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This test method covers the atmospheric distillation of petroleum products using a laboratory batch distillation unit to determine quantitatively the boiling range characteristics of such products as natural gasoline, light and middle distillates, automotive sparkignition fluids, aviation gasoline, aviation turbine fuels, diesel fuels, petroleum spirits, naphthas, white spirits, kerosenes, and Grades 1 and 2 burner fuels.

Hydrocarbon solvents are also included in the scope of D86. The test method is designed for distillate fuels; it is not applicable to products containing appreciable quantities of residual materials. This test method includes both manual and automated instruments.

Distillation is a method of separating mixtures based on differences in volatility of components in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction.

There are a number of terms frequently used in the distillation measurement of petroleum products. Some of the terms pertinent to the discussions are described below. Initial Boiling Point (IBP) The corrected temperature reading that is observed at the instant the first drop of condensate falls from the lower end of the condenser tube.

X% Boiling Point (e.g., 5%boiling point) The corrected temperature reading corresponding to when X % of the distillate has been recovered in the receiving flask. End Point (EP) or Final Boiling Point (FBP) The maximum corrected temperature reading obtained during the test. This usually occurs after the evaporation of all liquid from the bottom of the flask.

Dry Point (DP) The corrected temperature reading that is observed at the instant the last drop of liquid (exclusive of any drops or film of liquids on the side of the flask or on the temperature measuring device), evaporates from the lowest point in the distillation flask.

The end point or final boiling point, rather than dry point, is intended for general use. The dry point is normally reported for special purpose naphthas such as hydrocarbon solvents used in the paint and coatings industry. Dry point is also substituted for the end point (final boiling point) whenever the sample is of such nature that the precision of the end point (final boiling point) cannot consistently meet the requirements given in the precision section of the method.

Front End Loss Loss due to evaporation during transfer from the receiving cylinder to the distillation flask, vapor loss during the distillation, and uncondensed vapor in the flask at the end of the distillation.

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Percent Recovered The volume of condensate observed in the receiving cylinder, expressed as a percentage of the charge volume associated with a simultaneous temperature reading. Percent Recovery The maximum amount of condensate recovered in the receiving cylinder expressed as a percentage of the charge volume.

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Percent Total Recovery The combined percent recovery and the residue in the flask. Percent Loss The difference between 100 and the percent total recovery. Percent Evaporated The sum of the percent recovered and the percent loss.

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Based on its composition, vapor pressure, expected IBP or expected EP (FBP), or combination thereof, the sample is classified into one of five Groups. Apparatus arrangements, condenser temperature, and other operational variables are defined by the Group into which the sample falls.

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A 100 mL specimen of the sample is distilled under prescribed conditions for the Group in which the sample falls. The distillation is performed in a laboratory batch distillation unit at ambient atmospheric pressure under conditions that are designed to provide approximately one theoretical plate fractionation.

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Systematic observations of temperature readings and volumes of condensate are made, depending on the needs of the user of the data. The volume of the residue and the losses are also recorded.

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At the conclusion of the distillation, the observed vapor temperatures can be corrected for barometric pressure and the data are examined for conformance to procedural requirements such as distillation rates.

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The test is repeated if any specified condition has not been met. The results are commonly expressed as percent evaporated or percent recovered versus corresponding temperature readings. The detailed procedure section is in Sec. 10 of ASTM D86-04b Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure.

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The distillation characteristics of petroleum products have an important effect on their safety and performance, especially in the case of fuels and hydrocarbon solvents. The boiling range gives information on the composition, the properties, and the behavior of the fuel during storage and use.

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The distillation characteristics are critically important for both automotive and aviation gasoline, affecting starting, warm-up, and the tendency to vapor lock at high operating temperature or at high altitude, or both. The presence of high boiling components in these and other fuels can significantly affect the degree of formation of solid combustion deposits.

