Indirect method for determining oxygenate content using near-infrared absorption spectra

• US 5,362,965 A
• Filed: 05/10/1993
• Issued: 11/08/1994
• Est. Priority Date: 05/27/1992
• Status: Expired due to Term

• Current Assignee: Marathon Petroleum Company LLC (Marathon Petroleum Corporation)
• Original Assignee: Ashland Oil, Inc. (Ashland Global Holdings, Inc.)
• Inventors: Maggard, Steven M.
• Primary Examiner(s): Hannaher, Constantine
• Application Number:
  US08/059,700
• Time in Patent Office: 547 Days
• Field of Search: 250/339, 250/340, 250/343, 250/339.12
• US Class Current: 250/339.12
• CPC Class Codes: G01N 21/3577 for analysing liquids, e.g. polluted water
• CPC Class Codes: G01N 21/359 using near infrared light
• CPC Class Codes: G01N 33/2829 Mixtures of fuels

Abstract

Method for determining oxygenate content and/or octane of hydrocarbon fuels suitable for automotive vehicles. Selecting nanometer frequencies in the range 1,300 to 1,350 reduces the temperature dependence of calibration equations that predict values representative of both oxygenate content and octane. This can be further improved by using only derivatives of selected temperature-dependent frequencies in addition to those in the 1,300 to 1,350 nanometer range. The selected frequencies preferably primarily correspond to C-H vibrational modes.

Claims

1. A method for controlling total oxygenate content of a composition that comprises at least 1% by volume of oxygenate content, comprising in combination the steps:

a. measuring the value of at least one absorbance in at least one wavelength between about 1,300 to1,350 nanometers; and

b. substituting said value into an equation to obtain a prediction of oxygenate content of said composition, whereby the effect of temperature on said prediction is reduced; and

c. controlling said composition in response to said prediction.

2. The improved method of claim 1, wherein said valve is measured at at least one other wavelength within the infrared spectrum of said composition, whereby the temperature dependence of said prediction of oxygenate content is reduced or the Standard Error of Estimate for said prediction of oxygenate content is improved.

3. The improved method for claim 2, wherein said at least one other absorbance band which reduces temperature dependence comprises using frequencies that involve C-H stretching or bending vibrations.

4. The improved method of claim 1 wherein oxygenate content involves oxygen present in species selected from the group consisting of:

alcohols and ethers.

5. The improved method of claim 4 wherein the alcohols and ethers are selected from the group consisting of methanol, ethanol, propanol, iso-propanol, n-butanol, isobutanol, t-butanol, iso-amyl alcohol, t-amyl alcohol, methyl t-butyl ether, ethyl t-butyl ether, methyl iso-amyl ether, ethyl iso-amyl ether, methy t-amyl ether, and ethyl t-amyl ether.

6. The improved method of claim 1, wherein said value is changed by a mathematical transformation prior to substitution into said calibration equation.

7. The improved method of claim 6, wherein said mathematical transformation of said at least one absorption band in the near infrared involves a finite difference derivative having a number of segments in the range 6 to 25 and a gap in the range 0 to 5.

8. The improved method of claim 7 wherein said number of segments is in the range 15 to 25.

9. An improved method for controlling octane of a composition that contains at least 1% by volume of an alcohol, comprising in combination:

a. measuring the absorbance of said composition in at least one band in the infrared spectrum;

b. transforming said absorbance by a mathematical transformation comprising taking its derivative of first or higher order

c. substituting said derivative into an equation which provides a prediction to predict octane of said composition and

d. controlling blending of components, including said alcohol, which affect the octane of said composition, in response to said prediction.

10. The improved method of claim 9 wherein said at least one absorption band is selected from the group consisting of a first band in the range 1576 to 1596 nm.

11. The improved method of claim 10, wherein there is an additional absorption band in the range 1140 to 1266 nm that is also used in said calibration equation.

12. The improved method of claim 10, wherein said absorbance is measured at at least one other wavelength in the range 1576 to 1596 nm and is transformed into a finite difference derivative of at least first order prior to use in said calibration equation.

13. The improved method for claim 9 wherein said frequencies that involve C--H stretching or bending vibrations, comprise methyne bands and their overtones.

14. An improved method for controlling alcohol content of an at least 1% by volume oxygenate-containing composition comprising:

a. measuring absorbance in an infrared band in the range 1576 to 1596 nm;

b. transforming said absorbance by a mathematical transformation;

c. substituting said absorbance so changed into an equation which defines a prediction of values representative of alcohol content of said composition; and

d. controlling blending of said composition in response to said prediction.

15. The improved method of claim 14, wherein said mathematical transformation is at least a first order finite difference derivative.

16. The improved method of claim 15, wherein said at least first order finite difference derivative involves a number of segments in the range 4 to 30 and a gap in the range 0 to 4.

17. The improved method claim 16 wherein said number of segments is in the range 15 to 25.

18. The improved method of claim 14, wherein at least one other infrared spectral absorbance of said oxygenate-containing composition is selected from frequencies which reduce temperature dependence or which improves the Standard Error of Estimate for said alcohol content.

19. An improved method for controlling alcohol content of an at least 1% by volume oxygenate-containing composition comprising:

a. measuring absorbance in an infrared band in the range 1310 to 1340 nm;

b. transforming said absorbance by a mathematical transformation;

c. substituting said absorbance so changed into an equation which defines a prediction of values representative of alcohol content of said composition; and

d. controlling blending of said composition in response to said prediction.

20. The improved method for determining octane of claim 19, wherein said at least one absorption band is changed by a mathematical transformation prior to use in a calibration equation from which values representative of said octane are defined in relation to said at least one mathematically transformed absorption band.

21. The improved method for determining octane of claim 20, wherein said mathematical transformation is selected from a group consisting of finite difference derivatives of first and higher orders.

22. The improved method for determining octane of claim 19, wherein there is additionally used an absorbance within the spectrum of absorbances for said composition corresponding to a band selected from a methyne band and their overtones determined by taking at least first order finite difference derivatives of said spectrum.