Process and apparatus for analysis of hydrocarbons by near-infrared spectroscopy

• US 5,349,189 A
• Filed: 11/05/1992
• Issued: 09/20/1994
• Est. Priority Date: 04/09/1990
• 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): FIELDS, CAROLYN
• Application Number:
  US07/972,259
• Time in Patent Office: 684 Days
• Field of Search: 250/339, 250/343
• 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 2201/129 Using chemometrical methods
• CPC Class Codes: G01N 33/2829 mixtures of fuels, e.g. determining the RON-number

Abstract

Certain selected wavelengths in the near infrared spectra permit analysis of weight percent, volume percent, or even mole percent of each component, e.g. PIANO (paraffin, isoparaffin, aromatic, napthenes, and olefins), octane (preferably research, motor or pump), and percent of various hydrocarbons, e.g. alpha olefins. Analysis can be nearly continuous analysis on-line or at-line, as well as batch analysis, e.g. in a quality control laboratory. Preferably the NIR data is converted to a second derivative of the spectra and multiple linear regression performed to model the individual PIANO concentrations, and to predict physical properties of fuel blending components, e.g. research octane of reformate, etc.

Claims

1. In a process for the control of hydrocarbons and substituted hydrocarbons in a complex mixture comprising as components;

paraffins, isoparaffins, aromatics, naphthenes, or olefins to determine component concentration, the improvement comprising in combination;

a. measuring the near infrared absorbance at at least three wavelengths comprising at least one wavelength in any of the following bands;

1672-1698, 1700-1726, 1622-1650, 1092-1156, 824-884, 1656-1692, 880-974, 1152-1230, 1320-1380, 1470-1578, 1614-1644, 1746-1810, 1940-2000, and/or 2058-2130 nanometers (nm),

b. taking each of the absorbances measured, or a mathematical function thereof,

c. performing statistical treatment using said absorbances or functions as the individual independent variables,

d. assigning and applying weighting constants or their equivalents to said independent variables,

applying the above steps using known compositions in a calibration step to calibrate the instrument and determine said weighting constants or equivalents,

repeating said steps a. and b. with unknown compositions, applying the weighting constants or equivalents determined during said calibration with known compositions to output a signal or signals indicative of a paraffin, is oparaffin, aromatic, or naththene component or components concentration,

controlling blending, hydrocarbon refining or chemical process by means of apparatus responsive to said signal or signals.

8. A process according to claim 1, 6 or 7 wherein said statistical treatment comprises partial least squares analysis.

9. A process according to claim 1, 6, or 7, wherein said hydrocarbons comprise reformer feed, reformate (stabilized and/or unstabalized), fluid catalytic cracker product, alkylate gasoline, polymerization gasoline, isomerate gasoline, and raffinate, or other refinery blending streams or mixtures thereof.

10. A process according to claim 1, 6, or 7, wherein said composition comprises alpha olefins or mixtures thereof.

11. A process according to claim 1, 6, or 7, wherein said mixture flows substantially intermittently or continuously past the point of measuring said absorbance.

12. A process according to claim 1, or 6, wherein said functions comprise a derivative of said absorbance.

13. A process according to claim 1, 6, or 7, wherein said functions are obtained by a process comprising a base line offset correction.

14. A process according to claim 1, 6, or 7, wherein said weighting constants are obtained by a process comprising partial least squares analysis, principal component regression, Gauss-Jordan row reduction or multiple linear regression.

15. A process according to claim 1, 6, or 7, wherein said signal controls a fuel blending system feeding blending components having different PIANO compositions into a common zone, whereby a product having a desired octane, cetane, or PIANO composition is produced.

16. A process according to claim 1, 6, or 7, wherein said complex mixture is gasoline.

17. A process according to claim 1, 6, or 7, wherein said complex mixture comprises diesel fuel.

18. A process according to claim 1, or 7, wherein the hydrocarbons and/or substituted hydrocarbons being monitored are involved in a chemical reaction.

19. A process according to claim 1, 6, or 7 wherein said weighting constants are obtained by a process comprising principal component regression analysis.

20. A process according to claim 1, 6, or 7 wherein said absorbance is measured at wavelength within the 824-884 nm band.

