Octan number

The analyst now has available the complete details of the chemical composition of a gasoline all components are identified and quantified. From these analyses, the sample s physical properties can be calculated by using linear or non-linear models density, vapor pressure, calorific value, octane numbers, carbon and hydrogen content. 

Because of the existence of numerous isomers, hydrocarbon mixtures having a large number of carbon atoms can not be easily analyzed in detail. It is common practice either to group the constituents around key components that have large concentrations and whose properties are representative, or to use the concept of petroleum fractions. It is obvious that the grouping around a component or in a fraction can only be done if their chemical natures are similar. It should be kept in mind that the accuracy will be diminished when estimating certain properties particularly sensitive to molecular structure such as octane number or crystallization point. 

However, in practice the octane number has a ceiling imposed by refining industry constraints such as composition, lead reduction or elimination, cost, and demand volume and distribution. 

For many years the development of refining processes and the formulation of gasolines has centered around the octane number. It is therefore appropriate to explain briefly what is the current situation and what are the prospects in this area. 

In order to characterize the behavior of motor fuels or their components with regard to knocking resistance but without involving chemical composition criteria which are complex and not easy to quantify, the traditional method that has been universally employed for more than 50 years consists of introducing the concept of octane number. 

A motor fuel has an octane number X if it behaves under tightly defined experimental conditions the same as a mixture of X volume % of isooctane and (100 - X)% of n-heptane. The isooctane-heptane binary mixtures are called primary reference fuels. Octane numbers higher than 100 can also be defined the reference material is isooctane with small quantities of tetraethyl lead added the way in which this additive acts will be discussed later. 

Measurement of octane numbers is carried out using a reference motor called CFR (Cooperative Fuel Research), referring to a series of studies conducted in 1928 in the United States in order to standardize the methods for characterizing motor fuels. 

There are two standard procedures for determining the octane numbers Research or FI and the Motor or F2 methods. The corresponding numbers are designated as RON (Research Octane Number) and MON (Motor Octane Number) which have become the international standard. 

The measurement error for conventional motor fuels is around 0.3 points and 0.7 points for the RON and the MON respectively. The RON is the characteristic more often used and more widespread than the MON moreover, when the octane number is used without reference either procedure, it is taken to be the RON. 

Specifications for octane numbers of motor fuels in France. 

In every part of the world, the same type of classification as above is found for fuels premium or regular, with or without lead. The octane numbers can be different from one country to another depending on the extent of development of their car populations and the capabilities of their local refining industries. The elimination of lead is becoming the rule wherever there are large automobile populations and severe anti-pollution requirements. Thus the United States, Japan and Canada no longer distribute leaded fuels. (... 

To evaluate the real behavior of fuels in relation to the segregation effect, the octane numbers of the fuel components can be determined as a function of their distillation intervals In this manner, new characteristics have been defined, the most well-known being the delta R 100 (A7 100) and the Distribution Octane Number (DON). Either term is sometimes called the Front-End Octane Number . 

Another characteristic similar to A/ 100 is the Distribution Octane Number (DON) proposed by Mobil Corporation and described in ASTM 2886. The idea is to measure the heaviest fractions of the fuel at the inlet manifold to the CFR engine. For this method the CFR has a cooled separation chamber placed between the carburetor and the inlet manifold. Some of the less volatile components are separated and collected in the chamber. This procedure is probably the most realistic but less discriminating than that of the AJ 100 likewise, it is now only of historical interest. 

The octane numbers for olefins, as for paraffins, depends on the length and ramification of their chains. Olefin RONs are generally higher than those for paraffins having the same carbon skeleton. The displacement of the... 

Naphthenes always have higher octane numbers —RON and MON— than their non-cyclic homologs for example, the RON of n-hexane is 24.8 while cyclohexane attains 83. 

The preceding information indicates the paths to follow in order to obtain stocks of high octane number by refining. The orientation must be towards streams rich in aromatics (reformate) and in isoparaffins (isomerization, alkylation). The olefins present essentially in cracked gasolines can be used only with moderation, considering their low MONs, even if their RONs are attractive. 

Table 5.10 gives octane number examples for some conventional refinery stocks. These are given as orders of magnitude because the properties can vary according to process severity and the specified distillation range. 

Figure 5.5 can be used to place the different product streams with respect to the objectives required for commercial octane numbers for Eurosuper and Superplus. It is clearly evident that the preparation of Superplus (RON 98, MON 88) will require careful screening of its components. 

Formulation consists of mixing the effluent streams coming from the different refining units in order to obtain products conforming to the specifications. It is also at this point that additives are added, the reasons for which and whose action will be described later. One can easily see that as far as octane numbers are concerned, or for that matter any other parameter, the... 

Octane numbers (RON and MON) of some conventional refinery streams (orders of magnitude). 

More general techniques covering a wider range employ gas chromatography (Durand et al., 1987). This enables identification and analysis of the nearly 200 gasoline components whose octane numbers are known. 

To predict the octane numbers of more complex mixtures, non-linear models are necessary the behavior of a component i in these mixtures depends on its hydrocarbon environment. 

Adding lead to a fuel increases octane numbers by several points. From an RON of around 92, the increase is on the order of 2 to 3 points for 0.15 g Pb/1 and of 5 to 6 points for 0.4 g Pb/1. For higher concentrations the effect of saturation appears and additional improvement in the octane number becomes more modest. The preceding values concern the RON as well as the MON. Nevertheless, one more often observes slightly larger increases for the RON. In other words, lead addition tends to increase the sensitivity slightly (on an order of one point for 0.4 g Pb/1). 

The gradual reduction and ultimate elimination of lead has seen considerable effort by the refiner to maintain the octane numbers at satisfactory levels. In Europe, the conventional unleaded motor fuel, Eurosuper, should have a minimum RON of 95 and a minimum MON of 85. These values were set in 1983 as the result of a technical-economic study called RUFIT (Rational Utilization of Fuels in Private Transport). A compromise was then possible between refining energy expenses and vehicle fuel consumption (Anon., 1983). 

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