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Volatility, as it affects the rate of evaporation, is an important factor in the application of many solvents, particularly in the paints and coatings industry. Distillation limits are often included in petroleum product specifications, in commercial contract agreement, process refinery/control applications, and for compliance to various regulations.

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It has often been said the laboratory measurement result is only as good as the sample with which the test has been done. This is particularly true for petroleum products because of the complex nature of the components making up the sample.

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If precautions are not taken to get a representative sample of the product being tested, then the reported test results may not give an accurate value of the property being measured. ASTM D4057 Standard Practice for Manual Sampling of Petroleum and Petroleum Products is often quoted as the standard practice for the manual sampling of petroleum and petroleum products,

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and ASTM D4177 Standard Practice for Automatic Sampling of Petroleum and Petroleum Products is the standard practice for the automated sampling of petroleum and petroleum products. Assume that the sample that gets to the laboratory is a good and representative sample of the product being tested for distillation by D86.

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When the representative sample arrives at the lab, the first thing that the test operator needs to know is to what group category or characteristic the sample belongs in order to determine the applicable operational and test parameters necessary to do the distillation.

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The group characteristics are based on the sample composition, vapor pressure, expected initial boiling point (IBP), or expected final boiling point FBP or combination thereof. Table 1 gives the various parameters that are used to determine into which group a particular sample belongs.

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Group 0 If the sample is natural gasoline, i.e., a volatile hydrocarbon liquid extracted from natural gas, such as condensates that have properties somewhat similar to but more volatile than refinery gasoline, then the sample is classified as a Group 0. Natural gasolines were popular during the early days of petroleum refining, but are limited to specific markets these days. These materials are generally not sold to the general public. They are intermediate products suitable for transport and storage, but intended for further processing.

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Group 1 If the sample has a vapor pressure of P 65.5 kPa (9.5 psi) at 37.8 C (100 F) and a FBP or EP of O 250 C (482 F), then the sample is classified as a Group 1 material. Most spark-ignition engine gasolines that have been made by blending components fall into this category. Most refinery intermediate streams such as catalytic cracker light naphtha and similar materials are also Group 1 distillation material.

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Group 2 If the sample has a vapor pressure of < 65.5 kPa (9.5 psi) at 37.8 C (100 F) and an FBP or EP of O 250 C (482 F), then the sample is classified as a Group 2 material. Most hydrocarbon solvents are in this category. Aviation gasoline also falls into this group. Some intermediate refinery streams such as atmospheric and vacuum debutanizer bottoms, fluid catalytic naphtha, power former feed, are classified as Group 2 distillation materials.

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Group 3If the sample has a vapor pressure of < 65.5 kPa (9.5 psi) at 37.8 C (100 F), an IBP of O100 C (212 F), and a FBP or EP of O 250 C (482 F), then the sample is classified as a Group 3 material.

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Group 4 If the sample has a vapor pressure of < 65.5 kPa (9.5 psi) at 37.8 C (100 F), an IBP of > 100 C (212 F), and a FBP or EP of > 250 C (482 F), then the sample is classified as a Group 4 material. Examples of Group 4 materials are aviation turbine (Jet-A) gasoline, kerosene, and diesel fuels. Intermediate refinery streams such as atmospheric and vacuum heavy naphtha, heavy atmospheric gas oil, light atmospheric gas oil, hydrocracker distillate, and similar material belong to Group 4. Some heavy isoparaffinic and aromatic solvents also fall into this category.

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After deciding which distillation Group the sample belongs to, Table 2 should be consulted for the correct temperature required for sample storage or conditioning as may be required. It is important that these sample storage and conditioning temperatures be adhered to if the results are to be reported as having been run according to ASTM D86.

