Vapor Pressure Of Petroleum Merchandise
Many problems involving hydrocarbon methods include a specification of some sort of vapor pressure measurement. The vapor pressure of a mixture is commonly defined as the pressure where the first bubble of vapor is formed at a given temperature however there are different definitions primarily based on standardized experimental measurements or correlations. Examples of these definitions are: Reid Vapor Stress, Vapor Strain of Crude Oils and Vapor Stress of Liquefied Petroleum Gases, all of them outlined by ASTM (American Society for Testing Supplies) standard methods [1, three, 4].
The target of this article is to current and discuss the several types of vapor stress calculations available in VMGSim together with describing their calculation procedures, ranges of validity and units. Validation examples are also included.
Vapor Strain Definitions
The following vapor strain definitions might be accessed in VMGSim from the Special Properties unit operation, as well because the Refinery and Pure Gas tabs from the material Stream. These properties are obtained from flash-based mostly calculations in the coal gasification process carbon monoxide that rely on the selected property package deal.
Vapor Strain, also referred to as bubble point pressure and true vapor stress, is the pressure the place the primary bubble of vapor is formed at a given temperature. The composition (in the case of a mixture) also influences this equilibrium pressure.
VMGSim calculates the vapor strain by flashing the mixture of interest using a vapor fraction equal to zero on the temperature specified in the stream that accommodates the mixture.
The Vapor Stress is reported in absolute pressure units.
True Vapor Stress @ one hundred F
This property is similar to the Vapor Strain calculation except that the flash calculation is carried out at a selected temperature of 100 F.
The Vapor Pressure @ 100 F is reported in absolute pressure models.
True Vapor Stress @ Storage Temperature
It’s defined because the vapor stress of a liquid hydrocarbon calculated primarily based on the ASTM D6377-10  customary method and the Environmental Safety Company (EPA) publication AP-forty two .
This property is calculated based on an equation presented within the EPA publication, derived from a nomogram first published by the American Petroleum Institute (API), which is based on the Reid Vapor Strain Equal of non – pressurized vessels (see definition below) and the storage temperature. The storage temperature is defined by the desired temperature in the stream that contains the mixture of interest.
The Vapor Strain @ Storage Temperature is reported in absolute pressure units.
Reid Vapor Stress (RVP) (D323)
The Reid Vapor Pressure is a vital property of gasolines and jet fuels and it in the coal gasification process carbon monoxide is used as a criterion for blending of products. Additionally it is a useful parameter for the estimation of losses from storage tanks throughout filling or draining.
The Reid Vapor Strain is outlined because the vapor stress of a mixture as it was measured in accordance with the experimental technique depicted in the ASTM D323-99a commonplace methodology . This take a look at method covers the Reid Vapor Strain dedication of gasoline, unstable crude oils, and different risky petroleum products.
The usual technique establishes that the analyzed mixture must be positioned in a pattern container kept in a cooling bath at 32 F. Air saturation of the sample is carried out by vigorously shaking the container and returning it to the cooling bath. The pattern is transferred to a test apparatus consisting of two interconnected liquid and vapor chambers and equipped with an appropriate pressure-measuring machine. The ratio of the quantity of the vapor chamber to the volume of the liquid chamber is 4. The complete system is immersed in a water bath at one hundred F and as soon as equilibrium is attained the noticed strain from the measuring system is reported as the Reid Vapor Strain.
VMGSim calculates the Reid Vapor Strain by simulating the ASTM D323-99a experimental procedure. The mixture from the stream of interest is saturated with air (N2 seventy nine%, O2 21% mol) at 32 F and 1 atm. Each N2 and O2 have to be current within the component listing from the property package for the correct use of this method. The resulting saturated mixture is then flashed at a hundred F and a constant vapor/liquid volumetric ratio of 4 to 1 (vapor volume fraction = zero.8), and the calculated strain is reported as the Reid Vapor Pressure (D323).
Earlier calculations in VMGSim did not take into consideration the air saturation, which brought on the outcomes to be decrease. That is not the case since VMGSim 9.5 includes an choice to enable the air saturation of the mixture. This feature is activated by way of a check box that can be found in the Particular Properties Unit Operation or the Refinery and Pure Gasoline tabs from the fabric Stream as seen in the next figures. If N2 and O2 aren’t current in the element record the calculation is carried out without air saturation.
As established in ASTM D323-99a, the Reid Vapor Stress is absolutely the stress that is essential to exert on a petroleum product in order to obtain a Vapor/Liquid ratio of four at 37.Eight C (a hundred F). There was widespread confusion associated to the stress items of this property. Since most vapor pressures are reported in absolute pressures, most observers count on the Reid Vapor Strain to observe this norm.
