PROCESSES AND SYSTEMS FOR CHARACTERIZING AND BLENDING REFINERY FEEDSTOCKS

• US 20120160709A1
• Filed: 12/20/2011
• Published: 06/28/2012
• Est. Priority Date: 12/28/2010
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Kusinski, Grzegorz Jan, Devine, Thomas M.
• Granted Patent: US 9,103,813 B2
• Time in Patent Office: Days
• US Class Current: 205/782
• CPC Class Codes: G01N 17/02 Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
• 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

Abstract

Refinery feedstocks can be characterized based on any of: dissociation of acids in the crude, breakup of naphthenic acid molecular associations, and/or dissociation of sulfur compounds in the feedstocks. The characterization is performed as a function of temperature via any of electrical resistivity measurement, vibrational spectroscopic analysis, voltammetry, electrochemical impedance spectroscopy (EIS) and combinations thereof The method can be practiced in any of refinery, terminal, and laboratories. It can be used in conjunction with models and hardware to optimize the usage of refinery feedstocks in the blending and valuation of the feedstocks. In one embodiment, the characterization of refinery feedstocks is via the use of EIS.

Claims

1. A method for evaluating the corrosivity of a crude oil, comprising:

withdrawing a representative sample of a crude oil feedstock to a refinery;

performing impedance measurements on the crude oil sample as a function of temperature to obtain a first electrochemical impedance spectroscopy (EIS) data, wherein the first EIS data include data for at least three frequencies;

obtaining a second EIS data on a reference crude oil sample having known corrosion properties, wherein the second EIS data include data for at least three frequencies;

analyzing the first EIS data relative to the second EIS data to evaluate the corrosivity of the crude oil feedstock, wherein the step of comparing the first EIS data with the second EIS data including comparing at least one of a resistance reading and a dielectric constant reading.

2. The method of claim 1, wherein the impedance measurements are carried out using a two-electrode chemical cell with an ultramicroelectrode as working electrode and a second electrode serving as both reference electrode and counter electrode.

3. The method of claim 1, wherein the ultramicroelectrode comprises platinum.

4. The method of claim 1, wherein the impedance measurements are carried out at a temperature ranging from ambient to 700°

F.

5. The method of claim 1, wherein the impedance measurements are carried out as a function of temperature and oxygen concentration, wherein the crude oil is enriched with oxygen at a concentration from 10 to 500 ppm O₂.

6. The method of claim 1, wherein the impedance measurements are carried out as a function of temperature and oxygen concentration, and wherein the crude oil is enriched with water and/or steam at a concentration from 2 ppm to 2 wt. %.

7. The method of claim 1, where the frequencies for the first and second EIS data include at least one frequency less than one Hertz, and at least one frequency greater than one Hertz.

8. The method of claim 1, wherein the step of analyzing the first EIS data relative to the second EIS data comprises using statistical techniques.

9. The method of claim 8, wherein the statistical techniques include at least one of Principal Component Analysis, Multivariate Least Squares Regression, Principal Component Regression, Pattern Recognition analysis, Cluster analysis, Neural Net analysis, and Group Methods of Data Handling.

10. The method of claim 1, wherein the step of analyzing the first EIS data relative to the second EIS data comprises using a look up table containing EIS data correlating to corrosion properties of a plurality of reference crude oil samples.

11. The method of claim 1, wherein obtaining a second EIS data on a reference crude oil sample having known corrosion properties comprises adding known concentrations of acids to the reference crude oil sample to measure dissociation of the acids in the reference crude oil sample.

12. The method of claim 11, wherein obtaining a second EIS data on a reference crude oil sample having known corrosion properties further comprises obtaining impedance measurements as a function of temperature on the reference crude oil sample having known concentrations of acids.

13. The method of claim 12, wherein the impedance measurements of the reference crude oil sample are carried out at a temperature ranging from ambient to 700°

F.

14. The method of claim 1, wherein obtaining a second EIS data on a reference crude oil having known corrosion properties comprises adding known concentrations of sulfur compounds to the reference crude oil sample to measure dissociation of the sulfur into ionic species in the reference crude oil sample.

15. A method for evaluating the corrosivity of a crude oil feedstock by correlating its corrosivity with dissociation of acids in the crude oil, comprising:

withdrawing a representative sample of the crude oil feedstock, wherein the crude oil feedstock has a certain amount of acids;

detecting the dissociation of the acids in the crude oil feedstock sample as a function of temperature by obtaining impedance measurements of the crude oil feedstock over a range of temperature from ambient to 700°

F.;

providing impedance measurements of at least a reference oil feedstock having a known dissociation of acids;

comparing the impedance measurements of the crude oil feedstock sample with the impedance measurements of the reference oil feedstock to evaluate the corrosivity of the crude oil feedstock;

wherein the impedance measurements of the crude oil feedstock sample and the reference oil feedstock are carried out using a two-electrode chemical cell with an ultramicroelectrode as working electrode and a second electrode serving as both reference electrode and counter electrode.

16. The method of claim 15, further comprising using a look up table to evaluate the corrosivity of the crude oil feedstock sample.

17. The method of claim 15, wherein the impedance measurements of the reference oil feedstock having a known dissociation of acids are measured before and after adding a known concentration of acids to the reference oil feedstock.

18. The method of claim 15, wherein the impedance measurements of the crude oil feedstock sample are carried out as a function of temperature and oxygen concentration and wherein the crude oil feedstock sample is enriched with oxygen at a concentration from 10 to 10,000 ppm O₂.

19. A method for evaluating the corrosivity of a crude oil feedstock in operations by correlating its corrosivity with molecular associations of naphthenic acid in the crude oil feedstock upon contact with at least a metal, comprising:

withdrawing a representative sample of the crude oil feedstock, wherein the crude oil feedstock has a certain amount of naphthenic acid;

exposing a metal specimen to the crude oil feedstock sample;

detecting the molecular associations of naphthenic acid in the crude oil feedstock sample upon exposure to the metal specimen as a function of temperature by obtaining electrical resistivity measurements of the crude oil feedstock sample over a range of temperature from ambient to 700°

F.;

providing resistivity measurements of at least a reference oil feedstock having a known corrosion rate upon exposure to the metal specimen;

comparing the resistivity measurements of the crude oil feedstock sample with the resistivity measurements of the reference oil feedstock to evaluate the corrosivity of the crude oil feedstock.

20. The method of claim 19, wherein the electrical resistivity measurements are obtained via a four-point probe instrument.

21. The method of claim 19, wherein the electrical resistivity measurements are obtained via a four-point probe instrument comprising platinum electrodes.