Naphtha fraction

The tops/naphtha fraction is similar to straight-mn material. 

Gas oil fractions (204—565°C) from coal Hquefaction show even greater differences in composition compared to petroleum-derived counterparts than do the naphtha fractions (128). The coal-gas oils consist mostly of aromatics (60%), polar heteroaromatics (25%), asphaltenes (8—15%), and saturated... 

The primary difference in shale oils produced by different processing methods is in boiling point distribution. Rate of heating, as well as temperature level and duration of product exposure to high temperature, affect product type and yield (28). Gas combustion processes tend to yield slightly heavier hquid products because of combustion of the lighter, ie, naphtha, fractions. 

The naphtha fraction is dorninated by saturates having lesser amounts of mono- and diaromatics (Table 2, Eig. 4). Whereas naphtha (ibp to 210°C) covers the boiling range of gasoline, most raw petroleum naphtha molecules have a low octane number and most raw naphtha is processed further, to be combined with other process naphthas and additives to formulate commercial gasoline. 

The 3 -heterocychcs ia the mid-distiUate range are primarily the thiacyclanes, ben2othiophenes, and diben2othiophenes. There are lesser amounts of dialkyl—, diaryl—, and aryl—alkyl sulfides (29). Alkylthiophenes are scarce or absent, but some evidence exists for ben2thiacyclanes (Fig. 6). As for the naphtha fractions, these sulfur species account for a minimal fraction of the total sulfur ia the cmde. 

The main limitation to thermal conversion is that the products can be unstable. Thermal cracking at low pressure gives olefins, particularly in the naphtha fraction such olefins yield an unstable product that tends to form gum as well as heavier products that form sediments (5). 

Gasoline. The naphtha fraction from cmde oil distillation is ultimately used to make gasoline. The two streams are isolated early in the refining scheme so that each can be refined separately for optimum blending in order to achieve the required specifications (see Gasoline and other motor fuels). 

First, the tar acids were removed from the naphtha fractions of light oils and, in the case of CVR tars, carboHc oil. The oils were then mixed with 25—35% sulfuric acid. After separation of the sulfates, the aqueous solution was diluted with water and the resinous material skimmed off. The diluted sulfate solution was boiled to expel any neutral oils, dried by the addition of soHd caustic soda or a2eotropically with ben2ene, and fractionated to yield pyridine, 2-methylpyridine (a-picoline), and a fraction referred to as 90/140 bases, which consisted mainly of 3- and 4-methylpyridines and 2,6-dimethylpyridine (2,6-lutidine). Higher boiling fractions were termed 90/160 and 90/180 bases because 90% of the product distilled at 160 and 180°C, respectively. 

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... 

Refinery group" = low pressure naphtha fractionators, gasoline splitters, crude flash towers, etc. 

In one process the naphtha fraction boiling between 160 and 180°C is washed with caustic soda to remove the acids and then with suilphuric acid to remove basic constituents such as pyridine and quinoline. The naphtha is then frozen to remove naphthalene, and agitated with sulphuric acid, then with caustic soda and finally with water. Concentrated sulphuric acid is then run into the purified naphtha at a temperature below 0°C. The reaction is stopped by addition of water after 5-10 minutes, any sediment is removed, and the solution is neutralised and then washed with water. Residual naphtha is distilled off under vacuum, leaving behind the resin, which is run into trays for cooling. 

Figure 2.16 Clirotnatograms of a pentane extract of a water sample containing 200 ppb of a naphtha fraction (a) sample extracted by using a continuous flow system, where a pressurized bottle was employed as the sample-delivery system (b) batch-extracted sample. Reprinted from Journal of Chromatography, A 330, J. Roeraade, Automated monitoring of organic Race components in water. I. Continuous flow exti action together with on-line capillary gas cliro-matography , pp. 263 - 274, copyrigth 1985, with permission from Elsevier Science.

