Process for analysis of asphaltene content in hydrocarbon mixtures by middle infrared spectroscopy

• US 6,087,662 A
• Filed: 05/22/1998
• Issued: 07/11/2000
• Est. Priority Date: 05/22/1998
• Status: Expired due to Term

• Current Assignee: Marathon Petroleum Company LP (Marathon Petroleum Corporation)
• Original Assignee: Marathon Ashland Petroleum LLC (Marathon Petroleum Corporation)
• Inventors: Wilt, Brian K., Welch, William T.
• Primary Examiner(s): Hannaher, Constantine
• Assistant Examiner(s): GAGLIARDI, ALBERT J
• Application Number:
  US09/083,913
• Time in Patent Office: 781 Days
• Field of Search: 250/339.09, 250/338.5, 250/339.01, 250/339.1, 250/339.11, 250/339.12, 250/341.5, 250/341.8, 436/52, 436/60, 436/139, 436/140, 436/141
• US Class Current: 250/339.12
• CPC Class Codes: G01N 21/3577 for analysing liquids, e.g. polluted water
• CPC Class Codes: G01N 33/2823 raw oil, drilling fluid or polyphasic mixtures hydrocarbon content of earth materials G01N33/241; prospecting G01V; drilling per se E21B
• CPC Class Codes: G01N 33/2835 specific substances contained in the oil or fuel
• CPC Class Codes: Y10T 436/21 Hydrocarbon

Abstract

Asphaltene concentration of a hydrocarbon feed is measured by IR spectroscopy using mid-range IR frequencies between 3800 cm^-1 and 650 cm^-1 (corresponding to wavelengths between 2630 nanometers (nm) and 15,380 nm) together with mathematical techniques and statistical techniques in which measurements of absorption are made, and combines these with multiple regression analysis, or other statistical technique and modeling to determine asphaltene concentration. The output signal can be used to control refinery and chemical processes, e.g., atmospheric crude column, vacuum distillation column, solvent deasphalting and visbreaking.

Claims

1. A process for determining asphaltene concentration in an asphaltene-containing hydrocarbon mixture using infrared spectroscopy and a multiple variable regression analysis to determine asphaltene concentration, comprising in combination:

a. measuring at at least one frequency, the infrared absorption in the band of 3800-700 cm^-1 ;

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

c. performing statistical treatment using the above absorbances or to functions as individual independent variables;

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

e. applying the above steps using compositions of known asphaltenes concentration to calibrate the instrument and determine said weighting constants or equivalents;

f. repeating said steps with unknown compositions, and applying the weighting constants or equivalents determined during said calibration with compositions of known asphaltenes concentration to output a signal or signals indicative of asphaltenes concentration for the unknown compositions.

2. The process according to claim 1 wherein absorption is measured over the length of the band of 3800-700 cm^-1, or of a portion thereof.

3. The process according to claim 1 wherein absorption is only measured over the length of the band of 900-700 cm^-1, or of a portion thereof.

4. The process according to claim 1 wherein absorption is only measured at the frequencies of the bands of 1615-1300 cm^-1, 1100-1000 cm^-1 and 975-700 cm^-1, or of a portion thereof.

5. The process according to claim 1 wherein said statistical treatment is a technique selected from the group consisting of absorbance base line off-set corrected absorbance data;

taking the first, second, third, fourth or higher derivative of the absorbance spectrum;

dividing the absorbance at one wavelength by another;

spectral subtraction;

curve fitting techniques of Savitsky-Golay;

curve fitting techniques of Kubelka-Munk;

N-point smoothing (signal averaging);

principle component analysis/regression (PCA/PCR);

Gauss-Jordan Row reduction;

multiple linear regression analysis (MLR);

partial least squares analysis (PLS); and

Neural Networks (NN).

6. The process according to claim 5 wherein said statistical treatment is a technique comprising taking the second derivative of the absorbance spectrum.

7. The process of claim 5 wherein said statistical treatment is multiple linear regression analysis.

8. The process of claim 5 wherein said statistical treatment is partial least squares analysis.

9. The process according to claim 1 wherein said mixture flows substantially intermittently or continuously past the point of measuring said absorbance.

10. The process according to claim 1 wherein the hydrocarbon mixture is a pipelined crude oil.

11. The process according to claim 1 wherein the hydrocarbon mixture is a desalted crude oil.

12. The process according to claim 11 wherein said signal is used to control the severity of an atmospheric distillation column by adjusting temperature, throughput, and/or unit space velocity.

13. The process according to claim 1 wherein the hydrocarbon mixture is an atmospheric bottoms.

14. The process according to claim 13 wherein said signal is used to control the severity of a vacuum distillation column by adjusting cut point, temperature, throughput, and/or unit space velocity.

15. The process according to claim 1 wherein the hydrocarbon mixture is a vacuum bottoms.

16. The process according to claim 15 wherein said signal is used to control the severity of a solvent deasphalting unit by adjusting temperature, throughput, unit space velocity and/or alkane solvent to vacuum bottoms ratio.

17. The process according to claim 16 wherein said signal is used to control the severity of a visbreaker by adjusting temperature, throughput, and/or unit space velocity.

18. The process according to claim 1 wherein the hydrocarbon mixture is a solvent deasphalting product.

19. A process according to claim 1 wherein said signal is used to control at least one process selected from the group of:

a. atmospheric distillation, whereby a bottoms product having a desired asphaltene concentration is produced, by adjusting throughput, temperature, or unit space velocity;

b. vacuum distillation, whereby a bottoms product having a desired asphaltene concentration is produced, by adjusting temperature, throughput and/or unit space velocity;

c. solvent deasphalting, whereby a deasphalted oil product having a desired asphaltene concentration is produced, by adjusting temperature, throughput, unit space velocity and/or alkane solvent to vacuum bottoms ratio; and

d. visbreaking whereby a visbreaker product of desired asphaltene concentration is produced by adjusting temperature, throughput, and/or unit space velocity.