UOP 375-2007 CALCULATION OF UOP CHARACTERIZATION FACTOR AND ESTIMATION OF MOLECULAR WEIGHT OF PETROLEUM OILS.pdf

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1、 IT IS THE USERS RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS PROCEDURE IN THE MANNER PRESCRIB

2、ED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS (MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION EQUIPMENT (PPE). COPYRIGHT 1959, 1986, 2007 UOP LLC. All rights r

3、eserved. Nonconfidential UOP Methods are available from ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA 19428-2959, USA. The UOP Methods may be obtained through the ASTM website, www.astm.org, or by contacting Customer Service at serviceastm.org, 610.832.9555 FAX, or

4、610.832.9585 PHONE. Calculation of UOP Characterization Factor and Estimation of Molecular Weight of Petroleum Oils UOP Method 375-07 Scope This method is for calculating the UOP Characterization Factor of petroleum oils from API gravity and distillation or viscosity data. Average molecular weight o

5、f petroleum oils is estimated from API gravity and distillation data. The UOP Characterization Factor, commonly called K, is indicative of the general origin and nature of a petroleum stock. Values of 12.5 or higher indicate a material predominantly paraffinic in nature. Highly aromatic materials ha

6、ve characterization factors of 10.0 or less. References ASTM Method D 86, “Distillation of Petroleum Products at Atmospheric Pressure,” www.astm org ASTM Method D 88, “Saybolt Viscosity,” www.astm org ASTM Method D 445, “Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of D

7、ynamic Viscosity),” www.astm org ASTM Method D 1160, “Distillation of Petroleum Products at Reduced Pressure,” www.astm org ASTM Method D 1250, “Guide for the Use of Petroleum Measurement Tables,” www.astm org ASTM Method D 1298, “Density, Relative Density (Specific Gravity), or API Gravity of Crude

8、 Petroleum and Liquid Petroleum Products by Hydrometer Method,” www.astm org ASTM Method D 2161, “Practice for Conversion of Kinematic Viscosity to Saybolt Universal Viscosity or Saybolt Furol Viscosity,” www.astm org Smith, R. L., and Watson, K. M., Ind. Eng. Chem., 29, 1408 (1937) Watson, K. M., N

9、elson E. F., and Murphy, G. B., Ind. Eng. Chem., 27, 1460 (1935) Outline of Method The UOP Characterization Factor, K, can be calculated using either distillation or viscosity data. The distillation data procedure calculates the K factor using data obtained from ASTM D 1298, “Density, 2 of 14 UOP 37

10、5-07 Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method,” in combination with either ASTM D 86, “ Distillation of Petroleum Products AT Atmospheric Pressure,” or ASTM D 1160, “Distillation of Petroleum Products at Reduced Pressur

11、e,” dependent on the sample, and the nomographs or engineering charts incorporated in the method. The viscosity data procedure calculates the K factor using data obtained from ASTM D 1298 in combination with either ASTM D 445, “Kinematic Viscosity of Transparent and Opaque Liquids (or the calculatio

12、n of Dynamic Viscosity),” or ASTM D 88, “ Saybolt Viscosity” and the nomographs incorporated in the method. The Average molecular Weight is estimated using the same data as for the K factor distillation data procedure, but with a different set of nomographs. The Appendix describes a procedure to cal

13、culate the K factor and the molecular weight using the relative density and ASTM Distillation data and equations that were derived from curve fits of the nomographs. If the sample is beyond the scopes of these methods, other standard methods may be substituted. In some cases, this may involve additi

14、onal calculations to convert the observed data to the appropriate units. Definitions Cubic average boiling point is the cube of the sum of the products of the volume fraction multiplied by the cube root of the boiling point of each component expressed in degrees Rankine. Mean average boiling point i

15、s the arithmetic average of the true molal boiling point and the cubic average boiling point expressed in degrees Fahrenheit. Molecular weight, as employed herein, is that average molecular weight of a petroleum fraction and not that of a single, pure compound. True molal average boiling point is th

16、e sum of the products of the mol fraction multiplied by the boiling point of each component. UOP Characterization Factor, K, of a petroleum oil is defined as the cube root of its cubic average boiling point, in degrees Rankine, divided by its relative density at 60F (15.56C). Volumetric average boil

17、ing point is the arithmetic average boiling point over the range of 10% to 90% of the ASTM distillation. Apparatus No additional apparatus is required beyond the apparatus listed in the above methods. Procedure Determine the API gravity or relative density at 60F of the sample according to ASTM D 12

18、98. Perform an ASTM distillation by either ASTM D 86 or D 1160, as appropriate for the sample. Correct the data to 760 mm Hg and for material loss as specified in these methods. Convert temperatures recorded in degrees Celsius to degrees Fahrenheit. Characterization factor may also be estimated usin