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Group 0 Requires sample storage and conditioning at < 5 C(40 F). Group 1 Requires sample storage and conditioning at < 10 C (50 F). Group 2 Requires sample storage and conditioning at < 10 C (50 F). Group 3 Requires sample storage at ambient temperature, and sample conditioning at ambient or 9 to 21 C (48 to 70 F) above pour point. Group 4 Requires sample storage at ambient temperature, and sample conditioning at ambient or 9 to 21 C (48 to 70 F) above pour point.
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Table 2 also gives some guidance on what to do regarding wet samples. If the sample is wet when it is delivered to the lab, another sample should be obtained that is free from suspended water (resample). If the resample is still wet, or if the sample is known to be wet, dry the sample by following 7.5.2 or 7.5.3 of D86-04b using anhydrous sodium sulfate or other suitable drying agent.

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Once the sample shows no visible signs of water, use a decanted portion of the sample maintained at < 10 C (50 F) for Groups 0, 1, and 2 or ambient temperature for Groups 3 and 4. The report shall note that the sample has been dried by the addition of a desiccant.

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Figure 1 shows a schematic illustration of the early manual D86 distillation unit. Figure 2 shows a schematic diagram of a setup using electric heaters. Figure 3 shows an example of the many automated D86 distillation units currently available on the market.

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Once the Group category of a given sample received in the laboratory is determined, and the sample is stored and conditioned as required, the next step is to set up the apparatus. Regardless of whether the manual or automated distillation units is used, the basic components of the distillation units are the same; namely,

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the distillation flask, the flask support board, the condenser and associated cooling system, the heat source, the temperature measuring device, and the receiving cylinder to collect the distillate

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Figure 4 shows the distillation flask dimensions for three type of flasks specified in D86: Flask A (100 mL) is for Group 0 materials (natural gasoline), Flask B (125 mL) for Group 1 to 4, and Flask B with ground glass joint for Groups 1 to 4. Figure 5 gives the detail of the upper neck section of the distillation flask with a ground glass joint.

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Table 3 gives the flask support board hole diameter for Group 0 to 4 material. For Group 0, the support board hole is indicated to be Type A with a diameter of 32 mm (1.25 in.). Groups 1 and 2 require a Type B support board with a hole diameter of 38 mm (1.5 in.). Type C support board for Groups 3 and 4 have a hole diameter of 50 mm(2.0 in.).

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The flask support board and hole diameter shall be of the prescribed dimension for each Group to ensure that the thermal heat to the flask comes only from the central opening and that extraneous heat to the flask other than through the central opening hole is minimized.

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It is important that the right size flask support hole is used for a material classified as belonging to a particular group. If a flask support hole larger than specified for a given group is used, more heat than what is required would be directed onto the flask, thus making the distillation go faster with possible lower distillation temperatures being recorded.

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Conversely, if a smaller flask support hole than specified for a given group is used, less heat than what is required would be directed onto the flask, thus making the distillation go more slowly with possible higher distillation temperatures being recorded.

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Using the wrong flask support hole diameter can also affect the time from the start of distillation to IBP, the time from IBP to 5 %, the average rate of distillation, and the EP rate/or temperature.

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In addition to giving the correct flask support hole diameter for each Group, Table 3 also gives information on the temperature of the flask and specimen at the start of the test and the receiving cylinder. Maintaining the temperature of the receiving cylinder at the prescribed temperature is easily done with automated instruments.

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However, such is not the case with the manual instrument. If the receiver cylinder temperature is much greater than what is prescribed, this could cause a loss of distillate, resulting in potentially higher distillation temperatures being reported.

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If no losses occur, potentially lower distillation temperature could be reported due to thermal expansion. Conversely, if the receiver temperature is much less than what is prescribed, the distillation temperatures may be higher due to thermal contraction.

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Table 4 gives the critical conditions that have to be met in order to be in compliance with the test requirements of D86. One of the parameters indicated is the temperature of the condenser, which is controlled by the cooling bath or cooling system employed in the apparatus.

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For Groups 0 and 1, the condenser temperature is required to be 0 C to 1 C (32 F to 34 F). Groups 2 and 3 require a condenser temperature of 0 C to 5 C (32 F to 40 F), while Group 4 would need to be maintained from 0 C to 60 C (32 F to 140 F).

