Of diesel fuel

The field of application for liquid chromatography in the petroleum world is vast separation of diesel fuel by chemical families, separation of distillation residues (see Tables 3.4 and 3.5), separation of polynuclear aromatics, and separation of certain basic nitrogen derivatives. Some examples are given later in this section. 

Power output is controlled, not by adjusting the quantity of fuel/air mixture as in the case of induced spark ignition engines, but in changing the flow of diesel fuel introduced in a fixed volume of air. The work required to aspirate the air is therefore considerably reduced which contributes still more to improve the efficiency at low loads. 

The characteristics of diesel fuel taken into account in this area are the cloud point, the pour point, and the cold filter plugging point (CFPP). 

The cold filter plugging point (CFPP) is the minimum temperature at which a given volume of diesel fuel passes through a well defined filter in a limited time interval (NF M 07-042 and EN 116 standards). For conventional diesel fuels in winter, the CFPP is usually between —15 and —25°C. 

The experimental conditions used to determine the CFPP do not exactly reflect those observed in vehicles the differences are due to the spaces in the filter mesh which are much larger in the laboratory filter, the back-pressure and the cooling rate. Also, research is continuing on procedures that are more representative of the actual behavior of diesel fuel in a vehicle and which correlate better with the temperature said to be operability , the threshold value for the Incident. In 1993, the CEN looked at two new methods, one called SFPP proposed by Exxon Chemicals (David et al., 1993), the other called AGELFI and recommended by Agip, Elf and Fina (Hamon et al., 1993). 

In Europe, the classification of diesel fuels according to cold behavior is shown in Tables 5.13 and 5.14. The products are divided into ten classes, six for temperate climates, four for arctic zones. 

Figure 5.9 shows an example of the efficiency of these products. The reductions of CFPP and pour point can easily attain 6 to 12°C for concentrations between 200 and 600 ppm by weight. The treatment cost is relatively low, on the order of a few hundredths of a Franc per liter of diesel fuel. In practice, a diesel fuel containing a flow improver is recognized by the large difference (more than 10°C) between the cloud point and the CFPP. 

The procedure for determining the cetane number in the CFR engine is not extremely widespread because of its complexity and the cost of carrying it out. There also exist several methods to estimate the cetane number of diesel fuels starting from their physical characteristics or their chemical structure. 

As we have shown previously, obtaining both good cold operation characteristics and sufficient cetane numbers constitutes the principal objective for the refiner in the formulation of diesel fuel. To this is added the need for deep desulfurization and, perhaps in the future, limitations placed on the chemical nature of the components themselves, e.g., aromatics content. 

The most important point in the use of diesel fuel is its cold temperature behavior. The subject has been addressed previously because it directly affects the engine operation in winter conditions. 

Two criteria are used to characterize the behavior of diesel fuel in this area these are color and resistance to oxidation. 

We have previously stated that the sulfur content of diesel fuel will be limited in Europe to 0.2% as of 1 October 1994 and to 0.05% as of 1 October 1996. 

The main justification for diesel fuel desulfurization is related to particulate emissions which are subject to very strict rules. Part of the sulfur is transformed first into SO3, then into hydrated sulfuric acid on the filter designed to collect the particulates. Figure 5.21 gives an estimate of the variation of the particulate weights as a function of sulfur content of diesel fuel for heavy vehicles. The effect is greater when the test cycle contains more high temperature operating phases which favor the transformation of SO2 to SO3. This is particularly noticeable in the standard cycle used in Europe (ECE R49). 

In any and all cases, desulfurization of diesel fuel is a necessary condition for attaining very low particulate levels such as will be dictated by future regulations (Girard et al., 1993). 

Numerous works have been directed towards studying the influence of diesel fuel hydrotreatment on emissions. 

The role of detergent additives is to maintain clean injectors so as to insure good distribution of diesel fuel in the cylinder. The structure of these compounds is similar to that of detergents for gasoline engine admission systems. Commercialized compounds are from the succinimide family (see Figure 9.1). 

The reaction mechanism for these products is not clearly understood, but the introduction of organo-metallic compounds (barium or iron salts in colloidal suspension) has been shown to have a beneficiai action on the combustion of diesel fuel in engines and reduce smoke. However, these products cause deposits to form because they are used in relatively large proportions (on the order 0.6 to 0.8 weight %) to be effective. 

Additives for Improving the Cold Behavior of Diesel Fuel (Coley, 1989)... 

The elimination of lead, the reduction of aromatics in gasoline, and the desulfurization of diesel fuels are oing to require significant reformulations of these products that will irripiy development of specific additives that allow the refiner to optimize costs while meeting the required specifications. 

Although lubricant base stocks have been subjected to dewaxing processes, they still contain large amounts of paraffins that result in a high pour point for the oil. In the paragraph on the cold behavior of diesel fuels, additives were mentioned that modify the paraffin crystalline system and oppose the precipitation of solids. 

Glavincevski, B., O.L. Gulder and L. Gardner (1984), Cetane number estimation of diesel fuels from carbon type structural composition . SAE paper No. S4- 34, International fuels and lubricants meeting, Baltimore, MD. 

Martin, B. and P.-H. Bigeard (1992), Hydrotreatment of diesel fuels -its impact on light- duty diesel engine pollutants . SAE paper No. 92-2268, International fuels and lubricants meeting, San Francisco, CA. 

However, this conventional method presents a certain number of limitations. In the first place, the traditional end-use property itself can be difficult to determine. Consider the cetane number for example is it a good characterization of diesel fuel with respect to its behavior in commercial diesel engines In the second place, concern for protecting the environment imposes new specifications which are often specifications linked to the composition of products very low content of certain contaminants, reduced levels of certain families of compounds, or even a specific compound as already discussed. 

The fire ha2ard of methanol appears to be substantially smaller than the fire ha2ard of gasoline, although considerably greater than the fire ha2ard of diesel fuel. The lack of luminosity of a methanol flame is stiH a concern to some, and M85 (or some other methanol fuel with an additive for flame luminosity) may become the standard fuel for this reason. 

The procedure for measuring the cetane number of diesel fuel (ASTM D613) is similar to that used for measuring gasoline octane number. Cetane... 

ASTM specifications for different grades of diesel fuel are summarized in Table 11. 

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