. In general, normal paraffins have high cetane numbers, isoparaffins and aromatics have low cetane numbers, and olefins and cycloparaffins fall somewhere in between. Diesel fuels marketed in the United States have cetane numbers ranging between 35 and 65. Most manufacturers specify a minimum cetane number of 40—45. 

Hydrocarbons, compounds of carbon and hydrogen, are stmcturally classified as aromatic and aliphatic the latter includes alkanes (paraffins), alkenes (olefins), alkynes (acetylenes), and cycloparaffins. An example of a low molecular weight paraffin is methane [74-82-8], of an olefin, ethylene [74-85-1], of a cycloparaffin, cyclopentane [287-92-3], and of an aromatic, benzene [71-43-2]. Cmde petroleum oils [8002-05-9], which span a range of molecular weights of these compounds, excluding the very reactive olefins, have been classified according to their content as paraffinic, cycloparaffinic (naphthenic), or aromatic. The hydrocarbon class of terpenes is not discussed here. Terpenes, such as turpentine [8006-64-2] are found widely distributed in plants, and consist of repeating isoprene [78-79-5] units (see Isoprene Terpenoids). 

Gycloparaffins. Members of this class produce effects much like the paraffins, except that unsaturated cycloparaffins are more noxious than the saturated counterparts. Breathing high concentrations of cycloparaffin vapors can result in irritation and anesthesia. 

Highly pure / -hexane can be produced by adsorption on molecular sieves (qv) (see Adsorption, liquid separation) (43). The pores admit normal paraffins but exclude isoparaffins, cycloparaffins, and aromatics. The normal paraffins are recovered by changing the temperature and/or pressure of the system or by elution with a Hquid that can be easily separated from / -hexane by distillation. Other than ben2ene, commercial hexanes also may contain small concentrations of olefins (qv) and compounds of sulfur, oxygen, and chlorine. These compounds caimot be tolerated in some chemical and solvent appHcations. In such cases, the commercial hexanes must be purified by hydrogenation. 

Cyclohexane [110-82-7] CgH 2> is a clear, essentially water-insoluble, noncorrosive Hquid that has a pungent odor. It is easily vaporized, readily flammable, and less toxic than benzene. StmcturaHy, it is a cycloparaffin. Cyclohexane was synthesized by Baeyer in 1893 and it was discovered by Markovnikov in Caucasian petroleum fractions shordy thereafter. Its presence in United States cmde oils was estabUshed in 1931 (45). Cyclohexane was produced first by hydrogenation of benzene in 1898 (46). 

Cyclohexane is present in all cmde oils in concentrations of 0.1—1.0%. The cycloparaffinic cmde oils, such as those from Nigeria and Venezuela, have high cyclohexane concentrations, and the highly paraffinic cmde oils, such as those from Indonesia. Saudi Arabia, and Pennsylvania, have low concentrations and concentrations of cycloparaffins in cmde oils from Texas, Oklahoma, and Louisiana tend to fall in between (see Petroleum). 

Pig. 6. Typical stmctures in lube oil (a) / -paraffin, (b) isoparaffin, (c) cycloparaffin, (d) aromatic hydrocarbon, and (e) mixed aUphatic and aromatic ring... 

Although most greases offer some inherent protection against msting, additives, eg, amine salts, sodium sulfonate, cycloparaffin (naphthenate) salts, esters, and nonionic surfactants (qv), are often used to provide added protection against water and salt-spray corrosion. A dispersion of sodium nitrite has been particularly effective in some multipurpose greases. 

Interest in synthetic naphthenic acid has grown as the supply of natural product has fluctuated. Oxidation of naphthene-based hydrocarbons has been studied extensively (35—37), but no commercially viable processes are known. Extensive purification schemes must be employed to maximize naphthene content in the feedstock and remove hydroxy acids and nonacidic by-products from the oxidation product. Free-radical addition of carboxylic acids to olefins (38,39) and addition of unsaturated fatty acids to cycloparaffins (40) have also been studied but have not been commercialized. 