21. A process according to claim 1, 6, or 7, wherein said absorbance is measured in the 1672-1698 nm band.

22. A process according to claim 1, 6, or 7, wherein said absorbance is measured in the 1700-1726 nm band.

23. A process according to claim 1, 6, or 7, wherein said absorbance is measured in the 1622-1650 nm band.

24. A process according to claim 1, 6, or 7, wherein said absorbance is measured substantially in the 1092-1156 nm band.

25. A process according to claim 1, 6, or 7, wherein said absorbance is measured substantially in the 1656-1692 nm band.

26. A process according to claim 1, 6, or 7, wherein said absorbance is measured substantially in the 1320-1380 nm band.

27. A process according to claim 1, 6, or 7, wherein said absorbance is measured in the 1470-1578 nm band.

28. A process according to claim 1, 6, or 7, wherein said absorbance is measured in the 1614-1644 nm band.

29. A process according to claim 1, 6, or 7, wherein said absorbance is measured in the 1746-1810 nm band.

30. A process according to claim 1, 6, or 7, wherein said absorbance is measured in the 1940-2000 nm band.

31. A process according to claim 1, 6, or 7, wherein said absorbance is measured in the 2058-2130 nm band.

32. A process according to claim 1, 6, or 7 wherein said absorbance is measured in the 1152-1230 nm band.

34. A process according to claim 1, 6, or 7 comprising measuring said absorbance in the 880-974 nm band.

2. In a process for the control of hydrocarbons and substituted hydrocarbons in a complex mixture comprising naphthenes to determine naphthene component concentration, the improvement comprising in combination:

producing signal indicative of the near infrared absorbance of said mixture in three wavelength substantially as follows;

1710, 1428, and 1496 or 1420, 1678 and 1538 nm, and using said signal for controlling naphthene concentration.

3. In a process for the analysis of hydrocarbons and substituted hydrocarbons in a complex mixture comprising olefins to determine olefin concentration, the improvement comprising in combination:

producing a signal indicative of the near infrared absorbance of said mixture in three wavelengths substantially as follows;

2114, 2148 and 1638 or 1636, 1312, and 1454 nm, and using said signal for controlling olefin concentration.

4. In a process for the analysis of hydrocarbons and substituted hydrocarbons in a complex mixture comprising aromatics to determine aromatic concentration, the improvement comprising in combination:

producing a signal indicative of the near infrared absorbance of said mixture in three wavelengths substantially as follows;

2062, 1148, and 1908, or 1148, 2060 and 1196 nm, and using said signal for controlling aromatic concentration.

5. In a process for the analysis of hydrocarbons and substituted hydrocarbons in a complex mixture comprising paraffins or isoparaffins to determine paraffin and/or isoparaffin component concentration, the improvement comprising in combination:

producing a signal indicative of the near infrared absorbance of said mixture in the wavelengths of 1468, 1934, 1986, and 2058 or 1288, 1468, 890 and 2048 nm for paraffins, or 1330, 858, 1190 and 1020 or 1384, 1648, 1230 and 1062 nm for isoparaffins, and using said signal for controlling paraffin and/or isoparaffin component concentration.

6. In a process for the control of hydrocarbons and substituted hydrocarbons in complex mixtures comprising as components;

paraffins, aromatics, naphthenes, or olefins to determine component concentration, the improvement comprising in combination;

a. measuring the infrared absorbance at at least three wavelengths comprising at least one wavelength in each of two or more of any of the following bands;

1672-1698, 1700-1726, 1622-1650, 2064-2234, 1092-1156, 824-884, 1656-1692, 880-974, 1152-1230, 1320-1380, 1470-1578, 1614-1644, 1746-1810, 1940-2000, and/or 2058-2130 nm.

b. taking each of the absorbances measured, or a mathematical function thereof,

c. performing statistical treatment using said absorbances or functions as the individual independent variables,

d. assigning and applying weighting constants or their equivalents to said independent variables,

e. applying the above steps using known compositions in a calibration step to calibrate the instrument and determine said weighting constants or equivalents,

f. repeating said steps a. and b. with unknown compositions, applying the weighting constants or equivalents determined during said calibration with known compositions to output a signal or signals indicative of a paraffin, aromatic, naphthene, or olefin (PIANO) component or components concentration,

g. controlling a blending hydrocarbon refining, or chemical process by apparatus responsive to said output signal.

33. A process according to claim 6, or 7 wherein said absorbance is additionally measured in the 2064-2234 nm band.

7. In a process for the analysis and control of hydrocarbons and substituted hydrocarbons in complex mixtures comprising as components;

paraffins, aromatics, naphthenes, or olefins to determine component concentration, the improvement comprising in combination;

a. measuring the near infrared absorbance at at least three wavelengths comprising at least one wavelength in any two of the following bands;

1672-1698, 1700-1726, 1622-1650, 2064-2234, 1092-1156, 824-884, 1656-1692, 1152-1230, 1320-1380, 1470-1578, 1614-1644, 1746-1810, 1940-2000, and 2058-2130 nanometers (nm).

b. outputting a periodic or continuous signal indicative of a derivative of said absorbance in said wavelength or wavelengths in said band, or of a combination of mathematical functions thereof;

c. performing statistical treatment using said signal derivative of said absorbance or functions as the individual independent variables,

d. assigning and applying weighting constants or their equivalents to said independent variables,

e. applying the above steps using known compositions in a calibration step to calibrate the instrument and determine said weighting constants or equivalents,

f. repeating said steps a. and b. with unknown compositions, applying the weighting constants or equivalents determined during said calibration with known compositions to output a signal or signals indicative of a paraffin, aromatic, naphthene, or olefin (PIANO) component or components concentration,

g. controlling a blending, hydrocarbon refining or chemical process by apparatus responsive to said output signal.