Distillation and Vapor Pressure Measurement in Petroleum Products

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The assembly is then re-immersed and after another 2 minutes, it is removed, shaken and the pressure gauge is read again. This procedure is repeated until two successive readings are within 0. Vapor pressure is an important physical property of volatile liquids.


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It is of critical importance for automotive and aviation gasolines since it affect the starting and. Air pollution regulatory authorities mandate maximum gasoline vapor pressures in many areas so as to limit the evaporative emissions of smog-forming hydrocarbons from gasoline. Vapor pressure is also important as an indirect measure of the evaporation tendency of volatile petroleum solvents. Because of the presence air and its of water vapor content in the vapor space within the test method's sample container, as well as some small amount of sample vaporization during the warming of the sample to Environmental Protection Agency and available online.


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  • European countries use that standard or have their own standards which are generally the same is the ISO standard. Liptk Editor CRC Press. ISBN See page AP42, Chapter 7, Section 7. All units are U. The higher this value, the more volatile the sample and the more readily it will evaporate. Unlike distillation data, vapour pressure provides a single value that reflects the combined effect of the individual vapour pressure of the different petroleum fractions in accordance with their mole ratios.

    It is thus possible for two wholly different products to exhibit the same vapour pressure at the same temperature - provided the cumulative pressures exerted by the fractions are the same. A narrow-cut distillate, for example, may exhibit the same vapour pressure as that of a dumbbell blend, where the effect of heavy fractions is counterbalanced by that of the lighter ones.

    HK-1022 Reid Vapor Pressure Bath-ASTM D323

    In conjunction with other volatility data. Reid vapour pressure plays a role in the prediction of gasoline performance. True Vapor Pressure is the pressure of the vapor in equilibrium with the liquid at F it is equal to the bubble point pressure at F. Reid Vapor Pressure is the vapor pressure of a chilled sample of gasoline or other fuel as measured in a test bomb at F.

    The Reid Vapor Pressure differs from the True Vapor Pressure of the sample due to sample vaporization and the presence of water vapor and air in the confined space resulting from the Reid Vapor Pressure test method. To presaturate the sample for the Reid Vapor Pressure test, the streams are flashed at 1 atm and 33 F, and the resulting liquid product is then combined with air at the rate of 4 parts air and 1 part liquid.

    Next the system is flashed at constant volume at F. The resulting gauge pressure is the Reid vapor pressure. Because of this procedure, the Reid Vapor Pressure may be significantly different from the "True Vapor Pressure" if the Reid vapor pressure exceeds 26 psi.

    Immiscible Liquids and Steam Distillation

    The Reid vapor pressure is applicable only for gasoline, volatile crude oil, and other volatile petroleum products. It is not applicable for liquefied petroleum gases. The latest edition of the Standard is broader in scope; it has been modified in order to include the new fuel formulations which result from biofuel mixtures and the new criteria for repeatability and reproducibility calculation.

    This paper studies the most significant changes between the two versions of the ISO Standard together with a field study of commercial automotive fuel samples selection with and without biofuel blend and certified reference materials.

    Scientific Laboratory Equipment - Items

    Distillation - Innovative Applications and Modeling. At present, petroleum remains the major source of energy resources, and for more than years, it has been the main source of fuels used in alternative internal combustion engines in auto-motion as well, both for spark ignition engines SIE 1 , traditionally known as petrol engines, and for compression ignition engines CIE 2 , or diesel engines. Nevertheless, we must bear in mind that differences in the operation of spark ignition and compression ignition engines require very different types of fuels.

    When we speak about petroleum-derived fossil fuels, used as automotive fuel, we must remember that in a given series of hydrocarbons the ignition temperature decreases as the molecular weight increases because the cracking of large molecules needs less activation energies [ 1 ], whereby: The SIE require low boiling hydrocarbons, with a soft combustion temperature and a relatively high spontaneous ignition temperature.

    In the CIE, hydrocarbons with low spontaneous ignition temperatures are preferable, whereby the compounds of low boiling points are unsuitable. Additives are also present in their formulations [ 2 — 4 ]. Petroleum is, even today, the source of energy most used worldwide, but it is not an inexhaustible source of energy; this fact, together with the need to protect the environment, has led to the search for new automotive fuels and for the modification of the characteristics of the existing ones.

    One of the paths chosen in recent years has been to include biofuels in the formulation of conventional automotive fuels given their great capacity for blend with petroleum-derived fuels [ 5 ]. Now, any fuel which is in the market should guarantee that their use in an engine will provide the projected energy performance that it will satisfy any other capacity inherent to their use and it will perform to the environmental quality level required.

    In order to comply with these conditions, those fuels must comply with certain specifications, i. With the aim of controlling engine performance and the formation of vapours which may form explosive mixtures with air or escape to the atmosphere as emissions VOCs—volatile organic compounds , most of the specifications for petroleum distillate products, specially the main automotive engine fuels, limit the values of certain distillation characteristics volatility.

