Method for measuring physical properties of hydrocarbons

• US 5,412,581 A
• Filed: 11/05/1992
• Issued: 05/02/1995
• Est. Priority Date: 11/05/1992
• Status: Expired due to Term

• Current Assignee: Marathon Petroleum Company LP (Marathon Petroleum Corporation)
• Original Assignee: Marathon Oil Company (Marathon Oil Corporation)
• Inventors: Tackett, James E.
• Primary Examiner(s): Voeltz, Emanuel T.
• Assistant Examiner(s): ASSOUAD, PATRICK J
• Application Number:
  US07/971,886
• Time in Patent Office: 908 Days
• Field of Search: 250/343, 250/339, 250/345, 250/349, 250/339.01, 364/498, 364/497, 364/499
• US Class Current: 702/30
• CPC Class Codes: G01N 21/3577 for analysing liquids, e.g. polluted water
• CPC Class Codes: G01N 21/359 using near infrared light

Abstract

A system for measuring the physical characteristics of a hydrocarbon places a reference hydrocarbon cell in thermal contact with a sample cell containing an unknown hydrocarbon. A near infrared spectrum measurement is taken of both the cells. Measurement data from the sample cell is adjusted by the measurement data from the reference cell, and the adjusted measurement data is evaluated by a model to predict the characteristics of the sample. The model is built from a teaching set of hydrocarbons having known physical characteristics and the reference hydrocarbon. Each of the teaching set hydrocarbons is measured and then adjusted by a measurement of the same reference hydrocarbon, and the adjusted measurements are used to build the model.

Claims

1. A method for determining at least one physical property of a sample hydrocarbon using spectrometry, said method comprising the steps of:

(a) selecting a reference hydrocarbon;

(b) selecting a teaching set of hydrocarbons, each having at least one physical property of the at least one physical property to be determined;

(c) placing said reference hydrocarbon in a reference cell in thermal contact with a sample cell;

(d) placing one of said hydrocarbons from said teaching set into said sample cell;

(e) measuring a reference absorption spectrum of said reference hydrocarbon;

(f) measuring a teaching absorption spectrum of said hydrocarbon within said sample cell wherein a set of wavelengths used for said measuring is the same as a set used in step (e);

(g) combining said reference absorption spectrum and said teaching absorption spectrum to create a teaching adjusted spectrum;

(h) computing a plurality of teaching sample values, one for each of a plurality of sample points of said teaching adjusted spectrum;

(i) inputting each of said teaching sample values into a multivariate analysis system to build a multivariate calibration model;

(j) repeating steps (d) through (i) for each hydrocarbon in said teaching set;

(k) placing said reference hydrocarbon in a reference cell in thermal contact with a sample cell containing said unknown-hydrocarbon sample;

(l) measuring a test reference absorption spectrum of said reference hydrocarbon in said reference cell, wherein a set of wavelengths used for said measuring is the same as a set used in step (e);

(m) measuring a sample absorption spectrum of said unknown hydrocarbon in said sample cell wherein a set of wavelengths used for said measuring is the same as a set used in step (e);

(n) combining said test reference absorption spectrum and said sample absorption spectrum to create a test adjusted spectrum;

(o) computing a plurality of test sample values, one for each of a plurality of sample points of said second adjusted spectrum; and

(p) inputting each of said test sample values into said multivariate analysis system to compare said test sample values to said multivariate calibration model to determine said at least one physical property of said sample hydrocarbon.

2. The process of claim 1 wherein step (g) comprises the following steps (g1) and (g2) and wherein step (n) comprises the following steps (n1) and (n2):

(g1) measuring a peak location of said teaching reference spectrum;

(g2) subtracting said teaching reference absorption spectrum peak location from each wavelength of said teaching absorption spectrum and dividing said reference absorption area into each absorption value of said teaching reference absorption spectrum to create said teaching adjusted spectrum;

(n1) measuring a peak location and area of said test reference spectrum;

(n2) subtracting said test reference absorption spectrum peak location from each wavelength of said sample absorption spectrum and dividing said reference absorption area into each absorption value of said teaching reference absorption spectrum to create said test adjusted spectrum.

3. The method of claim 1 wherein each of said measuring steps uses a spectrometer for said measuring and wherein each of said measuring steps further comprises the step of connecting said reference cell and said sample cell to said spectrometer through fiber optics cables prior to said measurement.

4. The method of claim 1 wherein step (e) further comprises the step of selecting at least one set of wavelengths in the near infrared spectrum for said measuring.

5. The method of claim 4 further comprising the step of selecting wavelengths between 1100 nanometers and 1300 nanometers for said measuring.

6. The method of claim 1 wherein each of said teaching set hydrocarbons and said unknown hydrocarbon comprises gasoline.

7. The method of claim 6 wherein said reference hydrocarbon comprises equal parts by volume of p-cymene and 2-methylhexane.