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Sometimes, the importance of maintaining the correct condenser temperature is not appreciated, and using the incorrect condenser temperature can cause erroneous distillation results to be reported.

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If the condenser temperature in distilling a Group 0 or 1 material is greater than 1 C (33 F ), the condensation process in the condenser could be affected in such a way that the first drop of condensate is delayed, thereby resulting in a higher IBP value.

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In addition to the condenser temperature requirements for each distillation Group materials, Table 4 also gives other critical conditions that have to be met during the test in order to ensure conformance with the test method.

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These are: (1) time from the first application of heat to the IBP, in minutes; (2) time from IBP to 5% recovered in seconds or to 10% recovered for Group 0, in minutes; (3) average rate of distillation from 5 % recovered to about 5 mL in the flask, in mL/min; and (4) time recorded from 5 mL residue to EP or FBP, in minutes.

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Satisfying all these requirements during the early days of manual distillation was very difficult, especially when the heat source was a Bunsen burner. When D86-21T was published, both a gas burner as well as an electric heater were indicated to be acceptable heat sources.

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The critical parameter was the time from initial application of heat to IBP, and the distillation rate. Later versions of the test method introduced the other parameters. With electric heaters as the heat source, heat control was done mainly by adjusting the wattage setting. Considerable test operator time was spent in adjusting wattage settings to meet the required parameters.

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The manual D86 distillation procedure specifies two mercury-in-glass thermometers: ASTM 7C/IP 5C and ASTM 7F for low range distillation; i.e., 2 C to 300 C (30 F to 580 F), and ASTM 8C/IP 6C and ASTM 8F for high range distillation; i.e., 2 C to 400 C (30 F to 760 F).

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The automated D86 distillation procedure uses temperature measurement devices or systems other than the specified mercury-in-glass thermometers. Examples are thermocouples or platinum-resistance temperature probes.

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These other temperature measurement devices shall exhibit the same temperature lag, emergent stem effect, and accuracy as the equivalent mercury-in-glass thermometer. The electronic circuitry or algorithms, or both, used shall include the capability to simulate the temperature lag of a mercury-in-glass thermometer.

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More recently, other liquid-in-glass thermometer (non-mercury due to health exposure concerns) have become available. However, no published data comparing D86 results obtained using non-mercury liquid-in-glass thermometer and the specified mercuryin-glass thermometer is readily available.

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The mercury-in-glass thermometers specified in the manual procedure are full immersion thermometers. However, during the distillation measurement process, the thermometer is only partially immersed. This results in readings that are lower than those that would be obtained using partial immersion thermometers.

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Table 5 shows that the boiling point of toluene (used as a verification fluid) is determined to be 109.3 0.2 C when the distillation is done with an ASTM 7C thermometer relative to the 110.6 C reading obtained by a partial immersion thermometer, and 109.90.2 C for an ASTM8C thermometer. The same is true with the other types of temperature measuring device. Therefore, similar readings for the toluene boiling point should be obtained.

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The positioning of the temperature measuring device in the distillation flask is very important in order to get accurate results. Figure 6 shows the proper positioning of the thermometer in the distillation flask.

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Similar precaution needs to be observed for the other types of temperature measuring devices. For automated distillation instruments, follow the manufacturers instructions as to the proper placement position. In a major rewrite of D86 in 1996, the requirement for a temperature sensor centering device was introduced.

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The intent was to ensure that the temperature sensor is centered within the interior walls of the flask. Figure 7 shows an example of a centering device used for straight-bore neck flasks, and Fig. 8 shows a polytetrafluoroethylene (PTFE) centering device for flasks with a ground glass joint.

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Other centering devices are acceptable as long as they position and hold the temperature measurement device in the proper position in the neck of the distillation flask, as shown in Fig. 6. It is important to note that when running a distillation test using the manual procedure, products with a low IBP may have one or more readings obscured by the centering device.

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Calibration Calculation Results References

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