    A fuel distillation range provides decisive information about its composition, its use and its behaviour during storage. Among the wide variety of features to consider when establishing the quality of a fuel used in auto-motion, volatility stands out as one of the most critical ones since it is a characteristic directly related to engine performance and pollutant emissions [ 2 — 4 ]. Petrol is a fuel which is a liquid state in the fuel tank and in the fuel injectors or carburettor on older engines and which is nebulized with air before being injected into the combustion chamber: If the volatility of fuel is low, the petrol does not exist in the gas phase, and there will be difficulties with the starting up of the engine and the behaviour of the engines in cold regimes.

    As a consequence the injection rate is inadequate, and the engine drowns. The volatility characteristics of a diesel have a great influence on the performance of diesel engines: If the volatility is low, then high distillation end points are obtained, which are indicative of high combustion times and poor combustion of heavy hydrocarbons. This will lead to the formation of smoke, loss of power and increased fuel consumption. Volatility is not a physical magnitude that can be measured directly; it is necessary to define methods of evaluating it.

    One universally used method to determine the volatility of a fuel is the distillation test [ 10 , 11 ] that offers different information according to the type of fuel tested. The distillation test measures the percentage of vaporized fuel as the temperature increases. If this percentage is lower, then difficulties may occur at start-up; if it is too high, evaporation losses will occur in the fuel tank, and vapour bubbles may form in the intake manifold of the vehicle. Additionally, combustion may be hampered, causing irregular operation of the engine.

    Also, the presence of hydrocarbons of high boiling point in the petrol is decisive for the generation of polluting emissions.

    Crude Oil Refining

    In the regulations, there are no limitations in the light section of the curve but only for the end zone, where the fractionation of the components occurs. The distillation test, in this case, measures the percentage of fuel which is recovered as the temperature increases. In these, fuel is important to note: The temperature at which vaporization ends, since if this is very high, combustion of the less volatile components will be incomplete, fuel droplets may reach the cylinder walls and dilution of the lubricating oil may take place, thereby increasing wear and producing coke deposits in the combustion chamber and waste segments [ 3 ].

    The end point of the fractionation of the components. Belonging to a particular group defines the setup of the equipment to be used and the condenser temperature.

    During the testing process, a mL test portion is distilled under the specified conditions appropriate to the fuel group, and systematic observations of thermometer readings and volumes of condensate recovered are made. The introduction of new formulations in automotive fuels made necessary the adaptation of the standard in effect at the time of their appearance ISO , and, given the volatility characteristics of the new formulations, it was also necessary to validate the test method again based on new precision criteria.

    The new version of the ISO standard establishes new criteria, based on the group to which it belongs the sample tested, to determine the validity of two results obtained under the same conditions by one operator using the same apparatus, in the same operating conditions, on the same day, on identical samples repeatability, r or obtained by different operators working in different laboratories on identical material test reproducibility, R. A sample selection of automotive fuel petrol, diesel with and without blend of biofuel bioethanol, biodiesel for a field study is used.

    The variations in product volatility as a result of the presence of biofuel in its composition are checked. The changes in criteria established for repeatability and reproducibility in Standard ISO are studied; certified reference materials are used. Distillation flasks: flasks should have a capacity of mL and be constructed of heat-resistant glass, according to the dimensions and tolerances given in Standard ISO Receiving cylinder: graduate cylinder of mL capacity, with a mark at mL and metal base.

    Centring device, for centring the temperature sensor, adjusts the neck distillation flask, allows to centre the temperature sensor and prevents steam leaks. Automated equipment for petroleum product distillation satisfies the requirements established in the Standard ISO ; the maximum error tracking device level is 0. Clean the condenser tube, employing acetone. Dry thoroughly to remove any portion of acetone used for cleaning the device. Check that the temperature probe is properly seated in the centring device.

    Check your state and proper cleaning. Check that the value of atmospheric pressure recorded by the apparatus is coincident with that indicated by the recording barometer atmospheric pressure in the laboratory. Measure the test portion precisely to the mL mark of the receiving cylinder, and then transfer it as completely as practical to the distillation flask, taking care that none of the liquid flows into the vapour tube.

    If irregular boiling bumping is expected, add a small volume of clean and dry boiling chips to the test portion. Fit the flask vapour tube, provided with a silicone rubber stopper, tightly into the condenser tube. Adjust the distillation flask in a vertical position so that the vapour tube extends into the condenser tube for a distance of 25—50 mm. Raise and adjust the flask-support board to fit snugly against the bottom of the flask. Fit the receiving cylinder with a drip deflector, through which the distillate is going to drip. Place the receiving cylinder that was used to measure the test portion, without drying, into the bad under the lower end of the condenser tube so that the end of the condenser tube is centred in the receiving cylinder and extends therein for a distance of at least 25 mm.

    Any distillation that does not meet above conditions must be repeated, as well as those in which the actual loss differs by more than 2 mL from the estimated value. The fibre drop analyser: a new multianalyser analytical instrument with applications in sugar processing and for the analysis of pure liquids.

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