8. The method of claim 6 wherein said reference hydrocarbon comprises a highly branched dodecylbenzene isomer.

9. A method for determining at least one physical property of a sample hydrocarbon using spectrometry, said method comprising the steps of:

(a) selecting a reference hydrocarbon and placing said reference hydrocarbon in a reference cell adjacent a sample cell;

(b) selecting a teaching set of hydrocarbons, each having at least one physical property of the at least one physical property to be determined;

(c) selecting one hydrocarbon from said teaching set and placing said selected hydrocarbon in said sample cell;

(d) measuring a reference absorption spectrum of said reference hydrocarbon;

(e) measuring a teaching absorption spectrum of said hydrocarbon in said sample cell, wherein a set of wavelengths used for said measuring is the same as a set used in step (d);

(f) measuring a peak location and area of said reference spectrum;

(g) subtracting said reference absorption spectrum peak location from each wavelength of said teaching absorption spectrum and dividing said reference absorption area into each absorption value of said teaching absorption spectrum to create an adjusted spectrum;

(h) computing a plurality of sample values each sampling one point of said adjusted spectrum;

(i) inputting each of said teaching sample values into a multivariate analysis system to build a multivariate calibration model;

(j) repeating steps (c) through (i) for each hydrocarbon in said teaching set;

(k) placing said reference hydrocarbon in a reference cell in thermal contact with a sample cell containing said unknown hydrocarbon sample;

measuring a test reference absorption spectrum of said reference hydrocarbon in said reference cell, wherein a set of wavelengths used for said measuring is the same as a set used in step (d);

(m) measuring a sample absorption spectrum of said unknown hydrocarbon in said sample cell, wherein a set of wavelengths used for said measuring is the same as a set used in step (d);

(n) measuring a peak location and area of said test reference spectrum;

(o) subtracting said test reference absorption spectrum peak location from each wavelength of said unknown hydrocarbon absorption spectrum and dividing said reference absorption area into each absorption value of said unknown hydrocarbon absorption spectrum to create a test adjusted spectrum;

(p) computing a plurality of test sample values each sampling one point of said test adjusted spectrum; and

(q) inputting each of said test sample values into said multivariate analysis system to compare said test sample values to said multivariate calibration model to determine said physical properties.

10. The method of claim 9 wherein each of said measuring steps uses a spectrometer for said measuring and wherein each of said measuring steps further comprises the step of connecting said test reference cell and said test sample cell to said spectrometer through fiber optics cables prior to said measurement.

11. The method of claim 9 wherein step (d) further comprises the step of selecting at least one set of wavelengths in the near infrared spectrum for said measuring.

12. The method of claim 11 further comprising the step of selecting wavelengths between 1100 nanometers and 1300 nanometers for said measuring.

13. The method of claim 9 wherein each of said teaching set hydrocarbons and said unknown hydrocarbon comprises gasoline.

14. The method of claim 13 wherein said reference hydrocarbon comprises equal parts by volume of p-cymene and 2-methylhexane.

15. The method of claim 13 wherein said reference hydrocarbon comprises a highly branched dodecylbenzene isomer.

16. A method for determining the antiknock index of a sample gasoline using spectrometry, said method comprising the steps of:

(a) selecting a reference hydrocarbon and placing said reference hydrocarbon in a reference cell adjacent a sample cell;

(b) selecting a teaching set of gasolines, each having an antiknock index within a range of antiknock indexes for said sample gasoline;

(c) selecting one gasoline from said teaching set and placing said selected gasoline in said sample cell;

(d) measuring a reference absorption spectrum of said reference hydrocarbon;

(e) measuring a teaching absorption spectrum of one gasoline within said teaching set, wherein a set of wavelengths used for said measuring is the same as a set used in step (d);

(f) measuring a peak location and area of said reference spectrum;

(g) subtracting said reference absorption spectrum peak location from each wavelength of said teaching absorption spectrum and dividing said reference absorption area into each absorption value of said teaching absorption spectrum to create a teaching adjusted spectrum;

(h) computing a plurality of teaching sample values, one for each of a plurality of sample points of said teaching adjusted spectrum;

(i) inputting each of said sample values into a multivariate analysis system to build a multivariate calibration model;

(j) repeating steps (c) through (i) for each gasoline in said teaching set;

(k) placing said reference hydrocarbon in a reference cell in thermal contact with a sample cell containing said sample gasoline;

measuring a test reference absorption spectrum of said reference hydrocarbon in said reference cell, Wherein a set of wavelengths used for said measuring is the same as a set used in step (d);

(m) measuring a sample absorption spectrum of said sample gasoline in said sample cell, wherein a set of wavelengths used for said measuring is the same as a set used in step (d);

(n) measuring a peak location and area of said test reference spectrum;

(o) subtracting said test reference absorption spectrum peak location from each wavelength of said sample absorption spectrum and dividing said reference absorption area into each absorption value of said unknown hydrocarbon absorption spectrum to create a test adjusted spectrum;

(p) computing a plurality of test sample values, one for each of a plurality of sample points of said second adjusted spectrum; and

(q) inputting each of said test sample values into said multivariate analysis system to compare said test sample values to said multivariate calibration model to determine said antiknock index.

17. The method of claim 16 wherein each of said measuring steps uses a spectrometer for said measuring and wherein each of said measuring steps further comprises the step of connecting said test reference cell and said test sample cell to said spectrometer through fiber optics cables prior to said measurement.

18. The method of claim 16 wherein step (d) further comprises the step of selecting at least one set of wavelengths in the near infrared spectrum for said measuring.

19. The method of claim 18 further comprising the step of selecting wavelengths between 1100 nanometers and 1300 nanometers for said measuring.

20. The method of claim 19 wherein said reference hydrocarbon comprises equal parts by volume of p-cymene and 2-methylhexane.

21. The method of claim 19 wherein said reference hydrocarbon comprises a highly branched dodecylbenzene isomer.