The ASTM D323-99a method establishes that the Reid Vapor Pressure is read from a stress-measuring machine that’s hooked up to an ambient air filled chamber. The ASTM D323-99a methodology experiences that the Reid Vapor Pressure must be reported in units similar to “psi” or “kPa”; and, no place within the ASTM D323-99a normal states that models akin to “psia” or “kPa absolute” should be used.
Previous variations of VMGSim reported the Reid Vapor Strain with absolute strain items. That is not the case since it has been determined to report the Reid Vapor Pressure using “psi” and “kPa” models in an effort to honor the ASTM D323-99a method. Although the models have changed, the calculated values are the identical as in previous versions since the internal flash calculations are still the same and based mostly on absolute pressures.
Vapor Pressure of Liquefied Petroleum Gasoline (LPG) (D1267)
The Vapor Strain of Liquefied Petroleum Gases (LPG) is measured based on the ASTM D1267-12 customary technique [four], which differs from D323-99a in that the latter is used to measure vapor stress of gasoline and volatile petroleum merchandise.
The ASTM D1267-12 commonplace method follows an analogous process than the D323-99a method, except that the ratio of the quantity of the vapor chamber to the amount of the liquid chamber is 2. The sample is equally saturated with air at 32 F and the vapor pressure kind the system can also be learn from a pressure-measuring device attached to the apparatus.
VMGSim calculates this property by simulating the ASTM D1267-12 experimental procedure. The mixture from the stream of interest is saturated with air (N2 79%, O2 21% mol) at 32 F and 1 atm. The resulting saturated mixture is then flashed at a hundred F and a relentless vapor/liquid volumetric ratio of two to 1 (vapor volume fraction = 0.666), the calculated strain is reported because the Vapor Stress of LPG (D1267).
The air saturation could be activated by means of the same check field as within the Reid Vapor Stress calculation. If N2 and O2 are not current within the part listing the calculation is done with out the saturation half.
Previously, VMGSim labeled this property as Reid Vapor Pressure D1267 but this is not the case since it has been modified to Vapor Strain of LPG (D1267).
Like in the D323-99a method, there may be confusion concerning the items used for this property. The ASTM D1267-12 methodology states that the Vapor Pressure of the LPG have to be reported in “kPa” or “psi”. Just like the Reid Vapor Pressure, it has been decided to report the Vapor Stress of the LPG (D1267) with “psi” and “kPa” units with a purpose to honor the ASTM D1267-12 methodology.
Vapor Strain of Crude Oil (VPCRX) (D6377)
The ASTM D6377-10 methodology  covers the experimental process to obtain the vapor strain of crude oils. The strategy may be very just like D323-99a however in this case the air saturation shouldn’t be required. The vapor strain is determined by this method at a vapor/liquid ratio of X to 1 (the place X varies from zero.02 to 4) at one hundred F.
VMGSim calculates the Vapor Strain of the Crude Oils (D6377-10) by simulating the experiment described in the ASTM D6377-10 technique. The mixture of interest is flashed at 100 F and a relentless vapor/liquid volumetric ratio of X to 1 (X will be specified by the person and its default value is 4 as seen in the next figures). The resulting calculated pressure is reported as the Vapor Stress of Crude Oils (D6377-10).
In earlier versions of VMGSim this property was labeled because the Reid Vapor Stress Equal (RVPE), which is obtained by a different process. Now, the RVPE is obtained through a new property as shown below.
This ASTM D6377-10 technique also reviews that measurements have to be reported in “psi” or “kPa”. Therefore, in an effort to comply with the strategy, it was decided to report the Vapor Strain of Crude Oils (D6377-10) with “psi” and “kPa” models.
Reid Vapor Stress Equal (RVPE)
The Reid Vapor Strain Equivalent (RVPE) for pressurized and non-pressurized vessels are values calculated by the defined correlations from the ASTM D6377-10 normal technique (Appendix XI)  using a vapor/liquid ratio of four and a temperature of 100 F.
These properties are new to VMGSim and are labeled as:
– RVPE (Pressurized Vessels)
– RVPE (Non-Pressurized Vessels)
The non-pressurized value is utilized in a correlation from the EPA Publication AP-42  to acquire the True Vapor Pressure at Storage Temperature (see description above).
To be able to be in keeping with the previous vapor stress calculations from ASTM strategies the Reid Vapor Pressure Equivalent has units of “psi” and “kPa”.
Summary of Vapor Stress Definitions
The next tables show the principal traits of the beforehand described vapor strain definitions.