Nitrations are highly exothermic, ie, ca 126 kj/mol (30 kcal/mol). However, the heat of reaction varies with the hydrocarbon that is nitrated. The mechanism of a nitration depends on the reactants and the operating conditions. The reactions usually are either ionic or free-radical. Ionic nitrations are commonly used for aromatics many heterocycHcs hydroxyl compounds, eg, simple alcohols, glycols, glycerol, and cellulose and amines. Nitration of paraffins, cycloparaffins, and olefins frequentiy involves a free-radical reaction. Aromatic compounds and other hydrocarbons sometimes can be nitrated by free-radical reactions, but generally such reactions are less successful. 

Toluene, Benzene, and BTX Reeoveiy. The composition of aromatics centers on the C - and Cg-fraction, depending somewhat on the boihng range of the feedstock used. Most catalytic reformate is used directiy in gasoline. That part which is converted to benzene, toluene, and xylenes for commercial sale is separated from the unreacted paraffins and cycloparaffins or naphthenes by hquid—hquid extraction or by extractive distillation. It is impossible to separate commercial purity aromatic products from reformates by distillation only because of the presence of azeotropes, although comphcated further by the closeness in boihng points of the aromatics, t/o-paraffin, and unreacted C -, C -, and Cg-paraffins. 

So, Sulfolane and Carom, ca 1997, are two current rival processes. Sulfolane has a slight advantage over Carom ia energy consumption, while Carom has 6—8% less capital for the same capacity Sulfolane unit. In 1995, Exxon (37) commercialized the most recent technology for aromatics recovery when it used copolymer hoUow-fiber membrane ia concentration-driven processes, pervaporation and perstraction, for aromatic—paraffin separation. Once the non aromatic paraffins and cycloparaffins are removed, fractionation to separate the C to C aromatics is relatively simple. 

Gas turbine fuels can contain natural surfactants if the cmde fraction is high in organic acids, eg, naphthenic (cycloparaffinic) acids of 200—400 mol wt. These acids readily form salts that are water-soluble and surface-active. Older treating processes for sulfur removal can leave sulfonate residues which are even more powerful surfactants. Refineries have installed processes for surfactant removal. Clay beds to adsorb these trace materials are widely used, and salt towers to reduce water levels also remove water-soluble surfactants. In the field, clay filters designed as cartridges mounted in vertical vessels are also used extensively to remove surfactants picked up in fuel pipelines, in contaminated tankers, or in barges. 

Low temperature viscosities have an important influence on fuel atomisation and they affect engine starting. Cycloparaffinic and aromatic fuels reach unacceptably high viscosities at low temperatures. A kinematic viscosity of 35 mm /s (=cSt) represents the practical upper limit for pumps on aircraft, whereas much higher limits are acceptable for ground iastaHations. 

Catalytic Reforming. Worldwide, approximately 30% of commercial benzene is produced by catalytic reforming, a process ia which aromatic molecules are produced from the dehydrogenation of cycloparaffins, dehydroisomerization of alkyl cyclopentanes, and the cycHzation and subsequent dehydrogenation of paraffins (36). The feed to the catalytic reformer may be a straight-mn, hydrocracked, or thermally cracked naphtha fraction ia the... 

Fig. 6. Boiling points of C —hydrocarbons. P, iso and normal paraffins C, C - and Cg-cycloparaffins and A, aromatics.

The conversion proceeds through dimethyl ether as an intermediate and the products are paraffins, aromatics, cycloparaffins, and +olefins, all of which must involve alkylation reactions catalyzed by the strong acid function of the zeoHte. This technology represents a significant advancement in the potential for using coal as a raw material for gasoline and hydrocarbons. 

Naphthenic acid is a collective name for organic acids present in some but not all crude oils. In addition to true naphthenic acids (naphthenic carboxylic acids represented by the formula X-COOH in which X is a cycloparaffin radical), the total acidity of a crude may include various amounts of other organic acids and sometimes mineral acids. Thus the total neutralization number of a stock, which is a measure of its total acidity, includes (but does not necessaiily represent) the level of naphthenic acids present. The neutralization number is the number of milligrams of potassium hydroxide required to neutralize one gram of stock as determined by titration using phenolphthalein as an indicator, or as determined by potentiometric titration. It may be as high as 10 mg KOH/gr. for some crudes. The neutralization number does not usually become important as a corrosion factor, however, unless it is at least 0.5 mg KOH/gm. 

Propylcyclopentane 269 516 15 4.4 Four-Ring and Five-Ring Cycloparaffins ... 

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