Paraffinic diesel compounds

A novel method for production of paraffinic hydrocarbons, suitable as diesel fuel, from renewable resources was illustrated. The fatty acid ethyl ester, ethyl stearate, was successfully converted with high catalyst activity and high selectivity towards formation of the desired product, heptadecane. Investigation of the impact of catalyst reduction showed that the reduction pretreatment had a beneficial effect on the formation of desired diesel compound. The non-pretreated catalyst dehydrogenated ethyl stearate to ethyl oleate. The experiments at different reaction temperatures, depicted that conversion of ethyl stearate was strongly dependent on reaction temperature with Eact=69 kj/mole, while product selectivities were almost constant. Complete conversion of ethyl stearate and very high selectivity towards desired product (95%) were achieved at 360°C. 

Liquid alkanes with 9-17 carbon atoms have higher boiling points and are found in kerosene, diesel, and jet fnels. Motor oil is a mixture of liquid hydrocarbons and is used to lubricate the internal components of engines. Mineral oil is a mixture of liquid hydrocarbons and is used as a laxative and a lubricant. Alkanes with 18 or more carbon atoms are waxy solids at room temperatnre. Known as paraffins, these compounds are used in waxy coatings for fruits and vegetables to retain moisture, inhibit mold growth, and enhance appearance. Petrolatum, or Vaseline, is a semisolid mixtnre of liquid hydrocarbons with more than 25 carbon atoms nsed in ointments and cosmetics and as a lubricant. 

Unlike spark-induced combustion engines requiring fuel that resists autoignition, diesel engines require motor fuels, for vhich the reference compound is cetane, that are capable of auto-igniting easily. Additives improving the cetane number will promote the oxidation of paraffins. The only compound used is ethyl-2-hexyl nitrate. 

The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxyUc acids present in cmde oil. Naphthenic acids [1338-24-5] are classified as monobasic carboxyUc acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentane and cyclohexane derivatives. Naphthenic acids are composed predorninandy of aLkyl-substituted cycloaUphatic carboxyUc acids, with smaller amounts of acycHc aUphatic (paraffinic or fatty) acids. Aromatic, olefinic, hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic acids also contain varying amounts of unsaponifiable hydrocarbons, phenoHc compounds, sulfur compounds, and water. The complex mixture of acids is derived from straight-mn distillates of petroleum, mosdy from kerosene and diesel fractions (see Petroleum). 

In the case of diesel fuel, an important property that defines the fuel quality is the cetane number (CN). Fuels with low-CN have poor ignition quality (i.e. knocking, noise, PM emissions) and make starting the engine difficult on cold days.6,7 It is well known that CN is lowest for PAHs and highest for w-paraffins.8,9 In normal paraffins, CN increases with the number of carbon atoms in the molecule. For naphthenic compounds and iso-paraffins the CN falls between those of aromatics and w-paraffins. In iso-paraffins, the CN decreases as the degree of branching increases.10... 

In addition to CN and ON, the smoke point (SP), which is the maximum smoke-free laminar diffusion flame height, has been employed widely to evaluate the tendency of different fuels to form soot. This tool was first applied to kerosenes, later diesel, and then jet engine fuels.19,20 Researchers have tried to relate smoke points of pure compounds to their molecular structure. It was found that the inverse of smoke point, which measures the potential of a fuel to form soot, increases from n-paraffins to iso-paraffins to alkylbenzenes to naphthalenes.21,22 Since smoke points vary with experimental conditions, the concept of a threshold soot index (TSI), which is calculated from the smoke point, molecular weight, and experimental constants, has been used to compare the soot-formation tendencies of different fuel molecules.23... 

Cycle Oil. Heavier, distillate range compounds formed during FCC processing can accumulate within the FCC fractionator. The primary fraction is called light cycle oil (LCO) and contains high percentages of monoaromatic and diaromatic compounds plus olefins and heavier branched paraffins. Unhydrotreated LCO is often quite unstable and has a very low cetane number. For this reason, it is blended into diesel fuel in controlled amounts. Heavy cycle oil and heavy naphtha are additional side cuts that can be produced. These streams can be pumped around to remove heat from the fractionator, used to supply heat to other refinery units, or used as low-quality blendstock component. 

Conversion of heterocyclic aromatic compounds or other aromatic fuel components to paraffins by hydroprocessing can help increase the cetane number of diesel fuel. Fuel paraffins have significantly higher cetane number values than fuel aromatics. For this reason, the cetane number of ultra-low sulfur diesel fuel will typically be one to five numbers greater than higher-sulfur grade fuels. 

The chemical composition of diesel fuel is extremely complex, with an enormous number of compounds normally present (Table 8.2). For this reason, it usually is not practical to analyze diesel fuel for individual compounds but it is often advantageous to define the compounds present as broad classifications of compound types, such as aromatics, paraffins, naphthenes and olefins. 

Figure 1 shows the DTA curve obtained when a sample of diesel soot is burned in the absence of a catalyst. With increasing the temperature, four exothermic peaks appear. These peaks can be attributed to the combustion of different types of hydrocarbons constituting the soot (11). Indeed, it is known that a real soot consists of a volatile fraction, which is more active than a carbonaceous solid fraction. The composition of the volatile fraction can also vary depending on the quality of fuel and the engine s mode of operation. In some cases, aromatic, oxygenated and paraffinic compounds can be present, as well as residual coke of the lubricant (12). 

Kinetic modeling of diesel autothermal reforming is extremely complicated. Diesel fuel consists of a complex variable mixture of hundreds of hydrocarbon compounds containing paraffins, isoparaffins, naphthenes, aromatics, and olefins. To simplify the model, a steady-state power law rate expression for the diesel reforming over each type of catalyst used in this study was developed. A linearized least-squares method of data analysis was used to determine the power law parameters from a series of diesel ATR experiments. The power law rate model for diesel autothermal reaction may be written as ... 

Figure 3 Colour plot of a reversed-phase GCxGC separation of a diesel oil [30]. Although the column combination (first polar, second nonpolar) is decidedly nonorthogonal, the plot still exhibits the well-known clustering of related chemical groups. But now compounds of the least polar group, the paraffins, have the longest second-dimension retention times. The more polarizable groups — the mono- and di-aromatics — now have lower second-dimension retention times.

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