19、g kinematic viscosity at 100, 122 or 210F (38, 50 or 99C). Kinematic viscosity is determined directly from ASTM D 445. Saybolt viscosity, determined by ASTM D 88, can be converted to kinematic viscosity using ASTM D 2161. 3 of 14 UOP 375-07 Calculations UOP K Factor from API Gravity and ASTM Distill

20、ation Volumetric Average Boiling Point Calculate the volumetric average boiling point as the average of the 10, 30, 50, 70 and 90 vo1-% temperatures. Calculate the slope as F per percent (F/%) by subtracting the 10 vol-% temperature from the 90 vol-% temperature, and dividing the difference by 80 vo

21、l-%. Cubic Average Boiling Point Obtain the value of the correction to be applied to the volumetric average boiling point using Figure 1. Using the value of the slope calculated above, go to the bottom of the chart, then proceed vertically to the curve which represents the value of the volumetric av

22、erage boiling point. Interpolate between curves as needed. Read the value of the vertical scale on the left side corresponding to this point to obtain the value of the correction term. Subtract this term from the volumetric average boiling point to calculate the cubic average boiling point. UOP Char

23、acterization Factor, K Determine the UOP Characterization Factor, K, using the cubic average boiling point and API gravity. Locate the cubic average boiling point on the horizontal scale at the bottom of Figure 2. Locate the API gravity on the vertical scale at the left of the graph. Find the inters

24、ection of the vertical and horizontal lines from these points. Read the number of the curve nearest to this point. This number, corrected by interpolation for the distance of the point from the nearest curve, is the characterization factor, K. Example: Calculate the characterization factor for a gas

25、 oil of 28.7 API at 60F having the following distillation properties: ASTM Distillation (Corrected to 760 mm Hg Pressure) Volume-% 10 30 50 70 90 Temp., F 598 700 755 802 874 Volumetric average boiling point = 5874802755700598 += 746 Slope = 80598874 = 3.45F/volume-% Correction term = 5F from Figure

26、 1 Cubic average boiling point = 746 5 = 741F Characterization factor, K = 12.03 from Figure 2 UOP K Factor from API Gravity and Kinematic Viscosity Viscosities measured at high temperatures yield more reliable values for characterization factors than viscosities measured at low temperatures. Viscos

27、ity at low temperatures is influenced by the width of boiling range as well as by relative density and characterization factor. For samples that do not yield a 4 of 14 UOP 375-07 full distillation range by ASTM Method D 1160, the use of viscosities measured at 210F (99C) is preferred, where practica

28、l. Nomographs based on viscosities measured at 100F (38C) and 122F (50C) are also included for convenience. The UOP Characterization Factor, K, is determined from Figures 3, 4 or 5, respectively, by entering with the API gravity and kinematic viscosity at 100, 122 or 210F (38, 50 or 99C). Locate the

29、 API gravity on the horizontal scale at the bottom of the chart. Locate the kinematic viscosity on the vertical scale at the left of the chart. Find the intersection of the vertical and horizontal lines from these points. Read the number of the curve nearest to this point. This number, corrected by

30、interpolation for the distance of the point from this curve, is the characterization factor, K. Figure 1 Cubic Average Boiling Point from Volumetric Average Boiling Point and Distillation (Engler) Slope 5 of 14 UOP 375-07 Figure 2 UOP Characterization Factor K, from API Gravity and Cubic Average Boi

31、ling Point 6 of 14 UOP 375-07 Figure 3 Characterization Factor from Viscosity at 100 F and API 7 of 14 UOP 375-07 Figure 4 Characterization Factor from Viscosity at 122 F and API 8 of 14 UOP 375-07 Figure 5 Characterization Factor from Viscosity at 210 F and API 9 of 14 UOP 375-07 Example: Calculate

32、 the characterization factor for the gas oil of the previous example from API gravity and viscosity measured at 210F. From ASTM D 88: 39.7 Saybolt Universal Seconds From ASTM D 2161: 4.1 centistokes From ASTM D 1298: 28.7 API From Fig. 5: K = 12.0 Molecular Weight from API Gravity and ASTM Distillat

33、ion The molecular weight of typical petroleum fractions may be estimated by this method. It should not be applied to estimating the molecular weight of a pure hydrocarbon compound. Calculate the volumetric average boiling point and slope from the distillation data as in the previous section. Using F

34、igure 6, obtain the correction to be applied to the volumetric average boiling point. Enter Figure 6 on the horizontal scale at the value of the slope and proceed vertically to the curve which represents the value of the volumetric average boiling point, interpolating between curves if necessary. Re