Saturated cyclic hydrocarbons, normally known as naphthenes, are also part of the hydrocarbon constituents of crude oils. Their ratio, however, depends on the crude type. The lower members of naphthenes are cyclopentane, cyclohexane, and their mono-substituted compounds. They are normally present in the light and the heavy naphtha fractions. Cyclohexanes, substituted cyclopentanes, and substituted cyclohexanes are important precursors for aromatic hydrocarbons. 

The examples shown here are for three naphthenes of special importance. If a naphtha fraction contains these compounds, the first two can he converted to benzene, and the last compound can dehydrogenate to toluene during processing. Dimethylcyclohexanes are also important precursors for xylenes (see Xylenes later in this section). 

Naphthenic acids in the naphtha fraction have a special commercial importance and can be extracted by using dilute caustic solutions. The total acid content of most crudes is generally low, but may reach as much as 3%, as in some California crudes. 

Typical analyses of two straight-run naphtha fractions from two crude types... 

Improve the characteristics of a fuel. For example, a lower octane naphtha fraction is reformed to a higher octane reformate product. The reformate is mainly blended with naphtha for gasoline formulation or extracted for obtaining aromatics needed for petrochemicals production. 

Increasing the octane number of a low-octane naphtha fraction is achieved by changing the molecular structure of the low octane number components. Many reactions are responsible for this change, such as the dehydrogenation of naphthenes and the dehydrocyclization of paraffins to aromatics. Catalytic reforming is considered the key process for obtaining benzene, toluene, and xylenes (BTX). These aromatics are important intermediates for the production of many chemicals. 

The feed to a catalytic reformer is normally a heavy naphtha fraction produced from atmospheric distillation units. Naphtha from other sources such as those produced from cracking and delayed coking may also be used. Before using naphtha as feed for a catalytic reforming unit, it must be hydrotreated to saturate the olefins and to hydrodesulfurize... 

Isomerization is a small-volume but important refinery process. Like alkylation, it is acid catalyzed and intended to produce highly-branched hydrocarbon mixtures. The low octane C5/C6 fraction obtained from natural gasoline or from a light naphtha fraction may be isomerized to a high octane product. 

When liquid hydrocarbons such as a naphtha fraction or a gas oil are used to produce olefins, many other reactions occur. The main reaction, the cracking reaction, occurs by a free radical and beta scission of the C-C bonds. This could be represented as ... 

Cresylic acid is a commercial mixture of phenolic compounds including phenol, cresols, and xylenols. This mixture varies widely according to its source. Properties of phenol, cresols, and xylenols are shown in Table 4-5 Cresylic acid constitutes part of the oxygen compounds found in crudes that are concentrated in the naphtha fraction obtained principally from naphthenic and asphaltic-based crudes. Phenolic compounds, which are weak acids, are extracted with relatively strong aqueous caustic solutions. 

Benzoraffln A hydrofining process for treating naphtha fractions derived from coal. It is a fixed-bed, gas-phase process using a cobalt/molybdenum oxide catalyst. Developed jointly by BASF, Veba-Chemie, and Lurgi, Ground 1960. 

While a majority of laboratory-scale dehydrocyclization studies involve carefully chosen feedstocks, often a single alkane, commercial operators use a naphtha fraction consisting of a complex mixture of hydrocarbons. At least some of these will be incapable of easily undergoing direct dehydrocyclization and need to be isomerized into reactive structures if aromatics are to be formed. The work of Davis suggests that the acidity of dual function catalysts is an important added factor in these isomerizations, one which likely complements the different set of isomerizations that may be catalyzed by the platinum function. 

Apart from FT synthesis for naphtha, the MtSynfuels process has the advantage of sufficiently high octane numbers (RON 92) of the naphtha fraction. Therefore, this naphtha can be used directly as a fuel (gasoline) for petrol engines without further upgrading (Liebner et al., 2004). 

Hydrocarbon composition is also determined by mass spectrometry, a technique that has seen wide use for hydrocarbon-type analysis of naphtha and gasoline (ASTM D2789) as well as for the identification of hydrocarbon constituents in higher-boiling naphtha fractions (ASTM D2425). 

---