Pour points

The pour point of a sample is defined as the temperature normally 3 degrees above the point a sample no longer moves when inverted. This value is of particular importance for crudes that are transported through pipelines from source to load ports. 

Currently the method of choice for whole crudes is ASTM D5853 which handles crudes that have pour points greater than -36 °C. For crudes that have pour points lower than -36 °C ASTM D97 tends to be the method of choice. 

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The pour point of a cut or petroleum fraction can be derived from the characteristic properties by an expression published by the API ... 

M = molecular weight j/joo = kinematic viscosity at lOOT Tff = pour point temperature... 

Average error is about 5°C. The method should not be used for pour points less than 60°C. 

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). 

At lower temperatures, the crystals increase in size, and form networks that trap the liquid and hinder its ability to flow. The pour point is attained which can, depending on the diesel fuel, vary between -15 and -30°C. This characteristic (NF T 60-105) is determined, like the cloud point, with a very rudimentary device (maintaining a test tube in the horizontal position without apparent movement of the diesel fuel inside). 

One remaining possibility that is less costly from an energy point of view but needs to be carefully controlled is to incorporate additives called flow improvers. These materials favor the dispersion of the paraffin crystals and in doing so prevent them from forming the large networks which cause the filter plugging. The conventional flow improvers essentially change the CFPP and pour point, but not the cloud point. They are usually copolymers, produced, for example, from ethylene and vinyl acetate monomers ... 

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. 

It is mainly in cold behavior that the specifications differ between bome-heating oil and diesel fuel. In winter diesel fuel must have cloud points of -5 to -8°C, CFPPs from -15 to -18°C and pour points from -18 to 21°C according to whether the type of product is conventional or for severe cold. For home-heating oil the specifications are the same for all seasons. The required values are -l-2°C, -4°C and -9°C, which do not present particular problems in refining. 

The pour point is the lowest temperature at which an oil can still pour while it is cooled, without agitation, under standardized conditions. The pour point of paraffinic bases is linked to the crystallization of n-paraffins. The pour point of naphthenic bases is related to a significant viscosity increase at low temperatures. This property can be improved by additives. 

Large range of service temperatures Constant viscosity (viscosity index) Pour point, thermal stability... 

For combined cycle turbines Single lubrication system Low pour point Extreme pressure and anti-wear properties Hydrolysis stability Water separation... 

For gear trains Protection from seizing and rapid wear Extreme-pressure and anti-wear properties Resistance to oxidation Thermal stability High viscosity Low pour point Anti-foaming properties Anti-corrosion properties... 

Performance can be illustrated for example by the time necessary for deaeration or de-emulsification of oils, anti-rust properties, copper strip corrosion test, the flash point in closed or open cup, the cloud and pour points, the foaming characteristics, etc. 

During the production of mineral oils from vacuum distillates, one of the process steps, dewaxing , removes the high melting point materials in order to improve the oil s pour point. Dewaixing produces paraffins and waxes, the first coming from light distillates, and the second from medium or heavy distillates. 

Cloud point Pour point Neutralization index Sediment content... 

The pour point of crude oils is measured to give an approximate indication as to their pumpability . In fact, the agitation of the fluid brought on by pumping can stop, slow down or destroy the formation of crystals, conferring on the crude additional fluidity beyond that of the measured pour point temperature. 

Crude oil pour points usually are between -60°C and -(-30°C (Table 8.2). 

Crude oil name Country of origin Pour point, C... 

Certain calibrated orifice instruments (Engler-type) provide viscosity measurements at temperature lower than pour point. This is possible because the apparatus agitates the material to the point where large crystals are prevented from forming whereas in other methods, the sample pour point is measured without agitation. 

This is, for example, the case for crude from Dahra (Libya) which, with a pour point of - 1°C, gives a viscosity of 2.4°E or 16 mm /s at 0°C, or the crude from Coulomnes (France) whose viscosity is close to 20°E at 0°C whereas Its pour point is +12°C. 

It is possible to calculate the properties of wider cuts given the characteristics of the smaller fractions when these properties are additive in volume, weight or moles. Only the specific gravity, vapor pressure, sulfur content, and aromatics content give this advantage. All others, such as viscosity, flash point, pour point, need to be measured. In this case it is preferable to proceed with a TBP distillation of the wider cuts that correspond with those in an actual refinery whose properties have been measured. 

Figure 8.10 shows the aniiine points and the pour points for intermediate cuts from an Arabian Light crude. 

Residue cuts fmm Arabian Light crude. Pour point and Conradson carbon as a function of residue yield. 

The nature of these paraffins and their concentration in diesel fuel affect the three temperatures that characterize the cold behavior. The cloud point is the temperature at which crystals of paraffins appear when the temperature is lowered. The cold filter pluming point is defined as the temperature under which a suspension no ionger flows through a standard filter. Finally, the pour point is the temperature below which the diesel fuel no longer flows by simple gravity in a standard tube. These three temperatures are defined by regulations and the refiner has three types of additives to improve the quality of the diesel fuel of winter. 

Additives acting on the pour point also modify the crystal size and, in addition, decrease the cohesive forces between crystals, allowing flow at lower temperatures. These additives are also copolymers containing vinyl esters, alkyl acrylates, or alkyl fumarates. In addition, formulations containing surfactants, such as the amides or fatty acid salts and long-chain dialkyl-amines, have an effect both on the cold filter plugging point and the pour point. 

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. 

The problem is similar to the case of lubricating oils polyalkylnaphthalenes or alkyl polymethacrylates called pour point depressants have been commercialized to lower the pour point. 

Examples of pour point depressants for lubricating oils. 

These products have molecular weights between 2000 and 10,000, well below those of additives improving the viscosity index (100,000). They are added in very small concentrations (0.01 to 0.3 weight percent) and at these concentrations they can lower the pour point 30°C. 

Vise, at 100°C, mm2/s Viscosity index (V.l.) Pour point, °C Noack volatility, %... 

Pour point NF EN 23015 ISO 3015 ASTM D 97 Observation during gradual cooling... 

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