35、ad the value of the vertical scale on the left which corresponds to this point to obtain the value of the correction term. Subtract this term from the volumetric average boiling point to obtain the mean average boiling point. Determine the molecular weight using Figure 7. Locate the mean average boi

36、ling point on the horizontal scale at the bottom of the chart. Locate the API gravity on the vertical scale at the left of the chart. Find the intersection of the vertical and horizontal lines from these points. Read the number of the diagonal curve nearest this point. This number, corrected by inte

37、rpolation for the distance of the point from this curve, is the molecular weight. Example: Volumetric average boiling point = 746 Slope = 3.45 F/volume-% From Figure 6: Correction term = 17 F Mean average boiling point = 746 17 = 729F From Figure 7: Molecular weight = 345 Precision An estimated stan

38、dard deviation is not reported because insufficient data are available at present to permit this calculation with at least 4 degrees of freedom. The precision and accuracy of this method is dependent upon the precision and accuracy of the methods used to obtain the experimental data upon which the c

39、alculations are based. Precision is also dependent upon interpolation of the nomograph. Time for Analysis The elapsed time and labor requirement for one calculation are identical, 0.2 hour. 10 of 14 UOP 375-07 Figure 6 Mean Average Boiling Point from Volumetric Average Boiling Point and Distillation

40、 (Engler) Slope 11 of 14 UOP 375-07 Figure 7 Molecular Weight from Mean Average Boiling Point and API Gravity 12 of 14 UOP 375-07 Appendix If desired, computation by a computer or programmable calculator may be substituted for the nomographs using the equations given below. Except for Equations A1,

41、A2, A6, and A7, these relationships were derived from curve fits of Engineering Charts which, in turn, were derived from empirical data. Consequently, any attempt to use these equations to extrapolate beyond the limit of the nomographs will produce results that, at least, must be viewed with suspici

42、on. UOP K Factor from API Gravity and ASTM Distillation Calculate the volumetric average boiling point, F, as follows: V =5BBBBB9070503010+(A1) where: B10= temperature of ASTM distillation, 10% over, F 30= temperature of ASTM distillation, 30% over, F B50= temperature of ASTM distillation, 50% over,

43、 F 70= temperature of ASTM distillation, 70% over, F B90= temperature of ASTM distillation, 90% over, F V = volumetric average boiling point, F 5 = constant for averaging Calculate the slope of distillation, F/volume-%, as follows: S =80BB1090(A2) where: B10, B90= previously defined S = slope of dis

44、tillation, F/volume-% 80 = constant, volume-% (90-10 volume-%) Calculate the cubic average boiling point, F, as follows: C = A+VE (A3) where: A = defined by Equation A4 C = cubic average boiling point, F E = defined by Equation A5 V = volumetric average boiling point (Equation A1), F A = 0.581 S2 1.

45、339 S (A4) where: A = correction factor S = slope of the distillation (Equation A2) 0.581 = constant derived from curve fit of the nomograph 1.339 = constant derived from curve fit of the nomograph E = 0.000297 S2 +0.001438 S +1 (A5) where: E = correction factor S = previously defined 0.000297 = cur

46、ve fitting constant 0.001438 = curve fitting constant 13 of 14 UOP 375-07 Calculate the relative density at 60F, g/mL, as follows: D =G5.1315.141+(A6) where: D = relative density at 60F, g/mL G = API gravity, API 131.5 = constants, from ASTM D 1298 141.5 = constants, from ASTM D 1298 Relative densit

47、y can be determined directly, thus eliminating the need for this conversion. Calculate UOP Characterization Factor, K, as follows: K =D)7.459C(3/1+(A7) where: C = cubic average boiling point (Equation A3) D = relative density (Equation A6) K = UOP Characterization Factor 459.7 = constant to convert

48、degrees Fahrenheit to degrees Rankine Molecular Weight from Relative Density and ASTM Distillation Calculate the mean average boiling point, F, as follows: M =2VHFC +(A8) where: C = previously defined (Equation A3) F = defined by Equation A9 H = defined by Equation A10 M = mean average boiling point

49、, F V = volumetric average boiling point (Equation A1) F = 1.901 S2 7.498 S (A9) where: F = correction factor S = slope of the distillation (Equation A2) 1.901 = curve fitting constant 7.498 = curve fitting constant H = 0.000328 S2 +0.006081 S +1 (A10) where: H = correction factor S = slope of the distillation (Equation A2) 0.000328 = curve fitting constant 0.006081 = curve fitting constant Calculate the average molecular weight as follows: W = antilogIM +J +(L/M) (A11) where: 14 of 14 UOP 375-07 I = defined by Equatio