Feedback on Vapor Strain
If True or Reid Vapor Strain values are calculated for oils or its fractions, the oil pseudo-components should be modeled as accurately as doable with respect to the oil characterization knowledge. The calculation of the oil pseudo-elements bodily properties is very important since they outline the computation of fugacities and equilibrium ratios which can be a part of the flash calculations utilized in vapor strain willpower.
The chemical nature of the oil pseudo-elements additionally impacts these bodily properties and one approach to take this into account is by using VMGSim’s PIONA Characterization (see Instance three under).
The following examples, taken from literature, are used to show VMGSim’s functionality on calculating vapor pressures. All examples had been calculated using VMGSim 9.5 (construct 68).
Example 1 – Air Saturated Pure Component
The ASTM 6377-10 normal technique  publishes acceptable reference Reid Vapor Pressure (RVP) values for air saturated reference fluids. The following table exhibits the comparability of these values with these calculated from VMGSim:
VMGSim’s values were calculated utilizing the Superior Peng-Robinson property package. VMGSim reviews correct outcomes which might be within, or near, the reported uncertainty.
Example 2 – Pure Hydrocarbons Mixture
Campbell  and McKetta  give the RVP and TVP @ a hundred F values for the hydrocarbon mixture shown in the subsequent table. Campbell  studies that the air was removed from the cell the place the RVP was measured. Because of this the D6377 methodology will probably be used to calculate this worth.
The reported RVP is 18 psi and the TVP is 19.5 psia. Utilizing VMGSim, the values for RVP (truly the Vapor Strain of Crude Oils D6377) and TVP had been discovered to be 18.Forty five psi and 19.21 psia, respectively, as it may be seen in the subsequent determine. Calculations have been done using the Advanced Peng-Robinson property package deal.
Instance 3 – Gasoline Assay
Gardiner  confirmed an ASTM D86 distillation curve and an RVP D323 worth for a Gentle Isocrackate (LIC). The following desk shows the gasoline’s ASTM D86 distillation information, the LIC has a reported RVP value of 11.5 psi.
To characterize this fluid, VMGSim’s PIONA Characterization was used in order to reap the benefits of the bodily properties calculation primarily based on the chemical nature of the PIONA Slate.
This example has been completed using the Advanced Peng-Robinson property package deal. The following pure components had been added to the parts checklist: Nitrogen, Oxygen, Methane, Ethane, Propane, iso-Butane, n-Butane, iso-Pentane and n-Pentane and the PIONA Slate was constructed with the next traits:
Notice that Nitrogen and Oxygen have been added to the part listing so as to have the ability to perform air saturation within the pattern. Inside the flowsheet setting an Oil Supply unit operation was added and the D86 distillation curve was entered utilizing the Direct Calculation methodology (the IBP value from the adjustment in the coal gasification process carbon monoxide factors was set to zero.16 and the EBP worth to 0.03). Once this was executed, an in depth match between calculated and experimental values of the distillation curve was obtained.
To inspect the RVP a cloth Stream was linked to the Oil Source and a Particular Properties unit operation was then attached to the material Stream. In the Refinery Tab from the Particular Properties unit operation, the Reid Vapor Pressure (D323) was selected and the air saturation was included to acquire the RVP value:
The calculated RVP worth is 11.87 psi, which may be very near the experimental worth (eleven.5 psi). Be aware that this worth has been obtained with “out of the box” calculations from VMGSim, with no regressions involved aside from the oil characterization.
Herbert Loria, Ph.D, P.Eng. VMG Calgary
Please contact your local VMG workplace for extra data.
 ASTM International. ASTM D6377-10 Standard Test Methodology for Dedication of Vapor Strain of Curde Oil VPCRX (Expnasion Method) ASTM Worldwide, West Conshohocken, PA, 2010
 U. S. Environmental Protrection Agency Compilation of Air Pollutant Emissions, Ch. 7 Publication AP-forty two 5th Ed. 2006
 ASTM International. ASTM D323-99a Normal Check Methodology for Vapor Strain of Petroleum Merchandise (Reid Technique) ASTM Worldwide, West Conshohocken, PA, 1999
[four] ASTM Worldwide. ASTM D1267-12 Commonplace Test Technique for GageVapor Strain of Liquefied Petroleum (LP) Gases (LP-Gas Technique) ASTM Worldwide, West Conshohocken, PA, 2012
 Campbell, J. R. Gas Conditioning and Processing 7th Ed. Campbell Petroleum Seires, Norman, Ok, 1992
 McKetta Jr, J. J. Encyclopedia of Chemical Processing and Design: Vol.
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